JP2007521353A - Liquid adhesion promoter and metal or polymer substrate / rubber composition for cord reinforced rubber - Google Patents

Abstract

A rubber composition comprising a natural or synthetic rubber and an adhesive resin, by adding a long chain ester comprising mono-, di- and tri-esters and one or more reactive diluents, A rubber composition is disclosed that is capable of providing unexpected adhesion to cords in polymer and glass substrates, particularly radial tires, hoses, conveyor belts, transmission belts, and the like. In a preferred embodiment, the reactive diluent is (1) glycidyl ethers, (2) diglycidyl ethers, (3) aliphatic linear epoxides, (4) epoxidized vegetable oils, especially epoxidized soybean oil. , (5) cycloaliphatic epoxides, (6) glycidyl esters, and (7) diglycidyl esters.
[Selection figure] None

Description

  The present invention relates to adhesion promoters for elastomer adhesion, including natural or synthetic rubber, and cords or fiber substrates of synthetic polymers, and / or metal cords or metal substrates, in particular, for example, tires, hoses, conveyor belts, transmissions. In conjunction with cords in the manufacture of cord reinforced rubber products such as belts, in addition to the compositions described herein, a reactive diluent is included.

  Many rubber products include not only tires but also hoses, conveyor belts, power train belts, ie transmission belts, etc., which are usually reinforced with fibers or metal cords, Must be firmly bonded to the rubber. Therefore, whether the fiber is natural or synthetic fiber or metal and whether the rubber is natural or synthetic fiber are a problem.

  In conventional practice, fibers are prepared by pretreatment with a combination of hexamethoxymelamine or hexamethylenetetramine and a phenol formaldehyde condensation product, where phenol is almost always resorcinol. The mechanism is not fully understood, but the resin reacts with the fiber or rubber, affecting a firm reinforcing bond.

  One method of preparing cord-reinforced vulcanized rubber compositions involves mixing the rubber stock composition with the components of the adhesive resin condensation product. The components of the condensation product include a methylene acceptor and a methylene donor. The most commonly used methylene acceptor is a phenol such as resorcinol, while the most commonly used methylene donor is a melamine such as N- (substituted oxymethyl) melamine. The effect achieved is in situ during rubber vulcanization, regardless of whether the cord is pretreated with additional adhesives such as styrene-butadiene latex, isocyanate-blocked polyoxide, etc. A resin produced between a metal and a polymer cord.

  Vulcanizable rubber compositions that do not contain resorcinol are known. For example, U.S. Pat. No. 5,298,539 discloses at least one selected from uncured rubber, vulcanizing agent, melamine, acetoguanamine, benzoguanamine, cyclohexylguanamine, glycoluril monomer and oligomers thereof. A vulcanizable rubber composition containing an adhesive is disclosed. These derivatives are substituted with vinyl-terminated radicals on average on two or more positions on each monomer or oligomer unit and the composition does not contain resorcinol.

  Another method of omitting resorcinol from the vulcanizable rubber composition relies on the use of alternative co-reactants. U.S. Pat. No. 4,038,220 discloses a vulcanizable rubber composition containing rubber, a filler material, N- (substituted oxymethyl) melamine, and at least one of α- or β-naphthol. It is disclosed. In this document, when there is no resorcinol, α- or β-naphthol of monohydroxyl phenols is employed as a methylene acceptor in a resin forming reaction during vulcanization. Instead of resorcinol in vulcanizable rubber compositions, the use of resorcinol-formaldehyde resins is known. See, for example, A. Peterson, et al., “Resorcinol Bonding Systems for Steel Cord Adhesion”, Rubber World (August 1984).

  The increased need of the rubber fiber reinforced industry to withstand high dynamic pressures such as bends to avoid tire belt flaking is the continual of other better ways to achieve high bond strength Has been seeking.

  The tire typically has a structure such that the carcass, the end of the belt, the underbelt pad, and the like are intricately connected to each other at the shoulder. An underbelt pad that runs continuously along the circumferential shoulder of the tire between the tread rubber part and the carcass and extends outside the belt end along the width of the tire is probably the belt end This is a thick rubber layer having structural characteristics for relieving the shear stress generated between the part and the carcass. In addition, because the underbelt pad is repeatedly exposed to the load during running, heat tends to accumulate in the underbelt pad, which causes rubber breakage in the underbelt pad and between the rubber composition in the carcass. In addition, adhesion fails between the rubber part and the cord (steel cord). This causes belt end separation and carcass delamination, resulting in tire failure. One conventional approach to this problem is to form the underbelt pad with a rubber compound that reduces the amount of carbon black to suppress heat build-up.

  However, the rubber compound for the underbelt pad softens due to the reduction of carbon black therein. This also results in adhesion failure and internal rubber failure in the underbelt pad due to heat buildup, thereby causing delamination and underbelt peeling during travel. This approach is therefore not satisfactory with regard to tire durability. A decrease in tire durability resulting from heat buildup due to the structural characteristics of the underbelt pad is a significant problem. This is because recent improvements in vehicle performance require tires to be more durable at high speeds and loads.

