Polyester fiber composite material useful for reinforcing rubber articles and process for producing the same

Claim 2

A polyester fiber composite material useful for reinforcing rubber articles, comprising a substrate of a polyester fiber material impregnated with a polymeric impregnating material which comprises at least the four components of: (A) at least one polyepoxide composition, (B) at least one rubber latex, (C) at least one prepolymer of resorcin with formaldehyde and (D) from 0.1 to 10% of at least one water-soluble polyurethane compound based on the weight of the substrate, each of said components being heat-treated on said substrate at least once at a temperature of between 120° C. and the melting point of said polyester fiber material, said water-soluble polyurethane compound having the formula (I): ##STR9## wherein A represents a tri- or hepta-valent radical, X represents a monovalent residue of a blocking compound having an activated hydrogen atom which residue is capable of dissociating from the polyurethane compound when said heat-treatment is applied thereto; Y represents a monovalent residue of an anionic radical-containing compound selected from the group consisting of aminosulfonic acids having 2 to 6 carbon atoms and aminocarboxylic acids having 1 to 6 carbon atoms; n represents an integer of 5 to 30, and; l and m represent an integer of 1 to 5, respectively, the sum of l and m is an integer of 2 to 6.

Claim 3

A polyester fiber composite material as claimed in claim 1, wherein said substrate is first impregnated with a first impregnating material comprising said polyepoxide compound, said impregnated polymeric material being first heat-treated on said substrate at a temperature of from 150° to 260° C., to form a once impregnated substrate said once impregnated substrate is impregnated with a second impregnating material comprising said water-soluble polyurethane compound of the formula (I), said resorcin-formaldehyde prepolymer and said rubber latex, said once impregnated substrate impregnated with the second impregnating material having been heat-treated at a temperature of 150° to 260° C.

Claim 4

A polyester fiber composite material of claim 1, wherein said substrate is impregnated with a first impregnating material comprising said polyepoxide compound, said water-soluble polyurethane compound of the formula (I) and said rubber latex, said first impregnating material being heat-treated on said substrate at a temperature of between 180° C. and the melting temperature of said polyester fiber material to form a once impregnated substrate; and said once impregnated substrate is impregnated with a second impregnating composition comprising said resorcin-formaldehyde prepolymer and said rubber latex, said once impregnated substrate impregnated with a second impregnating composition having been heat-treated at a temperature of between 120° C. and the melting point of said polyester fiber material.

Claim 5

A polyester fiber composite material of claim 1, wherein said substrate is first impregnated with a first impregnating material comprising said polyepoxide compound, said first impregnating material having been heat-treated on said substrate at a temperature of 150° to 260° C. to form a first impregnated product; said first impregnated product is then impregnated with a second impregnating material comprising said water-soluble polyurethane compound of the formula (I), said first impregnated product impregnated with said second impregnating material having been heated treated at a temperature of between 180° C. and the melting point of said polyester fiber material to form a twice impregnated product, and; said twice impregnated product is impregnated with a third impregnating material comprising said resorcin-formaldehyde prepolymer and said rubber latex, said twice impregnated product impregnated with said third impregnating material having been heat treated at a temperature of between 120° C. and the melting point of said polyester fiber material.

Claim 6

A polyester fiber composite material as claimed in claim 1, 2, 3 or 4, wherein the entire dry weight of said polymeric impregnating material is in the range of from 2 to 20% based on the weight of said substrate.

Claim 7

A polyester fiber composite material as claimed in claim 1, 2, 3 or 4, wherein the dry weight of said polyepoxide compound is in the range of from 0.05 to 2.0% based on the weight of said substrate.

Claim 8

A polyester fiber composite material as claimed in claim 1, 2, 3 or 4, wherein the dry weight of said rubber latex is in the range of from 0.1 to 10% based on the weight of said substrate.

Claim 9

A polyester fiber composite material as claimed in claim 1, 2, 3 or 4, wherein the dry weight of said resorcin-formaldehyde prepolymer is in the range of from 0.01 to 5% based on the weight of said substrate.

Claim 10

A polyester fiber composite material as claimed in claim 1, wherein said polymeric impregnating material contains an additional component consisting of at least one member selected from the group consisting of ethylene urea compounds of the formula (II): ##STR10## wherein R stands for an aromatic or aliphatic hydrocarbon residue and n' is 0, 1 or 2, and blocked polyisocyanate compounds of the formula (IV): A'(NHCOX')r (IV) wherein X' represents a residue of a blocking compound which residue is capable of dissociating from the blocked polyisocyanate compound when heat-treated, r represent an integer of 2 or more and A; represents an r valent radical.

