WO2022130879A1 - 接着剤組成物、ゴム-有機繊維コード複合体及びタイヤ - Google Patents
接着剤組成物、ゴム-有機繊維コード複合体及びタイヤ Download PDFInfo
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- WO2022130879A1 WO2022130879A1 PCT/JP2021/042103 JP2021042103W WO2022130879A1 WO 2022130879 A1 WO2022130879 A1 WO 2022130879A1 JP 2021042103 W JP2021042103 W JP 2021042103W WO 2022130879 A1 WO2022130879 A1 WO 2022130879A1
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- Prior art keywords
- compound
- rubber
- organic fiber
- adhesive composition
- fiber cord
- Prior art date
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/80—Compositions for aqueous adhesives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2380/00—Tyres
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2421/00—Presence of unspecified rubber
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- C09J2475/00—Presence of polyurethane
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Definitions
- the present invention relates to an adhesive composition, a rubber-organic fiber cord composite and a tire.
- organic fibers such as polyester fibers have high initial elasticity and excellent thermal dimensional stability, so that they are in the form of filaments, cords, cables, cord fabrics, canvas, etc., such as tires, belts, and air. It is extremely useful as a reinforcing material for rubber articles such as springs and rubber hoses, and various adhesive compositions have been proposed in order to improve the adhesiveness between these fibers and rubber.
- an adhesive composition for example, an RFL (resorcin formalin-latex) adhesive containing resorcin, formalin, rubber latex, etc. is used, and the technique for ensuring adhesive strength by thermally curing the RFL adhesive is known. (For example, refer to Patent Documents 1 to 3 and the like).
- formalin which is generally used in the above-mentioned adhesive composition, is an important raw material for cross-linking resorcin, but in recent years, it has been required to reduce the amount used in consideration of the working environment. Furthermore, the amount of resorcin used is also required to be reduced from the viewpoint of the environment.
- an object of the present invention is to provide an adhesive composition capable of achieving excellent adhesiveness and mechanical stability even when it does not contain formalin and resorcin.
- Another object of the present invention is to provide a rubber-organic fiber cord composite and a tire, which have a low impact on the environment and are excellent in adhesiveness and productivity between rubber and an organic fiber cord.
- the present inventors have made the adhesive composition containing rubber latex contain a compound containing an acrylamide structure so that formalin and resorcin are not used even when formalin and resorcin are not used. It has been found that high adhesive strength can be realized, aggregation of rubber latex particles can be suppressed, and mechanical stability can be improved.
- the adhesive composition of the present invention is characterized by containing (A) a rubber latex and (B) a compound containing an acrylamide structure.
- the tire of the present invention is characterized in that the rubber-organic fiber cord composite of the present invention described above is used. With the above configuration, the load on the environment is small, and the adhesiveness between the rubber and the organic fiber cord can be improved.
- an adhesive composition capable of achieving excellent adhesiveness and mechanical stability even when it does not contain formalin and resorcin. Further, according to the present invention, it is possible to provide a rubber-organic fiber cord composite and a tire which have a small burden on the environment and are excellent in adhesiveness and productivity between rubber and an organic fiber cord.
- the adhesive composition for an organic fiber cord of the present invention (hereinafter, may be referred to as "adhesive composition of the present invention") is a compound containing (A) a rubber latex and (B) an acrylamide structure (hereinafter, referred to as “adhesive composition”). It may be referred to as an "acrylamide-containing compound”), and is characterized by containing.
- the acrylamide-containing compound suppresses the aggregation of the rubber latex particles, and (A) the rubber latex is uniformly dispersed, so that the mechanical stability of the adhesive composition can be improved. Furthermore, since the adhesive composition for organic fiber cords of the present invention does not contain resorcin or formalin, the burden on the environment can be reduced.
- the adhesive composition for an organic fiber cord of the present invention contains (A) rubber latex.
- the rubber latex is obtained by dispersing fine particles of rubber components in a solvent such as water.
- concentration of the rubber component in the latex can be in the range of 10 to 60% by mass, preferably in the range of 20 to 50% by mass.
- the rubber component of the rubber latex is not particularly limited, and in addition to natural rubber (NR), polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), and ethylene-propylene.
- -Synthetic rubbers such as diene rubber (EPDM), chloroprene rubber (CR), butyl halide rubber, acrylonilittle-butadiene rubber (NBR), and vinylpyridine-styrene-butadiene copolymer rubber (Vp) can be used. These rubber components may be used alone or in a blend of two or more.
- the content of the rubber latex in the adhesive composition of the present invention when the total content of the rubber latex (A) and the compound having the acrylamide structure (B) is 100% in terms of the amount of solid components.
- the ratio of the content of the rubber latex (A) is preferably 70 to 99.7%, more preferably 80 to 99.5%, and further preferably 85 to 99.5%. preferable. By containing the rubber latex in this range, more excellent adhesiveness can be obtained.
- the adhesive composition for an organic fiber cord of the present invention contains (B) a compound containing an acrylamide structure (acrylamide-containing compound) in addition to the above-mentioned (A) rubber latex.
- the acrylamide compound covers the surface of the rubber latex particles and suppresses the aggregation of the rubber latex particles with each other. ..
- the dispersibility of the rubber latex when subjected to a mechanical load is enhanced, and excellent mechanical stability can be realized.
- the content of acrylamide in the acrylamide-containing compound is not particularly limited, and may be not only polyacrylamide but also a copolymer of acrylamide and acrylic acid or a compound having an acrylamide structure as a part.
- anionic polyacrylamide, nonionic polyacrylamide, modified polyacrylamide and the like can be used as the acrylamide-containing compound.
- acrylamide-containing compound It is also possible to use a commercially available product for the acrylamide-containing compound.
- Commercially available products of the acrylamide-containing compound include, for example, Haricoat G-38, Haricoat G-50, Haricoat G-51, Haricoat GA-1, Harimide 1057, Harmide C-10 (all manufactured by Harima Chemicals Group, Inc.), polyacrylamide. (Manufactured by Sigma-Aldrich), WC-24 (manufactured by Arakawa Chemical Industry Co., Ltd.) and the like can be used.
- the molecular weight of the acrylamide-containing compound is preferably 10,000 to 7,000,000, preferably 50,000 to 6,000,000, and 50,000 to 3,000,000. It is more preferably 50,000 to 1,000,000, still more preferably 50,000 to 500,000, and particularly preferably 50,000 to 200,000. ..
- the molecular weight of the acrylamide-containing compound is 10,000 or more, aggregation of the rubber latex particles can be more reliably suppressed, and when the molecular weight of the acrylamide-containing compound is 7,000,000 or less, acrylamide is obtained. It does not cause problems such as cross-linking of the contained compound and gelation. Therefore, the mechanical stability of the adhesive composition can be further improved.
- the content of the acrylamide-containing compound in the adhesive composition for an organic fiber cord of the present invention is not particularly limited.
- the ratio of the content of the compound having the (B) acrylamide structure is preferably 0.3 to 20%, preferably 0.5 to 20%, and preferably 0.5 to 15%. More preferred.
- the ratio of the content of the compound having the (B) acrylamide structure when the total content of the (A) rubber latex and the compound having the (B) acrylamide structure is 100% is 0.
- it is 3% or more the aggregation of the rubber latex particles can be surely suppressed and the mechanical stability can be further improved, and when the ratio is 20% or less, the adhesiveness of the rubber latex to the rubber is achieved. Does not decrease.
- the total content of the (A) rubber latex and the (B) compound having an acrylamide structure in the adhesive composition for an organic fiber cord of the present invention is the solid component content of the (A) rubber latex.
- the total content of at least one selected from the group consisting of 100% is 100%
- the total content of the (A) rubber latex and the (B) compound having an acrylamide structure is 20 to 95%. It is preferably 25 to 95%, more preferably 25 to 95%.
- the adhesive composition for an organic fiber cord of the present invention in addition to the above-mentioned (A) rubber latex and (B) acrylamide-containing compound, (C) (C-1) epoxy compound and (C-2) polyphenol. Further comprising at least one selected from the group consisting of the compound and the (C-3) (thermally dissociable blocked) aqueous compound having an isocyanate group (hereinafter, collectively referred to as "component (C)"). Is preferable. By further containing these components, better adhesiveness can be realized.