  Despite its good frictional resistance, radial tires cannot be used earlier than bias tires due to belt stripping that occurs while the tread is still left. One where this problem is directed is to improve the tread or steel cord embedded rubber. For example, the improved tread has two layers: an inner layer (base tread adjacent to the belt) that suppresses heat generation by imitating friction resistance and an outer layer (cap tread) made of a rubber composition having high friction resistance. Layer structure. The improved steel cord embedded rubber also comprises a rubber composition that includes an adhesive, such as a cobalt salt of an organic acid, which increases the adhesion between the rubber and the steel cord. However, these improvements have not been fully successful.

  In an attempt to avoid belt delamination, other adhesion promoters, for example, vinylpyrimidine latex (VP latex, which is a copolymer of about 70% butadiene, about 15% styrene and about 15% vinylpyridine, are used. ) And other specific latexes are used. Examples of other latexes included in the adhesion promoter are acrylonitrile rubber, latex or styrene butadiene rubber latex. These can be used as such or in combination with each other. In particular, adhesion promoters suitable for polyethylene are those that have also been applied to multistage processes, for example, applied to combinations of polyoxides and their materials, followed by treatment with conventional resorcinol formaldehyde resins ( It is a blocked isocyanate that is subjected to (RFL immersion). It is also known to use combinations of RFL dipping with other adhesion promoters, such as triallyl cyanurate, resorcinol and formaldehyde, or reaction products of p-chlorophenol, resorcinol and formaldehyde.

It is necessary not only to have a high adhesive force between the rubber and a material such as a metal or a polymer cord, but also to reduce the decrease in the adhesive force while the tire is in use as small as possible. In fact, tires containing steel cord embedded rubber with good adhesion sometimes have a significant loss of initial adhesion after use. The following are possible reasons why the adhesion between the steel cord and the rubber is reduced during use of the tire.
(1) Tires are exposed to many small cracks when traveling over pebbles or pointed objects. This crack progresses into the thread, moisture penetrates into the tire, accelerates the aging and degradation of the embedded rubber, and rusts the steel cord. All of these lead to reduced adhesion.
(2) The adhesion improver contained in the steel cord embedded rubber diffuses and moves into the tread rubber during vulcanization or tire use. This leads to a decrease in adhesive strength.
(3) The softener and other additives contained in the tread move to the steel cord embedded rubber. This leads to a decrease in adhesive strength.

  Despite various proposals to improve the adhesion of cords to rubber, it is effective at improving the adhesion of rubber to fibers or metals in vulcanizable rubber compositions at a commercially available cost. There is a continuing demand for new adhesives.

  The adhesion promoter system of the present invention far exceeds the adhesion promoters known in the adhesion of metal oligomeric polymer cords to vulcanizable rubber.

Briefly, mono-, di- and / or tricarboxylic acids containing 1, 2 or 3 C ₆ -C ₂₄ long chain radicals or fatty acid residues, and alcohols containing C ₃ -C ₂₄ alkyl groups; For example, metal or polymer surfaces in natural or synthetic vulcanizates, particularly when added to melamine-containing resins or phenols such as resorcinol-containing adhesive resins such as novolak resins, When used in cords used for rubber reinforcement in tires, hoses, conveyor belts, motor mounts, drive belts including automobile transmission belts, etc., the adhesion between rubber and metal or polymer substrate It has been found that it leads to an unexpected increase.

  In accordance with the present invention, one or more organic solvents (diluents) described herein may be used in addition to or as a replacement for some or all of the solvent used to dissolve the adhesive resin. Adding to rubber unexpectedly increases the adhesion of the rubber composition to substrates such as polymer cords, metal cords, polymer fibers and metals, especially tires, hoses, conveyor belts, transmissions This is particularly noticeable in the production of cord reinforcement for rubber products such as belts.

  Examples of preferred reactive diluents include (1) glycidyl ether, (2) diglycidyl ether, (3) aliphatic linear epoxide, (4) epoxidized vegetable oil, especially epoxidized soybean oil, (5) cyclic Aliphatic epoxides, (6) glycidyl esters, and (7) diglycidyl esters are included.

Examples of suitable substrates include brass coated steel, brass, polyester, aramid, fiber, copper, glass and the like. Applications of the adhesion promoter of the present invention are directed to steel cords, brass coated steel cords, brass cords, polyester fiber cords, aramid fiber cords, glass cords, fabrics and planar metal surfaces. These resins have been used before gluing metal tire cords to vulcanizable rubber and theoretically bonding the rubber to the resin, but surprisingly good adhesion is achieved with C ₁₈ fatty acids and C ₃ -C ₂₄ alcohol, preferably by adding an additional C ₃ -C ₁₈ one or more long chain mono by reaction from alcohols, di-, and / or triesters, particularly Daimereto (dimerate) esters, it is found . Preferably, the ester provides an unexpectedly strong bond between the polymer or metal cord and the rubber when combined with an adhesion promoter. The long chain esters of the present invention adhere firmly to both rubber and resin, and the resin provides a sufficiently ionic bond to the reinforced cord.

  One feature of the compositions and products described herein is to provide a radial heavy tire for vehicles characterized by good adhesion between steel or polymer cord and steel cord embedded rubber. Yes, this adhesion persists over a long period of time while the tire is in use, with only a slight decrease. Another feature of the compositions and products described herein is to provide radial tires for vehicles and other cord-embedded rubber products that are excellent in bonding cords to rubber.