Claim 11

A polyester fiber composite material as claimed in claim 1, wherein said tri- to hepta-valent radical A is a residue of an organic polyisocyanate compound having 3 to 7 isocyanate radicals.

Claim 12

A polyester fiber composite material as claimed in claim 10, wherein said organic polyisocyanate compound is selected from the group consisting of triphenylmethane triisocyanate, polymethylenepolyphenylisocyanate having 3 to 7 isocyanate groups, addition products of lower polyols having 3 to 7 hydroxyl groups with diisocyanate compounds and trimer of hexamethylene diisocyanate.

Claim 13

A polyester fiber composite material as claimed in claim 1, wherein said blocking compound is selected from the group consisting of phenol compounds, aliphatic tertiary alcohol compounds, aromatic secondary amine compounds, aromatic imide compounds lactam compounds, oxime compounds and sodium hydrogen sulfite.

Claim 14

A polyester fiber composite material as claimed in claim 12, wherein said phenol compounds are selected from the group consisting of phenol thiophenol, alkylphenols in which the alkyl group has 1 to 9 carbon atoms and resorcin.

Claim 15

A polyester fiber composite material as claimed in claim 1, wherein said anionic radical-containing compound is selected from the group consisting of taurine, N-methyl taurine, N-butyl taurine, glycine and alanine.

Claim 16

A polyester fiber composite material as claimed in claim 1, wherein said polyepoxide compound (A) contains at least two epoxy groups per molecule thereof.

Claim 17

A polyester fiber composite material as claimed in claim 1, wherein said polyepoxide compound (A) is selected from the group consisting of reaction products of polyhydric alcohols with halogenated epoxide compounds, reaction products of polyhydric phenol compounds with halogenated epoxide compounds and oxidation products of unsaturated organic compounds having at least one aliphatic double bond with peracetic acid or hydrogen peroxide.

Claim 18

A polyester fiber composite material as claimed in claim 1, wherein said polyepoxide compound (A) is selected from polyglycidyl ethers of polyhydric alcohols, which are reaction products of epichlorohydrin with polyhydric alcohols.

Claim 19

A polyester fiber composite material as claimed in claim 16 or 17, wherein said polyhydric alcohol is selected from the group consisting of ethylene glycol, glycerol, diglycerol, diethylene glycol, sorbitol, pentaerythritol trimethylol propane, polyethylene glycols and polypropylene glycols.

Claim 20

A polyester fiber composite material as claimed in claim 16, wherein said halogenated epoxide compound is epichlorohydrin.

Claim 21

A polyester fiber composite material as claimed in claim 16, wherein said polyhydric phenol compound is selected from the group consisting of resorcin, catechol, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl) dimethylmethane, phenol-formaldehyde resins and resorcin-formaldehyde resins.

Claim 22

A polyester fiber composite material as claimed in claim 16, wherein said oxidation product is selected from the group consisting of 4-vinyl cyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexene carboxylate and bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate.

Claim 23

A polyester fiber composite material as claimed in claim 1, wherein said rubber latex (B) is selected from the group consisting of natural rubber latexes and synthetic rubber latexes.

Claim 24

A polyester fiber composite material as claimed in claim 22, wherein said synthetic rubber latex (B) is selected from the group consisting of styrene-butadiene copolymer latexes, butadiene-vinyl pyridine copolymer latexes, vinyl pyridine-styrene-butadiene terpolymer latexes, acrylonitrile rubber latexes acrylonitril-butadiene copolymer latexes and chloroprene rubber latexes.

Claim 25

A polyester fiber composite material as claimed in claim 1, wherein the molar ratio of said resorcin to said formaldehyde is in a range of from 1:0.1 to 1:8.

Claim 26

A polyester fiber composite material as claimed in claim 9, wherein said ethylene urea compound of the formula (II) is a reaction product of ethyleneimine with an isocyanate selected from the group consisting of octadecylisocyanate, hexamethylenediisocyanate, isophoronediisocyanate, tolylenediisocyanate, methaxylene diiisocyanate, diphenylmethanediisocyanate, naphthylenediisocyanate, and triphenylmethanetriisocyanate.