- the content of the component (C) in the adhesive composition for an organic fiber cord of the present invention is not particularly limited.
- the above (A) rubber latex, the above (B) compound having an acrylamide structure, and the above (C) in terms of the amount of solid components 100% total content of at least one selected from the group consisting of (C-1) epoxy compound, (C-2) polyphenol compound and (C-3) (thermally dissociable blocked) aqueous compound having an isocyanate group.
- the content of the component (C) is preferably 5 to 80%, more preferably 5 to 75%, and even more preferably 10 to 70%.
- epoxy compound As the (C-1) epoxy compound, various compounds having at least one epoxy group in one molecule can be used.
- the epoxy compound acts as a cross-linking agent for the adhesive composition, can realize excellent adhesiveness, and can improve heat resistance, durability, strength, flexibility, electrical insulation, and the like.
- the epoxy compound is not particularly limited, but is preferably a compound having two or more epoxy groups in one molecule, and more preferably a compound having four or more epoxy groups.
- the epoxy compound effectively functions as a cross-linking agent due to the epoxy group, and when it has four or more, cross-linking is performed more densely and the epoxy compound is flexible. Gender is also given more.
- the epoxy compound is not particularly limited, but preferably has 10 or less epoxy groups in one molecule. In this case, the crosslink density does not become excessive and the toughness is provided.
- the epoxy compound examples include diethylene glycol / diglycidyl ether, polyethylene / diglycidyl ether, polypropylene glycol / diglycidyl ether, neopentyl glycol / diglycidyl ether, 1,6-hexanediol / diglycidyl ether, and glycerol.
- Polyhydric alcohols such as polyglycidyl ether, trimethylolpropane / polyglycidyl ether, polyglycerol / polyglycidyl ether, pentaerythrithiol / polyglycidyl ether, diglycerol / polyglycidyl ether, sorbitol / polyglycidyl ether, and epichlorohydrin. Reaction products can be mentioned. When these compounds are used as the epoxy compounds, the adhesiveness between the organic fiber cord and the rubber can be further improved.
- the epoxy compound has the above-mentioned (C) (C-1) epoxy compound, (C-2) polyphenol compound and (C-3) (heat dissociable blocked) isocyanate group in terms of the amount of solid components.
- the content of the (C-1) epoxy compound is preferably 0.5 to 80%, and 10 to 77. It is more preferably%, and even more preferably 20 to 75%. When the content is within this range, the effect of the epoxy compound becomes remarkable.
- the polyphenol compound (C-2) can further enhance the adhesiveness of the adhesive composition by acting as a cross-linking agent and / or an adhesion promoter.
- the type of the polyphenol compound is not particularly limited, but it is preferable to have three or more hydroxyl groups from the viewpoint of obtaining excellent adhesiveness and reducing the load on the environment.
- the polyphenol compound at least one selected from the group consisting of phloroglucinol (lower formula (1)), morin (lower formula (2)), phloroglucinol (lower formula (3)), lignin, and tannin. Species can be used, and among these, it is more preferable that the polyphenol compound contains at least lignin.
- the lignin and tannin can be obtained from a plant, but the plant of origin is not particularly limited. Further, the lignin and tannin may be natural products themselves, or may be subjected to various chemical treatments. For example, examples of lignin include dealkali lignin, alkaline lignin, sodium sulfonate lignin and the like. Examples of tannins include plant tannins derived from mimosa and plant tannins derived from quebracho.
- the polyphenol compound may be used alone or in combination of two or more. Further, it is preferable to appropriately adjust the content of the polyphenol compound in the adhesive composition in consideration of the case of using it as a cross-linking agent or the case of using it as an adhesion promoter.
- the polyphenol compound has the above-mentioned (C) (C-1) epoxy compound, (C-2) polyphenol compound and (C-3) (heat dissociable blocked) isocyanate group in terms of the amount of solid components.
- the content of the (C-2) polyphenol compound is preferably 0.5 to 75%, and 0. It is more preferably 5 to 60%, and even more preferably 1 to 50%.
- the aqueous compound having the (C-3) (thermally dissociable blocked) isocyanate group is a compound having an action of promoting adhesion of the adhesive composition to a resin material as an adherend, and is a polar functional group. It is a compound having an isocyanate group.
- the "(heat dissociative blocked) isocyanate group" of the "aqueous compound having a (heat dissociative blocked) isocyanate group” means a heat dissociative blocked isocyanate group or an isocyanate group.
- B A heat-dissociative blocked isocyanate group generated by the reaction of an isocyanate group with a heat-dissociative blocking agent for the isocyanate group.
- B Isocyanate groups whose isocyanate groups have not reacted with the heat dissociative blocking agent for the isocyanate groups.
- C Isocyanate group generated by dissociation of a heat dissociative blocking agent from a heat dissociative blocked isocyanate group
- D Isocyanate group, including.
- aqueous of the aqueous compound having a (thermally dissociable blocked) isocyanate group indicates that it is water-soluble or water-dispersible, and the water-soluble does not necessarily mean completely water-soluble. It also means that it is partially water-soluble, or that it does not undergo phase separation in the aqueous solution of the adhesive composition of the present invention.
- the heat-dissociable blocking agent is a blocking agent compound capable of dissociating the blocking agent and restoring the isocyanate group by performing heat treatment as necessary while protecting the isocyanate group from an arbitrary chemical reaction. If there is, it is not particularly limited. Specifically, at the temperature of the heat treatment in which the adhesive treatment liquid is attached and dried and then heat-cured, the heat that can restore the crosslinking reactivity of the isocyanate group whose reactivity is suppressed by being sealed with the heat dissociable blocking agent. The dissociation temperature is preferred.
- the blocking agent include alcohol, phenol, active methylene, oxime, lactam, amine and the like, and are not particularly limited.
- Mercaptans such as hydroxypyridines, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazo, 4-bromo-3,5-dimethylpyrazole and 3-methyl- Pyrazoles such as 5-phenylpyrazole; dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, dicyclohexylamine, diphenylamine, xylidine, N, N-diethylhydroxyamine, N, N'-diphenylform amidine, 2- Amines such as hydroxypyridines, 3-
- the aqueous compound having a (heat dissociable blocked) isocyanate group specifically contains aromatic polyisocyanates or aromatic aliphatic polyisocyanates, and the aromatic isocyanates include m-phenylene.
- Phenylene diisocyanates such as diisocyanate and p-phenylenedi isocyanate; tolylene diisocyanates such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (TDI); 2,4'-diphenylmethane diisocyanate, 4,4'- Diphenylmethane diisocyanates such as diphenylmethane diisocyanate (MDI), dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate; polymethylenepolyphenylpolyisocyanate (polymeric MDI); m- or p-isocyanatophenylsulfony
- aromatic aliphatic polyisocyanates examples include xylylene diisocyanates such as m-xylylene diisocyanate, p-xylylene diisocyanate (XDI), and tetramethylxylylene diisocyanate; diethylbenzene diisocyanate; and ⁇ , ⁇ , ⁇ , ⁇ -tetra. Methylxylylene diisocyanate (TMXDI); and the like.
- modified products such as carbodiimide, polyol and allophanate of the above-mentioned polyisocyanate can be mentioned.
- aromatic isocyanates are preferable from the viewpoint of code focusing of the adhesive composition, and more preferably tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or polymethylene. It is a polyphenyl polyisocyanate (polymeric MDI), and particularly preferably diphenylmethane diisocyanate (MDI).
- the aqueous compound having a (heat dissociative blocked) isocyanate group is not particularly limited, but is more preferably an aqueous urethane compound having a (heat dissociative blocked) isocyanate group.
- the details of the aqueous urethane compound having a (heat dissociative blocked) isocyanate group will be described later.
- the content of the solid component is the above-mentioned (C) (C-1) epoxy compound, (C-2) polyphenol compound and (C-3) (Thermal dissociable block)
- the content of the aqueous compound having an isocyanate group is preferably 0.5 to 80%, more preferably 1 to 75%, still more preferably 5 to 70%.
- the ratio of the content of the aqueous compound having the (C-3) (heat dissociative blocked) isocyanate group is 0.5% or more, the adhesiveness between the resin and the coated rubber composition becomes better. Because. Further, when the above ratio is 75% or less, it is possible to secure the amount of other components such as rubber latex to be blended in the adhesive composition relative to a certain level or more, and as a result, it is possible to secure the amount of the adhered rubber. This is because the adhesiveness becomes better.