  The adhesion promoter system of the present invention includes at least one long chain ester compound and at least one adhesive resin. This adhesion promoter system is useful for improving the adhesion of rubber to metal or polymer substrates, particularly metal or polymer cords. Surprisingly, the adhesion promoter system described herein significantly increases the adhesion of the rubber composition to such metal or polymer substrates. In the present specification, “adhesion promoter system” and “adhesion promoter” are used interchangeably.

  In the adhesion promoter system of the present invention, long chain esters are typically added to natural or synthetic rubbers along with vulcanizing agents and adhesive resins. This adhesion promoter system is added to natural or synthetic rubber in an undiluted liquid to promote adhesion. Typically, however, the adhesion promoter is mixed with a dry carrier such as calcium silicate to form an alternative compounding system, which can be incorporated into natural or synthetic rubber. In such a method, the carrier facilitates the incorporation of the active adhesion promoter into the rubber. Yet another improvement of the present invention is that the adhesion promoter can be formulated as a “masterbatch”. In accordance with this aspect of the invention, the polymer (from about 6% to about 20% by weight) and the filler or inert component (from about 0% to about 14% by weight) are balanced in the adhesion promoter system (ie, At least one ester compound according to formulas I to IV and at least one adhesive resin such as melamine) are added to the natural or synthetic rubber. Typically, the masterbatch polymer and the rubber to which the masterbatch polymer is to be added are miscible. Preferably, the masterbatch polymer and rubber are the same.

  Throughout this specification, adhesion promoter systems are generally used between about 0.2% and about 30% by weight. Typically, each component of the adhesion promoter system of the present invention (ie, esters and adhesive resins according to Formulas I-IV) is about 0.1% by weight, based on the weight of natural or synthetic rubber in the composition. Between about 1% and about 15%, usually between about 1% and about 10%, most preferably between about 2% and about 8%. The reactive diluent is present between about 0.5% and about 50% by weight, based on the weight of the adhesion promoter system (esters of Formulas I-IV and adhesive resin). Usually, the reactive diluent is preferably between about 5 wt% and about 40 wt%, most preferably about 10 wt% to about 30 wt%, based on the total weight of the adhesive resin plus the ester of Formulas I-IV. % Is present.

  Here, ranges are expressed in the form of “about” or “approximately” one particular value and / or “about” or “approximately” another particular value. When such a range is displayed, another embodiment includes from one particular value and / or to another particular value. Similarly, when values are displayed as approximations by use of the preceding “about”, it is understood that the particular value forms another embodiment.

  Long chain esters can be monoesters, diesters, triesters or mixtures thereof, which are saturated or unsaturated, straight or branched hydrocarbons with 1, 2 or 3 diesters in the hydrocarbon chain. Has a double bond. The monoester has the following formula I:

ここで、Ｒ¹はＣ₃〜Ｃ₂₄のアルキル、好ましくはＣ₃〜Ｃ₁₈のアルキル、より好ましくはＣ₆〜Ｃ₁₈のアルキルであって、直鎖又は分岐の飽和又は１〜３個の炭素−炭素二重結合を有する不飽和のものである。Ｒ²は、Ｃ₃〜Ｃ₂₄の、好ましくはＣ₆〜Ｃ₂₄の、より好ましくはＣ₈〜Ｃ₁₈の不飽和炭化水素、又は１〜６個、好ましくは１〜３個の炭素−炭素二重結合を有する不飽和炭化水素である。

Where R ¹ is C ₃ -C ₂₄ alkyl, preferably C ₃ -C ₁₈ alkyl, more preferably C ₆ -C ₁₈ alkyl, linear or branched saturated or 1-3 An unsaturated compound having a carbon-carbon double bond. R ² is C ₃ -C ₂₄ , preferably C ₆ -C ₂₄ , more preferably C ₈ -C ₁₈ unsaturated hydrocarbon, or 1-6, preferably 1-3 carbon-carbon. It is an unsaturated hydrocarbon having a double bond.

  The diester has the following formula II or III.

ここで、ｎ＝３〜２４、好ましくは６〜１８、より好ましくは３〜１０であり、Ｒ³及びＲ⁴は、同じか又は異なっており、Ｃ₃〜Ｃ₂₄のアルキル、好ましくはＣ₃〜Ｃ₁₈のアルキル、より好ましくはＣ₆〜Ｃ₁₈のアルキルであって、直鎖又は分岐の飽和又は１〜３個の炭素−炭素二重結合を有する不飽和のものである。

Here, n = 3-24, preferably 6-18, more preferably 3-10, R ³ and R ⁴ are the same or different and are C ₃ -C ₂₄ alkyl, preferably C ₃ -C ₁₈ alkyl, more preferably C ₆ -C ₁₈ alkyl, which is saturated, linear or branched, or unsaturated with 1 to 3 carbon-carbon double bonds.