Claim 27

A process for producing a polyester fiber composite material useful for reinforcing rubber articles comprising impregnating at least once a substrate comprising a polyester fiber material with polymeric impregnating materials which comprises at least the four components: (A) at least one polyepoxide compound; (B) at least one rubber latex; (C) at least one prepolymer of resorcin with formaldehyde, and: (D) from 0.1 to 10% of at least one water-soluble polyurethane compound based on the weight of the substrate, alone or in combination and drying said impregnated substrate and heat treating said dried impregnated substrate after each impregnation at a temperature of between 120° C. and the melting point of the polyester fiber material, (1) by impregnating said substrate at least once, in each impregnating procedure, with an impregnating liquid containing at least one of said components, and (2) by applying, after each impregnating procedure, a drying procedure and a heat-treatment to said impregnated substrate at a temperature of between 120° C. and the melting point of said polyester fiber material, wherein said water soluble polyurethane compound having the formula (I): ##STR11## wherein A represents a tri- to hepta-valent radical; X represents a monovalent residue of a blocking compound having an activated hydrogen atom which residue is capable of dissociating from the polyurethane compound when said heat-treatment is applied thereto; Y represents a monovalent residue of an anionic group-forming compound selected from the group consisting of aminosulfonic acids having 2 to 6 carbon atoms and aminocarboxylic acids having 1 to 6 carbon atoms; n represents an integer of 5 to 30, and; l and m represent an integer of 1 to 5, respectively, and the sum of l and m is an integer of 2 to 6.

Claim 28

A process for producing a polyester fiber composite material useful for reinforcing rubber articles comprising impregnating at least once a substrate comprising a polyester fiber material with polymeric impregnating materials which comprises at least the four components: (A) at least one polyepoxide compound; (B) at least one rubber latex; (C) at least one prepolymer of resorcin with formaldehyde, and: (D) from 0.1 to 10% of at least one water-soluble polyurethane compound based on the weight of the substrate, alone or in combination and drying said impregnated substrate and heat treating said dried impregnated substrate after each impregnation at a temperature of between 120° C. and the melting point of the polyester fiber material, (1) by impregnating said substrate at least once, in each impregnating procedure, with an impregnating liquid containing at least one of said components, and (2) by applying, after each impregnating procedure, a drying procedure and a heat-treatment to said impregnated substrate at a temperature of between 120° C. and the melting point of said polyester fiber material, wherein said water soluble polyurethane compound having the formula (I): ##STR11## wherein A represents a tri- to hepta-valent radical; X represents a monovalent residue of a blocking compound having an activated hydrogen atom which residue is capable of dissociating from the polyurethane compound when said heat-treatment is applied thereto; Y represents a monovalent residue of an anionic group-forming compound selected from the group consisting of aminosulfonic acids having 2 to 6 carbon atoms and aminocarboxylic acids having 1 to 6 carbon atoms; n represents an integer of 5 to 30, and; l and m represent an integer of 1 to 5, respectively, and the sum of l and m is an integer of 2 to 6.

Claim 29

A process as claimed in claim 26, wherein said polyepoxide compound is heat-treated in the presence of an epoxy hardening agent consisting of at least one higher fatty acid-tert-amine compound of the formula (III): ##STR12## wherein R 1 represents a member selected from the group consisting of unsaturated and saturated alkyls having 8 to 22 carbon atoms, n" represents an integer of 2 or 3 and p and q represent an integer of 1 to 30, respectively.

Claim 30

A process as claimed in claim 26, wherein the amount of said epoxy-hardening agent is in the range of 5 to 30% based on the weight of said polyepoxide compound used.

Claim 31

A process of claim 26, wherein said substrate is first impregnated with a first impregnating liquid comprising said polyepoxide compound dried and heat-treated at a temperature of 150° to 260° C. to form a once impregnated product; impregnating the once impregnated product with a second impregnating liquid containing said water-soluble polyurethane compound of the formula (I), said resorcin-formaldehyde prepolymer and said rubber latex to form a twice impregnated product, and; drying the twice impregnated product and heat-treating the twice dried impregnated product at a temperature of 150° to 260° C.

Claim 32

A process as claimed in claim 29, wherein said once impregnated product is aged at a temperature of 40° to 100° C. for 8 hours or more, before said second impregnating procedure.

Claim 33

A process as claimed in claim 29, wherein the amount of said water-soluble polyurethane compound is in the range of 0.5 to 40% based on the weight of the sum of said resorcin-formaldehyde reaction product and said rubber latex.