- a polyester synthetic resin material such as polyethylene terephthalate, which is widely used as an organic fiber cord, is composed of a flat linear polymer chain.
- the surface of the polymer chain or the gaps between the polymer chains have a ⁇ -electron atmosphere derived from the aromatics and the like contained in the polymer chain.
- polyester has a particularly small number of hydroxyl groups on the surface as compared with 6,6-nylon. Therefore, conventionally, the adhesive composition for an organic fiber cord used for an organic fiber cord made of polyester has been used in order to obtain sufficient adhesive strength.
- the adhesive composition for the organic fiber cord is dispersed in the gaps between the polymer chains of the organic fiber cord
- -The adhesive layer of the adhesive composition for the organic fiber cord is the polymer chain of the organic fiber cord.
- Adhesion to the surface For the purpose of this, a molecule having a planar structure (“a portion easily diffused into an organic fiber cord”) having an aromatic ring having an aromatic ⁇ electron on the side surface has been contained as an adhesion promoter.
- an adhesion promoter conventionally, water dispersibility (thermally dissociable blocked) which is an addition product of the above-mentioned "polyisocyanate having an aromatic ring and a blocking agent having one or more active hydrogen groups” has been used.
- Isocyanate compounds have been used.
- the rubber-resin adhesive composition of the present invention in addition to the hydrophobic aromatic polyisocyanate portion which is a “portion which easily diffuses into the resin” in the molecular structure, a “portion which is difficult to diffuse into the resin”. It is more preferable to contain "an aqueous urethane compound having a (thermally dissociable blocked) isocyanate group" which also has a hydrophilic molecular chain portion.
- aqueous of the “aqueous urethane compound” indicates that it is water-soluble or water-dispersible, and the water-soluble does not necessarily mean completely water-soluble, but is partially water-soluble. Alternatively, it also means that no phase separation occurs in the aqueous solution of the adhesive composition.
- the "urethane compound” of the "aqueous urethane compound” is a compound having a covalent bond formed between nitrogen of an amine and carbon of a carbonyl group, and refers to a compound represented by the following general formula.
- R and R' represent a hydrocarbon group.
- the molecular weight of the "aqueous urethane compound having a (heat dissociative blocked) isocyanate group” is not particularly limited as long as it can maintain aqueous properties, but is preferably a number average molecular weight of 1,500 to 100. It is 000, and particularly preferably the number average molecular weight is 9,000 or less.
- the method for synthesizing the "aqueous urethane compound having a (heat dissociative blocked) isocyanate group” is not particularly limited, but the method described in JP-A-63-51474 and the like can be used. It can be a known method.
- a preferred embodiment of the above-mentioned "aqueous urethane compound having a (heat dissociative blocked) isocyanate group” is ( ⁇ ) An organic polyisocyanate compound having 3 or more and 5 or less functional groups and having a number average molecular weight of 2,000 or less. ( ⁇ ) A compound having 2 or more and 4 or less active hydrogen groups and having a number average molecular weight of 5,000 or less. A compound having ( ⁇ ) a thermally dissociative blocking agent and ( ⁇ ) at least one active hydrogen group and at least one anionic, cationic or nonionic hydrophilic group.
- the mixing ratio of each of ( ⁇ ), ( ⁇ ), ( ⁇ ) and ( ⁇ ) to the total amount is Regarding ( ⁇ ), 40% by mass or more, 85% by mass or less, Regarding ( ⁇ ), 5% by mass or more, 35% by mass or less, Regarding ( ⁇ ), 5% by mass or more, 35% by mass or less, and Regarding ( ⁇ ), 5% by mass or more, 35% by mass or less, It is a reaction product after mixing and reacting so that Moreover, when the molecular weight of the isocyanate group (-NCO) is 42, the composition ratio of the (heat dissociative blocked) isocyanate group in the reaction product is 0.5% by mass or more and 11% by mass or less. It is characterized by being.
- aqueous urethane compound having a (heat dissociative blocked) isocyanate group is urethane because it has both a site consisting of a (heat dissociative blocked) isocyanate group and a hydrophilic site having a hydrophilic group. This is because it has the advantage of increasing the self-hydrophilicity of the compound.
- the organic polyisocyanate compound having ( ⁇ ) 3 or more and 5 or less functional groups and having a number average molecular weight of 2,000 or less is not particularly limited, but is an aromatic polyisocyanate compound and its oligomer. It is preferable, and other aliphatic, alicyclic or heterocyclic polyisocyanate compounds and oligomers thereof may be used.
- the reaction product after reacting such an organic polyisocyanate compound having ( ⁇ ) 3 or more and 5 or less functional groups and having a number average molecular weight of 2,000 or less is "(thermally dissociable blocked)". This is because the "aqueous urethane compound having an isocyanate group" is more likely to be dispersed in the gaps between the polymer chains of the resin.
- aliphatic polyisocyanate compound ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecanediisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2 , 4,4-trimethylhexamethylene diisocyanate, dimerate diisocyanate, lysine diisocyanate and the like
- examples of the alicyclic polyisocyanate compound include cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate.
- Isophoron diisocyanate 4,4'-methylenebis (cyclohexylisocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, etc.
- the compound include a tolylene diisocyanate adduct of 1,3,5-tris (2'-hydroxyethyl) isocyanuric acid
- examples of the aromatic polyisocyanate compound include m-phenylenedi isocyanate and p-phenylenedi isocyanate.
- aromatic polyisocyanate compounds are preferable, and methylenediphenyl polyisocyanate, polyphenylene polymethylene polyisocyanate and the like are particularly preferable.
- Polyphenylene polymethylene polyisocyanate having a number average molecular weight of 2,000 or less is preferable, and polyphenylene polymethylene polyisocyanate having a number average molecular weight of 1,000 or less is particularly preferable.
- the reaction product after reacting such an organic polyisocyanate compound having ( ⁇ ) 3 or more and 5 or less functional groups and having a number average molecular weight of 2,000 or less is "(thermally dissociable blocked)". This is because the "aqueous urethane compound having an isocyanate group" is more likely to be dispersed in the gaps between the polymer chains of the resin.
- the compound having ( ⁇ ) 2 or more and 4 or less active hydrogen groups and having a number average molecular weight of 5,000 or less is not particularly limited, but specifically, the following (i) to (vii).
- Examples include compounds selected from the group consisting of: (I) Multihydric alcohols having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less.
- Multivalent amine C2-C4 alkylene oxide heavy adducts of polyhydric phenols and amino alcohols, C2-C4 alkylene oxide heavy adducts of C3 and above polyhydric alcohols, An alkylene oxide copolymer of C2 to C4 or an alkylene oxide polymer of C3 to C4.
- the active hydrogen group means active hydrogen (atomic hydrogen (hydrogen radical)) and active hydrogen when placed under suitable conditions. It refers to a group containing hydrogen that becomes a hydride ion (hydride). Examples of the active hydrogen group include an amino group and a hydroxyl group.
- At least one active hydrogen group and at least one anionic of the above-mentioned "compound having ( ⁇ ) at least one active hydrogen group and at least one anionic, cationic or nonionic hydrophilic group examples include, but are not limited to, amino sulfonic acids such as taurine, N-methyl taurine, N-butyl taurine and sulfanic acid, and amino carboxylic acids such as glycine and alanine. ..
- the method for synthesizing the "aqueous urethane compound having a (heat dissociative blocked) isocyanate group" by mixing and reacting the ( ⁇ ), ( ⁇ ), ( ⁇ ), and ( ⁇ ) is particularly limited. However, a known method such as the method described in JP-A-63-51474 can be used.
- aqueous urethane compound having a (heat dissociative blocked) isocyanate group is the following general formula (1):.
- A is a residue of the organic polyisocyanate compound from which the active hydrogen group has been eliminated.
- X is a residue of a polyol compound having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less from which the active hydrogen group has been eliminated.
- Y is the residue of the heat dissociative blocking agent from which the active hydrogen group has been eliminated.
- Z is a residue of a compound having at least one active hydrogen group and a group producing at least one salt or a hydrophilic polyether chain from which the active hydrogen group has been removed.