ここで、Ｒ⁵及びＲ⁷は、同じか又は異なっており、Ｃ₃〜Ｃ₂₄のアルキル、好ましくはＣ₆〜Ｃ₂₄のアルキル、より好ましくはＣ₈〜Ｃ₁₈のアルキルであって、直鎖又は分岐の飽和又は１〜６個の炭素−炭素二重結合を有する不飽和のものであり、Ｒ⁶及びＲ⁸は、同じか又は異なっており、Ｃ₃〜Ｃ₂₄のアルキル、好ましくはＣ₃〜Ｃ₁₈のアルキル、より好ましくはＣ₆〜Ｃ₁₈のアルキルであって、直鎖又は分岐の飽和又は１〜３個の炭素−炭素二重結合を有する不飽和のものであり、Ｒ¹⁰及びＲ¹¹は、同じか又は異なっており、Ｃ₃〜Ｃ₂₄の飽和炭化水素、好ましくはＣ₃〜Ｃ₁₈、より好ましくはＣ₆〜Ｃ₁₈の、直鎖又は分岐のもの、又は不飽和のＣ₃〜Ｃ₂₄炭化水素鎖で、好ましくはＣ₃〜Ｃ₁₈、より好ましくはＣ₆〜Ｃ₁₈の、直鎖又は分岐のものであって、１〜６個好ましくは１〜３個の炭素−炭素二重結合を有するものである。

Wherein R ⁵ and R ⁷ are the same or different and are C ₃ -C ₂₄ alkyl, preferably C ₆ -C ₂₄ alkyl, more preferably C ₈ -C ₁₈ alkyl, Chain or branched saturated or unsaturated having 1 to 6 carbon-carbon double bonds, R ⁶ and R ⁸ are the same or different and are C ₃ -C ₂₄ alkyl, preferably C ₃ -C ₁₈ alkyl, more preferably C ₆ -C ₁₈ alkyl, linear or branched saturated or unsaturated having 1 to 3 carbon-carbon double bonds, R ¹⁰ and R ¹¹ are the same or different and are C _{3 to} C ₂₄ saturated hydrocarbons, preferably C _{3 to} C ₁₈ , more preferably C _{6 to} C ₁₈ , linear or branched, or A saturated C ₃ -C ₂₄ hydrocarbon chain, preferably C ₃ -C ₁₈ , more preferably C ₆ -C ₁₈ , Is branched and has 1 to 6, preferably 1 to 3 carbon-carbon double bonds.

  The triester has the following formula IV:

ここで、Ｒ¹²、Ｒ¹⁴及びＲ¹⁸は、同じか又は異なっており、Ｃ₃〜Ｃ₂₄のアルキル、好ましくはＣ₆〜Ｃ₂₄のアルキル、より好ましくはＣ₈〜Ｃ₁₈のアルキルであって、直鎖又は分岐の飽和又は１〜６個、好ましくは１〜３個の炭素−炭素二重結合を有するものであり、Ｒ¹³、Ｒ¹⁵及びＲ¹⁹は、同じか又は異なっており、Ｃ₃〜Ｃ₂₄のアルキル、好ましくはＣ₃〜Ｃ₁₈のアルキル、より好ましくはＣ₆〜Ｃ₁₈のアルキルであって、直鎖又は分岐の飽和又は１〜３個の炭素−炭素二重結合を有する不飽和のものであり、Ｒ¹⁶、Ｒ¹⁷及びＲ²⁰は、同じか又は異なっており、Ｃ₃〜Ｃ₂₄の飽和炭化水素、好ましくはＣ₃〜Ｃ₁₈、より好ましくはＣ₆〜Ｃ₁₈の、直鎖又は分岐のもの、又は不飽和のＣ₃〜Ｃ₂₄炭化水素鎖で、好ましくはＣ₃〜Ｃ₁₈、より好ましくはＣ₆〜Ｃ₁₈の、直鎖又は分岐のものであって、１〜６個好ましくは１〜３個の炭素−炭素二重結合を有するものである。

Here, R ¹² , R ¹⁴ and R ¹⁸ are the same or different and are C _{3 to} C ₂₄ alkyl, preferably C _{6 to} C ₂₄ alkyl, more preferably C _{8 to} C ₁₈ alkyl. Linear or branched saturated or having 1 to 6, preferably 1 to 3 carbon-carbon double bonds, and R ¹³ , R ¹⁵ and R ¹⁹ are the same or different, C ₃ -C ₂₄ alkyl, preferably C ₃ -C ₁₈ alkyl, more preferably C ₆ -C ₁₈ alkyl, linear or branched saturated or 1 to 3 carbon-carbon double bonds R ¹⁶ , R ¹⁷ and R ²⁰ are the same or different and are C ₃ -C ₂₄ saturated hydrocarbons, preferably C ₃ -C ₁₈ , more preferably C _6- of C _18, a straight-chain or branched, or C ₃ -C ₂₄ hydrocarbon chain unsaturated, preferably C ₃ -C ₁₈ More preferably C ₆ -C _18, be of a straight chain or branched, is 1-6 preferably 1-3 carbon - are those having a carbon-carbon double bond.