Claim 34

A process as claimed in claim 29, wherein in said second impregnating liquid, the ratio in weight of said resorcin-formaldehyde reaction product to said rubber latex is in the range of 1:1 to 1:15.

Claim 35

A process of claim 26, wherein said substrate is first impregnated with a first impregnating liquid containing said polyepoxide compound, said water-soluble polyurethane compound of the formula (I) and said rubber latex; dried; and heat-treated at a temperature of between 180° C. and the melting temperature of said polyester fiber material to form a once impregnated product; impregnating the once impregnated product with a second impregnating liquid containing said resorcin-formaldehyde prepolymer and said rubber latex to form a twice impregnated product, and; drying the twice impregnated product and heat-treating the dried twice impregnated product at a temperature of between 120° C. and the melting point of said polyester fiber material.

Claim 36

A process as claimed in claim 33, wherein in said first impregnating liquid, the ratio in weight of said polyepoxide compound to the sum of said polyepoxide compound and said water-soluble polyurethane compound of the formula (I) is in the range of from 0.05:1 to 0.9:1.

Claim 37

A process as claimed in claim 33, wherein in said first impregnating liquid, the ratio in weight of said rubber latex to the sum of the polyepoxide compound and said water-soluble polyurethane compound of the formula (I) is in the range of from 0.5:1 to 15:1.

Claim 38

A process as claimed in claim 33, wherein in said second impregnating liquid, the ratio in weight of said resorcin-formaldehyde prepolymer to said rubber latex is in the range of from 1:1 to 1:15.

Claim 39

A process as claimed in claim 33, wherein said second impregnating liquid contains an additional component consisting of at least one member selected from the group consisting of ethylene urea compounds of the formula (II): ##STR13## wherein R stands for an aromatic or aliphatic hydrocarbon residue and n' is 0.1 or 2; blocked polyisocyanate compounds of the formula (IV): A'(NHCOX')r (IV) wherein X' represents a residue of a blocking compound which residue is capable of dissociating from said blocked polyisocyanate compound when heat-treated, r represents an integer of 2 or more and A' represents a r valent radical, and; said water-soluble polyurethane compounds of the formula (I).

Claim 40

A process as claimed in claim 37, wherein said additional component is in the amount of 0.5 to 30% based on the sum of the weights of said resorcin-formaldehyde prepolymer and said rubber latex.

Claim 41

A process of claim 26, wherein said substrate is first impregnated with a first impregnating liquid containing said polyepoxide compound; dried, and heat-treated at a temperature of 150° to 260° C. to form a first impregnated product; impregnating the first impregnated product with a second impregnating liquid containing said water-soluble polyurethane compound of the formula (I) to form a twice impregnated product; drying the twice impergnated product and heat-treating the dried twice impregnated product at a temperature between 180° C. and the melting point of said polyester fiber material to form a heat-treated twice impregnated product; impregnating the heat-treated twice impregnated product with a third impregnating liquid containing said resorcin-formaldehyde prepolymer and said rubber latex to form a thrice impregnated product; drying the thrice impregnated product and; heat-treating the dried thrice impregnated product at a temperature of between 120° C. and the melting point of said polyester fiber material.

Claim 42

A process as claimed in claim 39, wherein said second impregnating liquid contains a polyepoxide compound in a concentration of 0.5 to 30% by weight.

Claim 43

A process as claimed in claim 39, wherein in said third impregnating liquid, the ratio in weight of said resorcin-formaldehyde prepolymer to said rubber latex is in the range of from 1:1 to 1:15.

Claim 44

A process as claimed in claim 39, wherein said third impregnating liquid contains an additional component consisting of at least one member selected from the group consisting of ethylene urea compounds of the formula (II): ##STR14## wherein R stands for an aromatic or aliphatic hydrocarbon residue and n' is 0.1 or 2; blocked polyisocyanate compounds of the formula (IV): A'(NHCOX')r (IV) wherein X' represents a residue of a blocking agent which residue is capable of dissociating from said blocked polyisocyanate compound when heat-treated, r represents an integer of 2 or more and A' represents an r valent radical, and; said water-soluble polyurethane compounds of the formula (I).

Claim 45

A process as claimed in claim 42, wherein said additional component in said third impregnating liquid is in an amount of 0.5 to 3% based on the dry weight of the sum of said resorcin-formaldehyde prepolymer and said rubber latex.