- aqueous urethane compound having a (heat dissociative blocked) isocyanate group is a urethane compound because it has both a site consisting of a (heat dissociative blocked) isocyanate group and a hydrophilic site having a hydrophilic group. This is because it has the advantage of increasing the self-water solubility of.
- the "organic polyisocyanate compound" of "residue from which the active hydrogen group is eliminated” of A in the formula (1) contains an aromatic ring.
- the "aqueous urethane compound having a (heat dissociative blocked) isocyanate group” is more easily dispersed in the gaps between the polymer chains of the resin.
- examples thereof include methylenediphenylpolyisocyanate and polyphenylenepolymethylenepolyisocyanate.
- Polyphenylene polymethylene polyisocyanate having a number average molecular weight of 6,000 or less is preferable, and polyphenylene polymethylene polyisocyanate having a number average molecular weight of 4,000 or less is particularly preferable.
- polyol compound having 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less is not particularly limited, but is specifically selected from the group consisting of the following (i) to (vi). Examples include compounds: (I) Multihydric alcohols having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less.
- aqueous urethane compound having a (heat dissociative blocked) isocyanate group is not particularly limited, but commercially available products such as Elastron BN27, BN77, BN11 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. are used. You can also.
- the BN77 was used in the following examples herein.
- the method for producing the adhesive composition for an organic fiber cord of the present invention is not particularly limited, but it can be produced, for example, by mixing and aging each material.
- the adhesive composition is usually used in the state of an aqueous solution, and the solid content in the aqueous solution of the adhesive composition is preferably in the range of 5 to 60% by mass, preferably in the range of 5 to 50% by mass. Is more preferable.
- the adhesive composition can be composed of a one-bath treatment liquid or a two-bath treatment liquid.
- the one-bath treatment is a treatment in which the adhesive composition is adhered to the surface of the organic fiber cord by dipping the organic fiber cord to be bonded into one treatment liquid (adhesive composition).
- the two-bath treatment is a treatment in which the adhesive composition is adhered to the surface of the organic fiber cord by dipping the organic fiber cord to be bonded into two treatment liquids in order. Therefore, when the adhesive composition is a two-bath treatment liquid, the combination of the first-bath and second-bath treatment liquids is the adhesive composition.
- the rubber-organic fiber cord composite of the present invention is a rubber-organic fiber cord composite including a rubber member and an organic fiber cord, and at least a part of the organic fiber cord of the present invention is described above. It is characterized by being coated with an adhesive composition for an organic fiber cord. Since the rubber-organic fiber cord composite of the present invention uses the adhesive composition for the organic fiber cord of the present invention, the load on the environment is small, the adhesiveness between the rubber and the organic fiber cord is excellent, and the productivity is excellent. Is high.
- the use of the rubber-organic fiber cord composite of the present invention is not particularly limited. For example, it can be used as a member such as a belt, an air spring, or a hose.
- the adhesive composition of the present invention may cover at least a part of the organic fiber cord, but the adhesiveness between the rubber and the organic fiber cord is further improved. From the possible point of view, it is preferable that the adhesive composition of the present invention is coated on the entire surface of the organic fiber cord.
- the method for coating at least a part of the organic fiber cord with the above-mentioned adhesive composition is not particularly limited, and examples thereof include dipping, coating, and spraying. When the above-mentioned adhesive composition contains a solvent, the solvent can be removed by a drying treatment after coating.
- the material of the organic fiber cord is not particularly limited and can be appropriately selected depending on the intended use.
- the organic fiber cord include a fiber cord made of polyester such as polyethylene terephthalate (PET), a fiber cord made of an aliphatic polyamide such as 6-nylon, 6,6-nylon, and 4,6-nylon, and a fiber made of polyketone.
- PET polyethylene terephthalate
- Examples thereof include a cord, a fiber cord made of an aromatic polyamide such as paraphenylene terephthalamide, and a cellulose-based fiber cord such as rayon.
- the adhesive composition of the present invention can improve the adhesiveness between the rubber member and the cord even if it is coated on a polyester fiber cord which is generally considered to have low adhesiveness to rubber.
- the rubber member of the rubber-organic fiber cord composite of the present invention various rubber compositions (raw materials) containing at least a rubber component can be used, and vulcanization obtained by vulcanizing the rubber composition. It is preferable to form the rubber member from rubber.
- the rubber composition contains, for example, a filler such as carbon black and silica, sulfur, peroxide and the like, for a rubber component made of natural rubber or synthetic rubber (butadiene rubber, styrene-butadiene rubber, isoprene rubber, etc.). It can be produced by blending a cross-linking agent, a cross-linking accelerator and the like, kneading, heating, extruding and the like.
- the organic fiber cord coated with the adhesive composition is used as the rubber member. It can be produced by coating with an unvulcanized rubber composition as a raw material of the above to prepare an unvulcanized rubber-organic fiber cord composite, and then vulcanizing.
- the tire of the present invention is characterized by using the rubber-organic fiber cord composite of the present invention described above.
- the rubber-organic fiber cord composite of the present invention described above can be used as, for example, a carcass ply, a belt layer, a belt reinforcing layer, a belt peripheral reinforcing layer such as a flipper, and the like.
- the tire of the present invention may be obtained by vulcanization after molding using an unvulcanized rubber composition depending on the type of tire to be applied, or semi-vulcanized rubber that has undergone a preliminary vulcanization step or the like is used. It may be obtained by further main vulcanization after molding.
- the organic fiber cord treated with the above-mentioned adhesive composition is used in any part of the tire, but the other members are not particularly limited and known members are used. can do.
- the tire of the present invention is preferably a pneumatic tire, and as the gas to be filled in the pneumatic tire, in addition to normal or air adjusted for oxygen partial pressure, inactivity such as nitrogen, argon and helium. Gas can be used.
- Samples 1-1 to 1-10 of the adhesive composition having the composition shown in Table 1 (an aqueous solution containing polyacrylamide and rubber latex in a predetermined solid content) were prepared.
- the mechanical stability of the adhesive composition was evaluated by the following method.
- Samples 2-1 to 2-15 of the adhesive composition (an aqueous solution containing each component in a predetermined solid content) having the formulations shown in Table 3 were prepared under the following conditions.
- a typical preparation method is shown below.
- a mixture of (A) rubber latex and (B) a compound having an acrylamide structure is prepared.
- water necessary for dilution was added to the compound (C), and the mixture was mixed and stirred to prepare the compound.
- the order of addition is not limited.
- the final mixture was mixed into one to prepare a liquid.
- the composition of the obtained adhesive composition is as shown in Table 3.
- the samples 2-16 to 2-19 of the adhesive composition (an aqueous solution containing each component in a predetermined solid content) having the formulations shown in Table 3 are adhesive compositions for organic fiber cords of a two-bath treatment liquid system. Therefore, the one-bath treatment liquid and the second bath treatment liquid were prepared under the following conditions.
- First bath treatment liquid As the first bath treatment solution of the example, "Denacol EX614B" (manufactured by Nagase ChemteX Corporation) was 1% by mass, and as an isocyanate compound, "Elastron BN77” (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was 3% by mass.
- the numerical value of each mass% is the mass% as a ratio when each component is blended as a liquid or a solid in the liquid of the first bath treatment liquid.
- “Denacol EX614B” is 38% by mass
- "Elastron BN77” is 35% by mass
- "Isoban” is 27% by mass.
- the final mixture was mixed into one to prepare a second bath treatment liquid.
- the composition of the obtained adhesive composition is as shown in Table 3. All mixing and stirring were carried out at room temperature (atmospheric temperature: about 27 ° C.), and the liquid was used within the range of about 1 day immediately after preparation.
- the composition of the second bath treatment liquid when the total mass is 100 is as shown in Table 3 (the numerical value of each mass% is the value when each component is blended as a liquid or a solid in the liquid of the second bath treatment liquid. It is mass% as a ratio of.).
- the first bath is formed by immersing a / 10 cm organic fiber cord (PET cord for tires), then drying the solvent in the first bath treatment liquid adhering to the PET cord for tires, and applying an adhesive treatment by heating.
- the drying treatment conditions were a dry temperature of 160 ° C.
- the adhesion treatment conditions by heating were a hot temperature of 205 ° C. and a hot time of 60 seconds.