The fatty acid residues or hydrocarbon chains R ² , R ⁵ , R ⁷ , R ¹² , R ¹⁴ and R ¹⁸ of the esters of the formulas I, II, III and IV are C _{3 to} C ₂₄ , preferably C _{6 to} C _24, more preferably any hydrocarbon chain C ₈ -C _18, is of a straight-chain or branched, 1-6 preferably 1-3 carbon - carbon double bond, butter , Lard, tallow, grease, herring, menhaden, pilchard, sardine, babas, castor, coconut, corn, cottonseed, jojoba, flaxseed, sika deer, olive, palm, palm kernel, peanut, rapeseed, safflower, soy, sunflower, tall And / or derived from fatty acids of animals or plants such as butterwood. Examples are hydrocarbon residues from the following fatty acids, the numbers in parentheses are the number of carbons and double bonds, ie (C _24-6 ) is 24 carbon atoms and 6 double bonds. Represents a hydrocarbon having the following: hexanoic (C _6-0 ), octanoic (C _8-0 ), decanoic (C _10-0 ), dodecanoic (C _12-0 ), 9-dodecenoic (CIS) (C _{12 -1} ), tetradecanoic (C _14-0 ), 9-tetradecenoic (CIS) (C _14-1 ), hexadecanoic (CIS) (C _16-0 ), 9-hexadeceno Ic (CIS) (C _16-1 ), octadecanoic (C _18-0 ), 9-octadecenoic (CIS) (C _18-1 ), 9-octadecenoic, 12-hydroxy- ( CIS) (C _18-2 ), 9,12-octadecadienoic (CIS, CIS) (C _18-2 ), 9, 12,15- octadecadienoic Triester Roh dichroic (CIS, CIS, CIS) ( C 18-3), 9,11,13- octadecadienoic Triester Roh dichroic (CIS, TRANS, TRANS) ( C 18-3), 9, 11,13-octadecatrienoic, 4-oxo (CIS, TRANS, TRANS) (C _18-3 ), octatetraenoic (C _18-4 ), eicosanoic (C ₂₀ ), 11-eicosenoic (C _{20 -1),} Eiko Saji enoic (C _20-2), eicosatrienoic enoic (C _20-3), 5,8,11,14 eicosatetraenoic enoic (C _20-4), eicosapentaenoic eno Quick (C _20-5), Dokosanoikku (C _22), 13- Dokosaenoikku (CIS) (C _22-1), docosapentaenoic tetra enoic (C _22-4), 4,8,12,15,19- Dokosapenta Enoic (C _{2 2-5),} docosahexaenoyl enoic (C _22-6), tetracosanol enoic (C _24-1), 4,8,12,15,18,21- tetracosahexaenoic enoic (C _24-6) It is.

  Examples of particularly useful diesters of formula (II) include saturated diesters formed by the reaction of sebacic acid and ethylhexyl alcohol.

式（II）の範囲内の他の有用なジエステルは、セバシン酸とトリデシルアルコールとの反応により形成される飽和ジエステルと、

Other useful diesters within the scope of formula (II) are saturated diesters formed by the reaction of sebacic acid and tridecyl alcohol;

セバシン酸とオレイルアルコールとの反応により形成される不飽和ジエステルとが含まれる。

And unsaturated diesters formed by the reaction of sebacic acid with oleyl alcohol.

式（III）に含まれる有用な環状ジエステルには、トール油脂肪酸由来のＣ₃₆ダイマー酸と、Ｃ₃〜Ｃ₂₄好ましくはＣ₃〜Ｃ₁₈より好ましくはＣ₆〜Ｃ₁₈の直鎖又は分岐の飽和又は不飽和の１〜３個の炭素−炭素二重結合を有するアルコールとの反応により形成されるダイメレートエステル構造が含まれている。このような環状エステルには、以下の構造が含まれ、構造Ａに対応するダイマー酸は、リノール酸の自己反応により生成され、構造Ｂに対応するダイマー酸は、リノール酸のオレイン酸との反応により生成され、構造Ｃに対応するダイマー酸は、リノール酸のリノレン酸との反応により生成されるが、

Wherein Useful cyclic diester contained in (III), and C ₃₆ dimer acid derived from tall oil fatty acids, linear or branched C ₃ -C ₂₄ is preferably more preferably C ₃ ~C ₁₈ C ₆ ~C ₁₈ The dimerate ester structure formed by reaction with an alcohol having 1 to 3 carbon-carbon double bonds, saturated or unsaturated, is included. Such cyclic esters include the following structures, where the dimer acid corresponding to structure A is produced by the self-reaction of linoleic acid, and the dimer acid corresponding to structure B is the reaction of linoleic acid with oleic acid. The dimer acid corresponding to structure C is produced by the reaction of linoleic acid with linolenic acid,

ここで、式（Ａ）、（Ｂ）及び（Ｃ）における各Ｒは、同じか又は異なっており、Ｃ₃〜Ｃ₂₄ラジカル、好ましくはＣ₃〜Ｃ₁₈、より好ましくはＣ₆〜Ｃ₁₈の直鎖又は分岐の飽和又は不飽和の１〜３個の炭素−炭素二重結合を有するものである。ＲＸ−１３８０４は、２−エチルヘキシルアルコールと反応した主にＣ₃₆ダイマー酸の反応により生成した不飽和ジエステル（ダイメレートエステル）の他の例である。ＲＸ−１３８２４は、主にＣ₃₆ダイマー酸のトリデシルアルコールとの反応により生成した不飽和ジエステル（ダイメレートエステル）の追加の例である。

Here, each R in the formulas (A), (B) and (C) is the same or different and is a C _{3 to} C ₂₄ radical, preferably C _{3 to} C ₁₈ , more preferably C _{6 to} C _18. Having 1 to 3 carbon-carbon double bonds, which are linear or branched, saturated or unsaturated. RX-13804 is another example of an unsaturated diester (dimerate ester) produced mainly by reaction of C ₃₆ dimer acid reacted with 2-ethylhexyl alcohol. RX-13824 is an additional example of an unsaturated diester (dimerate ester) produced primarily by reaction of C ₃₆ dimer acid with tridecyl alcohol.

  A representative example of a triester of formula IV (trimerate ester) is the following structure (D):

ここで、Ｒ¹、Ｒ²及びＲ³は、同じか又は異なっており、Ｃ₃〜Ｃ₂₄ラジカル、好ましくはＣ₃〜Ｃ₁₈、より好ましくはＣ₆〜Ｃ₁₈の直鎖又は分岐の飽和又は不飽和の１〜３個の炭素−炭素二重結合を有するものである。

Here, R ¹ , R ² and R ³ are the same or different and are C ₃ -C ₂₄ radicals, preferably C ₃ -C ₁₈ , more preferably C ₆ -C ₁₈ linear or branched saturated. Or it has 1 to 3 carbon-carbon double bonds which are unsaturated.

A particularly useful mixture of long chain esters is produced from a mixture of mono, dimer and trimer acids, for example products having CAS #: 61788-89-4. Esters prepared from these products are mixtures comprising mainly C ₃₆ and C ₅₄ dimerates and trimerate esters (A), (B), (C) and (D) as shown in the structural formula above, Mainly (more than 50% by weight) C ₃₆ dimerate esters (A), (B) and (C).

Reacts with an alcohol having 1 to 3 carbon-carbon double bonds of C _{3 to} C ₂₄ , preferably C _{3 to} C ₁₈ , more preferably C _{6 to} C ₁₈ , linear or branched, saturated or unsaturated. Commercially available mixtures of useful polybasic acids that can produce dimelate and trimerate as a mixture include EMPOL® 1010 Dimer Acid, EMPOL® 1014 Dimer Acid, EMPOL® 1016 Dimer Acid, EMPOL (R) 1018 DimerAcid, EMPOL (R) 1022 Dimer Acid, EMPOL (R) 1024 Dimer Acid, EMPOL (R) 1040 Trimer Acid, EMPOL (R) 1041 Trimer Acid, EMPOL (R) 1052 Polybasic Acid, and similar PRIPOL (TM) products from Uniqema are included as well as the product UNIDYME (R) from Arizona Chemical.

Particularly useful long chain ester additives, mono-, dimers, and / or trimer acids, one or more linear or branched C ₃ -C _24, preferably C ₃ -C _18, more preferably C ₆ Prepared by reaction with alcohols of ˜C ₁₈ to give esters of formulas I, II, III and IV. The dimer, trimer and polybasic acid can be obtained by dimerizing, trimerizing and polymerizing (oligomerizing) the long chain carboxylic acid from the fatty acid. The fatty acid may be a mixture. Thus, dimer acids are prepared by dimerization of C ₁₈ carboxylic acids (typically stearic acid, oleic acid, linoleic acid, linolenic acid) and, after esterification, saturated and unsaturated esters according to formulas III and IV (I.e., some long chain esters may contain hydrocarbon chains having 1 to 6, generally 1 to 3 carbon-carbon double bonds) including many dimerate and trimellate mixtures Arise. Any or any mixture of formulas I, II, III and / or IV, when combined with an adhesive resin, a metal or polymer cord, such as a woven or non-woven fiber, a metal or polymer substrate, and It functions to increase the adhesion of natural or synthetic rubber to metal flat materials.

  The adhesion promoter comprises an adhesive resin, which is preferably a condensation product of formaldehyde or methylene donor and formaldehyde or methylene acceptor, both produced by precondensation or in situ condensation during contact with rubber. Is done. The term “methylene donor” refers to a compound that can react with a methylene acceptor (eg, resorcinol or an equivalent thereof having a reactive hydroxyl group) and produces a resin in situ outside the rubber composition. The components of the condensation product preferably contain a methylene acceptor and a methylene donor. The most commonly employed methylene acceptor is a phenol such as resorcinol, and the most commonly employed methylene donor is N- (substituted oxymethyl) melamine. The effect achieved is in situ resin formation during rubber vulcanization, forming a bond between the metal or polymer cord and the rubber, which cord is a styrene-butadiene latex, Regardless of whether it has been pretreated with an additional adhesive such as a polyepoxide having blocked isocyanate groups. The long chain ester additive / resin combination described herein is particularly useful for steel cords where pretreatment of the adhesive is not very effective.

  Examples of methylene donors suitable for use in the rubber compositions disclosed herein include melanin, hexamethylenetetramine, hexaethoxymethylmelamine, hexamethoxymethylmelamine, lauryloxymethyl-pyridinium chloride, ethoxymethylpyridinium chloride, trioxane. Hexamethoxy-methylmelamine, those in which the hydroxy group is esterified or partially esterified, and polymers of formaldehyde such as parallel formaldehyde are included. In addition, the methylene donor can be an N-substituted oxymethylmelamine represented by the general formula:

ここで、Ｘは１〜８個の炭素原子を有するアルキル基であり、Ｒ³，Ｒ⁴，Ｒ₅，Ｒ₆及び’Ｒ₇は、各々独立に、水素、１〜８個の炭素原子を有するアルキル基及び−ＣＨ₂ＯＸ基からなる群から選択される基である。具体的なメチレンドナーには、ヘキサキス（メトキシメチル）メラミン；Ｎ，Ｎ’，Ｎ”−トリメチル／Ｎ，Ｎ’，Ｎ”−トリメチロール−メラミン；ヘキサメチロールメラミン；Ｎ，Ｎ’，Ｎ”−ジメチルロールメラミン；Ｎ−メチロール−メラミン；Ｎ，Ｎ’−ジメチロール−メラミン；Ｎ，Ｎ’，Ｎ”−トリス（メトキシメチル）メラミン；及びＮ，Ｎ’，Ｎ”−トリブチル−Ｎ，Ｎ’，Ｎ”−トリメチロール−メラミンが含まれる。メラミンのＮ−メチロール誘導体は、公知の方法により調製される。

Here, X is an alkyl group having 1 to 8 carbon atoms, and R ³ , R ⁴ , R ₅ , R ₆ and 'R ₇ are each independently hydrogen, 1 to 8 carbon atoms. And a group selected from the group consisting of an alkyl group and a —CH ₂ OX group. Specific methylene donors include hexakis (methoxymethyl) melamine; N, N ′, N ″ -trimethyl / N, N ′, N ″ -trimethylol-melamine; hexamethylolmelamine; N, N ′, N ″ — N-methylol-melamine; N, N′-dimethylol-melamine; N, N ′, N ″ -tris (methoxymethyl) melamine; and N, N ′, N ″ -tributyl-N, N ′, N "-trimethylol-melamine is included. The N-methylol derivative of melamine is prepared by a known method.

  The amount of methylene donor and methylene acceptor included in the rubber composition can be varied in advance or considered locally. Typically, the pre-considered amounts of methylene donor and methylene acceptor range from about 0.1% to about 15.0%, or each separately, of natural and / or synthetic rubber in the composition. It can be added at about 0.1% to about 10% by weight. Preferably, the respective amount of methylene donor and methylene acceptor considered in the field ranges from about 2.0% to about 5.0% based on the weight of natural and / or synthetic rubber in the composition. The weight ratio of methylene donor and methylene acceptor may be varied. Generally speaking, the weight ratio is from about 1:10 to about 10: 1. Preferably, the weight ratio is from about 1: 3 to about 3: 1.

  Also, vulcanizable rubber compositions that do not contain resorcinol are useful in the rubber compositions described herein. For example, resorcinol free adhesive resins and adhesive compositions are useful in adhesion promoting systems (ie, when combined with the long chain esters described herein), which is disclosed in US Pat. No. 5,891,938. No. and 5,298,539, which are hereby incorporated by reference. The '938 patent discloses a vulcanizable rubber composition comprising unvulcanized rubber and a self-condensing alkylated triazine resin having imino and / or methylol functionality. US Pat. No. 5,298,539 is a substituted derivative based on cyclic nitrogen compounds such as melamine, acetoguanamine, cyclohexylguanamine, benzoguanamine, and similar alkyl, aryl or aralkyl substituted melamines, glycolurils and oligomers of these compounds. Certain rubber additives are disclosed. In particular, adhesive resins and adhesive compounds useful as adhesive resins in the rubber compositions described herein include: from melamine, acetoguanamine, benzoguanamine, cyclohexylguanamine and glycoluril monomers and oligomeric derivatives of these monomers. Adhesive resin selected, which is substituted with vinyl-terminated radicals at an average of two or more positions of each monomer or oligomer unit, and the vulcanizable rubber composition does not contain resorcinol And derivatives thereof further substituted by radicals having carbamylmethyl or amidomethyl at one or more positions.

  Furthermore, the adhesive resin is a compound of the following formula:

及びそれらの位置異性体の何れかであり得る。ここで、各モノマー及びオリゴマーの高分子化ユニットにおいて、Ｙは、メチル、フェニル及びシクロヘキシルから選択されるものであり、平均して、少なくとも２個のＲが−ＣＨ₂−Ｒ¹であり、残りのＲがＨであり、少なくとも２Ｒ¹が下記から選択されるラジカルであり、

And any of their positional isomers. Here, in each monomer and oligomer polymerization unit, Y is selected from methyl, phenyl and cyclohexyl, and on average, at least two Rs are —CH ₂ —R ¹ , and the rest R is H and at least 2R ¹ is a radical selected from:

ここで、Ｒ²は水素又はＣ₁−Ｃ₁₈のアルキルであり、Ｚは下記から選択されるラジカルであり、

Where R ² is hydrogen or C ₁ -C ₁₈ alkyl, Z is a radical selected from:

残りのＲ¹ラジカルは、下記から選択され、

The remaining R ¹ radicals are selected from:

ここで、Ｒ³は水素又はＲ⁴であり、Ｒ⁴はＣ₁−Ｃ₁₈のアルキル、脂環式の基、ヒドロキシアルキル、又は芳香族ラジカルであり、オリゴマーにおけるＰは２〜約１０であり、Ｌはメチレン又はラジカル−ＣＨ₂−Ｏ−ＣＨ₂−である。これらの接着化合物は特に有用で、ここで各モノマー又は各オリゴマー化されたユニットにおける平均で少なくとも一つのＲ¹は、−ＮＨ−Ｃ（Ｏ）−ＯＲ⁴、特に次の式の化合物である。