- Adhesion treatment of organic fiber cord (PET cord for tire) with second bath treatment liquid The tire cord bonded with each first bath treatment liquid is immersed in each second bath treatment liquid, and then the solvent in the second bath treatment liquid adhered to the tire cord is dried and bonded by heating. The tire cord was obtained by applying.
- the drying treatment conditions were a dry temperature of 160 ° C. and a dry time of 80 seconds
- the adhesion treatment conditions by heating were a hot temperature of 245 ° C. and a hot time of 60 seconds.
- the cord treated with the adhesive composition of each sample is in an unvulcanized state containing natural rubber, a rubber component composed of a styrene-butadiene copolymer, carbon black, and a cross-linking agent. It was embedded in a rubber composition to prepare a rubber-organic fiber cord composite, and further vulcanized at 160 ° C. for 20 minutes under a pressure of 20 kgf / cm 2 to prepare a sample of the rubber-organic fiber cord composite.
- an adhesive composition capable of achieving excellent adhesiveness and mechanical stability even when it does not contain formalin and resorcin. Further, according to the present invention, it is possible to provide a rubber-organic fiber cord composite and a tire which have a small burden on the environment and are excellent in adhesiveness and productivity between rubber and an organic fiber cord.
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Abstract
Description
また、ゴム部材との接着性を高めるため、接着剤組成物中にゴムラテックスを含む場合、ゴムラテックス粒子が凝集しやすく、機械的負荷を受けた際のゴムラテックスの分散性(接着剤組成物の機械的安定性)が悪化するという問題があり、この点についても改善が望まれていた。
また、本発明の目的は、環境への負荷が少なく、ゴムと有機繊維コードとの接着性及び生産性に優れた、ゴム-有機繊維コード複合体及びタイヤを提供することにある。
上記構成により、ホルマリン及びレゾルシンを含まない場合であっても、優れた接着性及び機械的安定性を実現できる。
また、本発明によれば、環境への負荷が少なく、ゴムと有機繊維コードとの接着性及び生産性に優れた、ゴム-有機繊維コード複合体及びタイヤを提供することができる。
本発明の有機繊維コード用接着剤組成物(以下、「本発明の接着剤組成物」ということがある。)は、(A)ゴムラテックスと、(B)アクリルアミド構造を含有する化合物(以下、「アクリルアミド含有化合物」ということがある。)と、を含むことを特徴とする。
ゴムラテックスを含む接着剤組成物中に、アクリルアミド構造を含有する化合物を含有させることによって、ホルマリン及びレゾルシンを用いない場合でも、ゴム部材と有機繊維コードとの間の接着力を高めることができるとともに、(B)アクリルアミド含有化合物がゴムラテックス粒子の凝集を抑制し、(A)ゴムラテックスが均一に分散するため、接着剤組成物の機械的安定性についても向上できる。
さらに、本発明の有機繊維コード用接着剤組成物は、レゾルシンやホルマリンを含んでいないため、環境への負荷を低減できる。
本発明の有機繊維コード用接着剤組成物は、(A)ゴムラテックスを含む。
ゴムラテックスを含む接着剤組成物を有機繊維コードにコーティングすることで、ゴム部材との接着性を高めることができる。
本発明の有機繊維コード用接着剤組成物は、上述した(A)ゴムラテックスに加えて、(B)アクリルアミド構造を含有する化合物(アクリルアミド含有化合物)を含む。
接着剤組成物中に、前記(A)ゴムラテックスとともに、(B)アクリルアミド含有化合物を用いることで、該アクリルアミド化合物が、ゴムラテックス粒子の表面を覆い、ゴムラテックス粒子同士が凝集することを抑制する。その結果、機械的負荷を受けた際のゴムラテックスの分散性が高まり、優れた機械的安定性を実現できる。
前記アクリルアミド含有化合物におけるアクリルアミドの含有量については、特に限定はされず、ポリアクリルアミドだけでなく、アクリルアミドとアクリル酸等との共重合体や、アクリルアミド構造を一部に有する化合物であってもよい。
また、前記アクリルアミド含有化合物として、アニオン性のポリアクリルアミド、ノニオン性のポリアクリルアミド、変性されたポリアクリルアミド等を用いることができる。
前記アクリルアミド含有化合物の分子量が10,000以上であることによって、前記ゴムラテックス粒子の凝集をより確実に抑えることができ、前記アクリルアミド含有化合物の分子量が7,000,000以下であることによって、アクリルアミド含有化合物が架橋してゲル化する等の問題を引き起こすこともない。そのため、接着剤組成物の機械的安定性をより向上させることができる。
固形成分量で、前記(A)ゴムラテックス及び前記(B)アクリルアミド構造を有する化合物の合計含有量を100%としたときの、前記(B)アクリルアミド構造を有する化合物の含有量の比率が0.3%以上の場合には、前記ゴムラテックス粒子の凝集を確実に抑え、機械的安定性をより高めることができ、当該比率が20%以下の場合には、前記ゴムラテックスによるゴムとの接着性を低下させることもない。
前記(A)ゴムラテックス及び前記(B)アクリルアミド構造を有する化合物の合計含有量を上記範囲とすることで、前記ゴムラテックスによるゴムとの接着性と、機械的安定性とをより高いレベルで両立できる。
例えば、他の物性に悪影響を与えることなくより優れた接着性を実現できる観点から、固形成分量で、前記(A)ゴムラテックス、前記(B)アクリルアミド構造を有する化合物、並びに、前記(C)(C-1)エポキシ化合物、(C-2)ポリフェノール化合物及び(C-3)(熱解離性ブロックド)イソシアネート基を有する水性化合物からなる群より選択される少なくとも一種の合計含有量を100%としたときの、前記(C)成分の含有量が5~80%であることが好ましく、5~75%であることがより好ましく、10~70%であることがさらに好ましい。
前記(C-1)エポキシ化合物としては、1分子中に少なくとも1つのエポキシ基を有する種々の化合物を使用できる。前記エポキシ化合物は、前記接着剤組成物の架橋剤として作用し、優れた接着性を実現でき、耐熱性、耐久性、強度、可撓性、電気的絶縁性等についても向上が可能となる。
また、前記エポキシ化合物は、特に限定されるものではないが、1分子中にエポキシ基を10個以下有することが好ましい。この場合、架橋密度が過度になりすぎず、靭性も備えるようになる。
前記ポリフェノール化合物(C-2)は、架橋剤及び/又は接着促進剤としての働きを行うことで、接着剤組成物の接着性をより高めることができる。
例えば、リグニンとしては、脱アルカリリグニン、アルカリリグニン、スルホン酸ナトリウムリグニン等が挙げられる。また、タンニンとしては、ミモサ由来の植物タンニン、ケブラチョ由来の植物タンニン等が挙げられる。
また、前記接着剤組成物中のポリフェノール化合物の含有量は、架橋剤として使用する場合や、接着促進剤として使用する場合を考慮して、適宜調整することが好ましい。
前記(C-3)(熱解離性ブロックド)イソシアネート基を有する水性化合物は、接着剤組成物の被着体である樹脂材料への接着を促進させる作用を有する化合物であって、極性官能基としてイソシアネート基を有する化合物である。
(イ)イソシアネート基が当該イソシアネート基に対する熱解離性ブロック剤と反応して生じた熱解離性ブロックドイソシアネート基、
(ロ)イソシアネート基が当該イソシアネート基に対する熱解離性ブロック剤と未反応であるイソシアネート基、
(ハ)熱解離性ブロックドイソシアネート基から熱解離性ブロック剤が解離して生じたイソシアネート基、
(ニ)イソシアネート基、
を含む。
ブロック剤は、アルコール、フェノール、活性メチレン、オキシム、ラクタム、アミン等が挙げられ、特に限定されないが、具体的にはε-カプロラクタム、δ-バレロラクタム、γ-ブチロラクタム等のラクタム類;フェノール、クレゾール、エチルフェノール、ブチルフェノール、オクチルフェノール、ノニルフェノール、ジノニルフェノール、チオフェノール、クロルフェノール、アミルフェノール等のフェノール類;メチルエチルケトキシム、アセトキシム、アセトフェノンオキシム、ベンゾフェノンオキシム、シクロヘキサノンオキシム等のオキシム類;メタノール、エタノール、ブタノール、イソプロピルアルコール、ブチルアルコール、シクロヘキサノールなどのアルコール類;ジメチルマロネート、ジエチルマロネート等のマロン酸ジアルキルエステル類;アセト酢酸メチル、アセト酢酸エチル、アセチルアセトン等の活性メチレン類、ブチルメルカプタン、ドデシルメルカプタン等のメルカプタン類;アセトアニリド、酢酸アミド等のアミド類;コハク酸イミド、フタル酸イミド、マレイン酸イミド等のイミド類;重亜硫酸ソーダ等の亜硫酸塩類;メチルセロソルブ、エチルセロソルブおよびブチルセロソルブ等のセロソルブ類;ピラゾール、3,5-ジメチルピラゾール、3-メチルピラゾール、4-ベンジル-3,5-ジメチルピラゾール、4-ニトロ-3,5-ジメチルピラゾー、4-ブロモ-3,5-ジメチルピラゾール及び3-メチル-5-フェニルピラゾール等のピラゾール類;ジメチルアミン、ジエチルアミン、ジ-n-プロピルアミン、ジイソプロピルアミン、ジシクロヘキシルアミン、ジフェニルアミン、キシリジン、N,N-ジエチルヒドロキシアミン、N,N’-ジフェニルホルムアミジン、2-ヒドロキシピリジン、3-ヒドロキシピリジンおよび2-メルカプトピリジン等のアミン類:及び1,2,4-トリアゾール等のトリアゾール類、等が挙げられる。これらの2種以上の混合物等を使用してもよい。
これらのブロック剤は、加熱での熱解離による接着剤組成物の熱硬化が安定して得られ易いフェノール、ε-カプロラクタムおよびケトオキシムを好適に用いることができる。
これらの芳香環を分子内に含むポリイソシアネートのうち、接着剤組成物のコード集束性の観点から、芳香族イソシアネートが好ましく、更に好ましくはトリレンジイソシアネート(TDI)、ジフェニルメタンジイソシアネート(MDI)あるいはポリメチレンポリフェニルポリイソシアネート(ポリメリックMDI)であり、特に好ましくは、ジフェニルメタンジイソシアネート(MDI)である。
前記(熱解離性ブロックド)イソシアネート基を有する水性ウレタン化合物については、その詳細を後述する。
前記(C-3)(熱解離性ブロックド)イソシアネート基を有する水性化合物の含有量については、固形成分量で、前記(C)(C-1)エポキシ化合物、(C-2)ポリフェノール化合物及び(C-3)(熱解離性ブロックド)イソシアネート基を有する水性化合物からなる群より選択される少なくとも一種の合計含有量を100%としたときの、前記(C-3)(熱解離性ブロックド)イソシアネート基を有する水性化合物の含有量が0.5~80%であることが好ましく、1~75%であることがより好ましく、5~70%であることがさらに好ましい。前記(C-3)(熱解離性ブロックド)イソシアネート基を有する水性化合物の含有量の割合が0.5%以上であれば、樹脂と被覆ゴム組成物の接着性がより良好なものになるからである。また、上記割合が75%以下であれば、接着剤組成物に配合するゴムラテックス等の他の成分の量を、相対して一定以上確保することが可能となり、その結果、被着ゴムとの接着性がより良好となるからである。
・前記有機繊維コード用接着剤組成物が有機繊維コードの高分子鎖の間隙へ分散すること、及び
・前記有機繊維コード用接着剤組成物による接着剤層が前記有機繊維コードの高分子鎖の表面に密着すること、
を目的として、芳香族性π電子を有する芳香環を側面に有する平面的な構造(「有機繊維コードに拡散しやすい部分」)の分子を、接着促進剤として含有してきた。
そのような接着促進剤の具体例としては、従来より、前記「芳香環を有するポリイソシアネートと活性水素基を1個以上有するブロック剤との付加生成物である水分散性(熱解離性ブロックド)イソシアネート化合物」が使用されてきている。
(α)3個以上、5個以下の官能基を有する、数平均分子量2,000以下の有機ポリイソシアネート化合物、
(β)2個以上、4個以下の活性水素基を有する、数平均分子量5,000以下の化合物、
(γ)熱解離性ブロック剤、並びに
(δ)少なくとも1つの活性水素基と、アニオン性、カチオン性、又は非イオン性の少なくとも1つの親水基と、を有する化合物、
を、(α)、(β)、(γ)及び(δ)の総和量に対する、それぞれの混合比率が、
(α)については、40質量%以上、85質量%以下、
(β)については、5質量%以上、35質量%以下、
(γ)については、5質量%以上、35質量%以下、及び、
(δ)については、5質量%以上、35質量%以下、
になるように混合して、反応させた後の反応生成物であり、
且つ、イソシアネート基(-NCO)の分子量を42としたときの、前記反応生成物中における、(熱解離性ブロックド)イソシアネート基の構成比率が、0.5質量%以上、11質量%以下である、ことを特徴とする。
この上記の「(熱解離性ブロックド)イソシアネート基を有する水性ウレタン化合物」は、(熱解離性ブロックド)イソシアネート基からなる部位と、親水性基を有する親水性の部位を併せ持つ為に、ウレタン化合物の自己水溶性が高まる利点を有するからである。
具体例として、脂肪族ポリイソシアネート化合物としては、エチレンジイソシアネート、1,4-テトラメチレンジイソシアネート、1,6-ヘキサメチレンジイソシアネート、1,12-ドデカンジイソシアネート、2,2,4-トリメチルヘキサメチレンジイソシアネート、2,4,4-トリメチルヘキサメチレンジイソシアネート、ダイマー酸ジイソシアネート、リジンジイソシアネート等、脂環式ポリイソシアネート化合物としては、シクロブタン-1,3-ジイソシアネート、シクロヘキサン-1,3-ジイソシアネート、シクロヘキサン-1,4-ジイソシアネート、イソホロンジイソシアネート、4,4’-メチレンビス(シクロヘキシルイソシアネート)、メチルシクロヘキサン-2,4-ジイソシアネート、メチルシクロヘキサン-2,6-ジイソシアネート、1,3-(イソシアナトメチル)シクロヘキサン等、複素環式ポリイソシアネート化合物としては、1,3,5-トリス(2’-ヒドロキシエチル)イソシアヌル酸のトリレンジイソシアネート付加物等、芳香族ポリイソシアネート化合物としては、m-フェニレンジイソシアネート、p-フェニレンジイソシアネート、2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、m-キシリレンジイソシアネート、p-キシリレンジイソシアネート、2,4’-ジフェニルメタンジイソシアネート、4,4’-ジフェニルメタンジイソシアネート、m-テトラメチルキシリレンジイソシアネート、p-テトラメチルキシリレンジイソシアネート、メチントリス(4-フェニルイソシアネート)、トリス(4-イソシアナトフェニル)メタン、チオリン酸トリス(4-イソシアナトフェニルエステル)、3-イソプロペニル-α’,α’-ジメチルベンジルイソシアネート及びこれらのオリゴマー混合物、或いはこれらのポリイソシアネート化合物のカルボジイミド、ポリオール及びアロファネート等の変性物等が挙げられる。
これらの中で、芳香族ポリイソシアネート化合物が好ましく、特に好ましくは、メチレンジフェニルポリイソシアネート、ポリフェニレンポリメチレンポリイソシアネート等が挙げられる。数平均分子量2,000以下のポリフェニレンポリメチレンポリイソシアネートが好ましく、数平均分子量1,000以下であるポリフェニレンポリメチレンポリイソシアネートが特に好ましい。このような(α)3個以上、5個以下の官能基を有する、数平均分子量2,000以下の有機ポリイソシアネート化合物を反応させた後の反応生成物である「(熱解離性ブロックド)イソシアネート基を有する水性ウレタン化合物」は、樹脂の高分子鎖の間隙へ、より分散しやすくなるからである。
(i)2個以上4個以下の水酸基を有する、数平均分子量5,000以下の多価アルコール類、
(ii)2個以上4個以下の第一級及び/又は第二級アミノ基を有する、数平均分子量5,000以下の多価アミン類、
(iii)2個以上4個以下の第一級及び/又は第二級アミノ基と水酸基を有する、数平均分子量5,000以下のアミノアルコール類、
(iv)2個以上4個以下の水酸基を有する、数平均分子量5,000以下のポリエステルポリオール類、
(v)2個以上4個以下の水酸基を有する、数平均分子量5,000以下の、ポリブタジエンポリオール類及びそれらと他のビニルモノマーとの共重合体、
(vi)2個以上4個以下の水酸基を有する、数平均分子量5,000以下の、ポリクロロプレンポリオール類及びそれらと他のビニルモノマーとの共重合体、
(vii)2個以上4個以下の水酸基を有する、数平均分子量5,000以下のポリエーテルポリオール類である、
多価アミン、
多価フェノール及びアミノアルコール類のC2~C4のアルキレンオキサイド重付加物、
C3以上の多価アルコール類のC2~C4のアルキレンオキサイド重付加物、
C2~C4のアルキレンオキサイド共重合物、又は
C3~C4のアルキレンオキサイド重合物。
Aは、有機ポリイソシアネート化合物の、活性水素基が脱離した残基、
Xは、2個以上、4個以下の水酸基を有し、数平均分子量5,000以下のポリオール化合物の、活性水素基が脱離した残基、
Yは、熱解離性ブロック剤の、活性水素基が脱離した残基、
Zは、少なくとも1個の活性水素基と、少なくとも1個の塩を生成する基又は親水性ポリエーテル鎖と、を有する化合物の、活性水素基が脱離した残基、
nは、2以上4以下の整数、
p+mは、2以上4以下の整数(m≧0.25)、
を表す]で表されることを特徴とする。
上記の「(熱解離性ブロックド)イソシアネート基を有する水性ウレタン化合物」は、(熱解離性ブロックド)イソシアネート基からなる部位と、親水性基を有する親水性の部位を併せ持つ為に、ウレタン化合物の自己水溶性が高まる利点を有するからである。
特に限定されるものではないが、例えば、メチレンジフェニルポリイソシアネート、ポリフェニレンポリメチレンポリイソシアネート等が挙げられる。数平均分子量6,000以下のポリフェニレンポリメチレンポリイソシアネートが好ましく、数平均分子量4,000以下であるポリフェニレンポリメチレンポリイソシアネートが特に好ましい。
(i)2個以上4個以下の水酸基を有する、数平均分子量5,000以下の多価アルコール類、
(ii)2個以上4個以下の第一級及び/又は第二級アミノ基と水酸基を有する、数平均分子量5,000以下のアミノアルコール類、
(iii)2個以上4個以下の水酸基を有する、数平均分子量5,000以下のポリエステルポリオール類、
(iv)2個以上4個以下の水酸基を有する、数平均分子量5,000以下の、ポリブタジエンポリオール類及びそれらと他のビニルモノマーとの共重合体、
(v)2個以上4個以下の水酸基を有する、数平均分子量5,000以下の、ポリクロロプレンポリオール類及びそれらと他のビニルモノマーとの共重合体、
(vi)2個以上4個以下の水酸基を有する、数平均分子量5,000以下のポリエーテルポリオール類である、
多価アミン、
多価フェノール及びアミノアルコール類のC2~C4のアルキレンオキサイド重付加物、
C3以上の多価アルコール類のC2~C4のアルキレンオキサイド重付加物、
C2~C4のアルキレンオキサイド共重合物、又は
C3~C4のアルキレンオキサイド重合物。
また、前記接着剤組成物は、通常、水溶液の状態で使用され、接着剤組成物の水溶液における、固形分の含有量は、5~60質量%の範囲が好ましく、5~50質量%の範囲がより好ましい。
本発明のゴム-有機繊維コード複合体は、ゴム部材と、有機繊維コードとを備えた、ゴム-有機繊維コード複合体であって、前記有機繊維コードの少なくとも一部に、上述した本発明の有機繊維コード用接着剤組成物がコーティングされていることを特徴とする。
本発明のゴム-有機繊維コード複合体は、本発明の有機繊維コード用接着剤組成物を用いているため、環境への負荷が少なく、ゴムと有機繊維コードとの接着性に優れ、生産性が高い。
ここで、本発明のゴム-有機繊維コード複合体の用途は、特に限定はされない。例えば、ベルト、空気ばね、ホース等の部材として用いることができる。
また、有機繊維コードの少なくとも一部に、上記の接着剤組成物をコーティングする方法としては、特に限定されず、例えば、浸漬、塗布、吹き付け等が挙げられる。また、上述した接着剤組成物が溶媒を含有する場合には、コーティング後、乾燥処理により溶媒を除去することができる。
本発明のタイヤは、上述した本発明のゴム-有機繊維コード複合体を、用いたことを特徴とする。
本発明のタイヤでは、述した本発明のゴム-有機繊維コード複合体を、例えば、カーカスプライ、ベルト層、ベルト補強層、フリッパー等のベルト周り補強層等として用いることが可能である。
また、本発明のタイヤは、空気入りタイヤであることが好ましく、該空気入りタイヤに充填する気体としては、通常の或いは酸素分圧を調整した空気の他、窒素、アルゴン、ヘリウム等の不活性ガスを用いることができる。
表1に示す配合の接着剤組成物(所定の固形分量でポリアクリルアミドとゴムラテックスとを含有する水溶液)のサンプル1-1~1-10を調製した。該接着剤組成物に対して、下記の方法で、機械的安定性を評価した。
各サンプルの接着剤組成物について、JIS-K6387に準拠したマロン式機械的安定度試験を、以下の条件で実施し、接着剤組成物中に生じたゴムラテックスの凝集物の量(ゲル化率)を測定した。測定結果を表2に示す。
●条件
各サンプルの接着剤組成物:100g
荷重:30kgf
ローター回転数:1000rpm
時間:10分
表3に示す配合の接着剤組成物(所定の固形分量で各成分を含有する水溶液)のサンプル2-1~2-15を、以下の条件で調製した。代表的な調製方法を下記に示す。
(A)ゴムラテックスと(B)アクリルアミド構造を有する化合物を混合・攪拌したものを用意する。並行して(C)の化合物に対して、希釈に必要な水を添加し混合・攪拌したものを作成する。ただし、C種が複数ある場合にその添加順序は問わない。最後に混合したもの同士を一つに混ぜ合わせて液を調製した。得られた接着剤組成物の組成は、表3に示す通りである。なお、混合・攪拌は全て常温(雰囲気温度:27℃程度)で実施し、液は作成直後~1日程度の範囲で使用した。
その後、得られた各サンプルの接着剤組成物に、タイヤ用のナイロンコード(ナイロン66(66Ny)製、コード構造:1400dtex/2、撚り数:39×39/10cm)を1分間浸漬して引き上げ、コードに接着剤組成物を付着させた。その後、接着剤組成物が付着したコードを、150℃で2分間乾燥させた後、熱処理機を用いて、接着剤組成物が付着したコードを、1.5~3.5kg/本の張力(コードテンション)をかけ、235℃で1.3分間熱処理した。
(第一浴処理液)
実施例の第一浴処理液として、「デナコール EX614B」(ナガセケムテックス(株)製)を1質量%、イソシアネート化合物として「エラストロン BN77」(第一工業製薬(株)製)を3質量%、「イソバン」((株)クラレ製)を6質量%、となるように水で希釈した溶液を調製した。なお、前記各質量%の数値は、第一浴処理液の液体中、液体又は固体として各成分を配合したときの比としての質量%である。なお、乾燥時の比率としては、「デナコール EX614B」が38質量%、「エラストロン BN77」が35質量%、「イソバン」が27質量%である。
(第二浴処理液)
(A)ゴムラテックスと(B)アクリルアミド構造を有する化合物を混合・攪拌したものを用意する。並行して(C)の化合物に対して、希釈に必要な水を添加し混合・攪拌したものを作成する。ただし、C種が複数ある場合にその添加順序は問わない。最後に混合したもの同士を一つに混ぜ合わせて第二浴処理液を調製した。得られた接着剤組成物の組成は、表3に示す通りである。なお、混合・攪拌は全て常温(雰囲気温度:27℃程度)で実施し、液は作成直後~1日程度の範囲で使用した。総質量を100としたときの第二浴処理液の配合を、表3の通りとした(各質量%の数値は、第二浴処理液の液体中、液体又は固体として各成分を配合したときの比としての質量%である。)。
上記各第一浴処理液中の成分が均一に分散するよう攪拌を行った後、該各第一浴処理液に、コード繊度1670dtex/2、下撚り数39回/10cm、上撚り数39回/10cmの有機繊維コード(タイヤ用PETコード)を浸漬し、次いで、該タイヤ用PETコードに付着した第一浴処理液中の溶媒を乾燥し、加熱による接着処理を施すことで、第一浴処理液による接着処理をしたタイヤ用PETコードを得た。ここで、乾燥処理条件は、ドライ温度が160℃で、ドライ時間が80秒であり、加熱による接着処理条件は、ホット温度が205℃で、ホット時間が60秒であった。
(有機繊維コード(タイヤ用PETコード)の第二浴処理液による接着処理)
各第一浴処理液による接着処理をしたタイヤ用コードを各第二浴処理液に浸漬し、次いで、該タイヤ用コードに付着した第二浴処理液中の溶媒を乾燥し、加熱による接着処理を施すことで、タイヤ用コードを得た。ここで、乾燥処理条件は、ドライ温度が160℃で、ドライ時間が80秒であり、加熱による接着処理条件は、ホット温度が245℃で、ホット時間が60秒であった。
上述したように、各サンプルの接着剤組成物で処理したコードを、天然ゴム、スチレン-ブタジエン共重合体からなるゴム成分、カーボンブラック、架橋剤を含む未加硫状態のゴム組成物に埋め込み、ゴム-有機繊維コード複合体を作製し、更に、160℃で20分間、20kgf/cm2の加圧下で加硫し、ゴム-有機繊維コード複合体のサンプルを作製した。
作製したゴム-有機繊維コード複合体の各サンプルから、有機繊維コードを掘り起こし、300mm/分の速度にて引っ張ることで、ゴム-有機繊維コード複合体の各サンプルからコードを剥離し、コード1本あたりの剥離抗力を求め、これを接着力(N/本)とした。得られた接着力は、表3に示す。
上記ゴム-有機繊維コード複合体のから剥離させた有機繊維コードについて、被覆ゴムの付着状態を目視観察し、下記基準に従いスコア付けを行った。得られた結果を表3に示す。
A:ゴム付着率:80%以上
B:ゴム付着率:60%以上、80%未満
C:ゴム付着率:40%以上、60%未満
D:ゴム付着率:20%以上、40%未満
E:ゴム付着率:20%未満
また、本発明によれば、環境への負荷が少なく、ゴムと有機繊維コードとの接着性及び生産性に優れた、ゴム-有機繊維コード複合体及びタイヤを提供することができる。
Claims (13)
- (A)ゴムラテックスと、
(B)アクリルアミド構造を有する化合物と、
を含むことを特徴とする、有機繊維コード用接着剤組成物。 - (C)(C-1)エポキシ化合物、(C-2)ポリフェノール化合物及び(C-3)(熱解離性ブロックド)イソシアネート基を有する水性化合物からなる群より選択される少なくとも一種を、さらに含むことを特徴とする、請求項1に記載の有機繊維コード用接着剤組成物。
- 前記(C-1)エポキシ化合物が、1分子に2個以上のエポキシ基を有することを特徴とする、請求項2に記載の有機繊維コード用接着剤組成物。
- 前記(C-2)ポリフェノール化合物が、3つ以上の水酸基を有することを特徴とする、請求項2に記載の有機繊維コード用接着組成物。
- 前記(C-3)(熱解離性ブロックド)イソシアネート基を有する化合物が、芳香環を有するポリイソシアネートと活性水素基を1個以上有するブロック剤との付加生成物である水分散性(熱解離性ブロックド)イソシアネート化合物であることを特徴とする、請求項2に記載の有機繊維コード用接着剤組成物。
- 前記(C-3)(熱解離性ブロックド)イソシアネート基を有する化合物が、(熱解離性ブロックド)イソシアネート基を有する水性ウレタン化合物であることを特徴とする、請求項2に記載の有機繊維コード用接着剤組成物。
- 前記(熱解離性ブロックド)イソシアネート基を有する水性ウレタン化合物が、
(α)3個以上、5個以下の官能基を有する、数平均分子量が2,000以下の有機ポリイソシアネート化合物、
(β)2個以上、4個以下の活性水素基を有する、数平均分子量が5,000以下の化合物、
(γ)熱解離性ブロック剤、並びに、
(δ)少なくとも1つの活性水素基と、アニオン性、カチオン性、又は非イオン性の少なくとも1つの親水基と、を有する化合物、
を、(α)、(β)、(γ)及び(δ)の総和量に対する、それぞれの混合比率が、
(α)については、40質量%以上、85質量%以下、
(β)については、5質量%以上、35質量%以下、
(γ)については、5質量%以上、35質量%以下、及び
(δ)については、5質量%以上、35質量%以下、
になるように混合して、反応させた後の反応生成物であり、
且つ、イソシアネート基(-NCO)の分子量を42としたときの、前記反応生成物中における、(熱解離性ブロックド)イソシアネート基の構成比率が、0.5質量%以上、11質量%以下であることを特徴とする、請求項6に記載の有機繊維コード用接着剤組成物。 - 前記(熱解離性ブロックド)イソシアネート基を有する水性ウレタン化合物が、下記一般式(1):
Aは、有機ポリイソシアネート化合物の、活性水素基が脱離した残基、
Xは、2個以上、4個以下の水酸基を有する、数平均分子量が5,000以下のポリオール化合物の、活性水素基が脱離した残基、
Yは、熱解離性ブロック剤の、活性水素基が脱離した残基、
Zは、少なくとも1つの活性水素基と、少なくとも1つの塩を生成する基又は親水性ポリエーテル鎖と、を有する化合物の、活性水素基が脱離した残基、
nは、2以上4以下の整数、
p+mは、2以上4以下の整数(m≧0.25)
を表す]で表されることを特徴とする、請求項6に記載の有機繊維コード用接着剤組成物。 - 前記(A)ゴムラテックスは、天然ゴム(NR)、ポリイソプレンゴム(IR)、スチレン-ブタジエン共重合体ゴム(SBR)、ポリブタジエンゴム(BR)、エチレン-プロピレン-ジエンゴム(EPDM)、クロロプレンゴム(CR)、ハロゲン化ブチルゴム、アクリロニリトル-ブタジエンゴム(NBR)及びビニルピリジン-スチレン-ブタジエン共重合体ゴム(Vp)からなる群より選択される少なくとも一種であることを特徴とする、請求項1~8のいずれか1項に記載の有機繊維コード用接着剤組成物。
- 前記(B)アクリルアミド構造を含有する化合物の分子量が、10,000~7,000,000であることを特徴とする、請求項1~9のいずれか1項に記載の有機繊維コード用接着剤組成物。
- 固形成分量で、前記(A)ゴムラテックス、前記(B)アクリルアミド構造を有する化合物、並びに、前記(C)(C-1)エポキシ化合物、(C-2)ポリフェノール化合物及び(C-3)(熱解離性ブロックド)イソシアネート基を有する水性化合物からなる群より選択される少なくとも一種の合計含有量を100%としたときの、前記(A)ゴムラテックス及び前記(B)アクリルアミド構造を有する化合物の合計含有量が20~95%であり、該(A)ゴムラテックス及び(B)アクリルアミド構造の合計含有量を100%としたときの、前記(B)アクリルアミド構造を含有する化合物の量が0.3~30%であることを特徴とする、請求項2~10のいずれか1項に記載の有機繊維コード用接着剤組成物。
- ゴム部材と、有機繊維コードと、を備えた、ゴム-有機繊維コード複合体であって、
前記有機繊維コードの少なくとも一部に、請求項1~11のいずれか1項に記載の接着剤組成物がコーティングされていることを特徴とする、ゴム-有機繊維コード複合体。 - 請求項12に記載のゴム-有機繊維コード複合体を用いたことを特徴とする、タイヤ。
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US18/255,871 US20230407147A1 (en) | 2020-12-15 | 2021-11-16 | Adhesive composition, rubber-organic fiber cord composite, and tire |
EP21906243.7A EP4265699A4 (en) | 2020-12-15 | 2021-11-16 | ADHESIVE COMPOSITION, RUBBER-CORD COMPOSITE OF ORGANIC FIBERS AND TIRE |
CN202180084287.9A CN116601253A (zh) | 2020-12-15 | 2021-11-16 | 粘合剂组合物、橡胶-有机纤维帘线复合体和轮胎 |
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