Where R ³ is hydrogen or R ⁴ , R ⁴ is a C ₁ -C ₁₈ alkyl, alicyclic group, hydroxyalkyl, or aromatic radical, and P in the oligomer is from 2 to about 10. , L is methylene or the radical —CH ₂ —O—CH ₂ —. These adhesive compounds are particularly useful where, on average, at least one R ¹ in each monomer or each oligomerized unit is —NH—C (O) —OR ⁴ , in particular a compound of the formula

特に有用な接着樹脂には、上記式のものであって各モノマー又は各オリゴマーにおいて平均で少なくとも１個のＲラジカルが−ＣＨ₂−ＮＨ−Ｃ（Ｏ）−ＯＲ⁴であり、Ｒ⁴はＣ₁−Ｃ₁₈のアルキル、脂環式の基、ヒドロキシアルキル、又は芳香族ラジカルであるもの、並びに平均で少なくとも１個のＲラジカルが、ＣＨ₂＝Ｃ(ＣＨ₃)−Ｃ(Ｏ)Ｏ−Ｃ₃Ｈ₆−Ｏ−ＣＨ₂−及びＣＨ₂＝ＣＨ₂−Ｃ(Ｏ)Ｏ−Ｃ₂Ｈ₄−Ｏ−ＣＨ₂−から選択されるものであり、少なくとも一つのＲラジカルが−ＣＨ₂−ＮＨ−Ｃ(Ｏ)−Ｏ−ＣＨ₃及び−ＣＨ₂−ＮＨ−Ｃ(Ｏ)−Ｏ−Ｃ₃Ｈ₇から選択されるものであるものが含まれる。

Particularly useful adhesive resins are those of the above formula where, on average, at least one R radical in each monomer or oligomer is —CH ₂ —NH—C (O) —OR ⁴ , where R ⁴ is C ₁ -C ₁₈ alkyl, alicyclic group, hydroxyalkyl, or aromatic radical, and on average at least one R radical is CH ₂ ═C (CH ₃ ) —C (O) O— C ₃ H ₆ —O—CH ₂ — and CH ₂ ═CH ₂ —C (O) O—C ₂ H ₄ —O—CH ₂ —, wherein at least one R radical is —CH ₂ Included are those selected from —NH—C (O) —O—CH ₃ and —CH ₂ —NH—C (O) —O—C ₃ H ₇ .

  These adhesive resins and compounds include additional additives, especially hydroxymethylated and alkoxymethylated (alkoxy groups having 1 to 5 carbon atoms), melamine, acetoguanamine, benzoguanamine, cyclohexylguanamine and glycol Derivatives of uril as well as oligomers thereof are included.

Further useful adhesive resins in the rubber compositions described herein include self-condensing alkylated triazine resins selected from the group consisting of (i), (ii) and (iii),
(I) a self-condensing alkylated triazine resin having at least one imino or methylol functional group and represented by the following formula (I):

（ii）（ｉ）のオリゴマー、又は
（iii）（ｉ）及び（ii）の混合物、であり、
ここで、Ｚは、−Ｎ(Ｒ)(ＣＨ₂ＯＲ¹)、６〜１０の炭素原子を有するアリール基、１〜２０の炭素原子を有するアルキル基、又はアシル基であり、
各Ｒは、各々独立に水素又は−ＣＨ₂ＯＲ¹であり、
各Ｒ¹は、少なくとも一つのＲが水素又は−ＣＨ₂ＯＨであり少なくとも一つのＲ¹がアルキル基であるならば、各々独立に水素又は１〜１２の炭素原子を有するアルキル基であり、ここで加硫可能なゴム組成物は、メチレンアクセプター共反応剤を実質的に含まないものである。

(Ii) an oligomer of (i), or (iii) a mixture of (i) and (ii),
Here, Z is —N (R) (CH ₂ OR ¹ ), an aryl group having 6 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an acyl group,
Each R is independently hydrogen or —CH ₂ OR ¹ ;
Each R ¹ is independently hydrogen or an alkyl group having 1 to 12 carbon atoms, provided that at least one R is hydrogen or —CH ₂ OH and at least one R ¹ is an alkyl group, The vulcanizable rubber composition is substantially free of methylene acceptor co-reactant.

These adhesive resins in which at least one R is hydrogen and / or at least one R ¹ is a lower alkyl group having 6 to 10 carbon atoms are particularly useful, especially when the resin is melamine, benzoguanamine, cyclohexylguanamine or aceto Useful when it is guanamine or oligomers thereof.

One particularly useful alkylated triazine adhesive resin of the above formula is that where Z is —N (R) (CH ₂ OR ¹ ).

  Other methods of removing resorcinol in the adhesive resin for rubber compositions are also useful and are at least one of N-substituted oxymethylmelamine and α- or β-naphthol. This adhesive resin employs monohydric phenol, α- or β-naphthol as a methylene acceptor in resin formation during vulcanization without resorcinol.

  Other adhesive resins useful in the rubber compositions described herein include special latexes, such as a copolymer of about 70% butadiene, about 15% styrene and about 15% 2-vinylpyridine. Vinyl-pyridine latex (VP latex), acrylonitrile rubber latex, and styrene-butadiene rubber latex are included. These can be used as such or in combination with others. Here, other adhesive resins particularly useful for polyethylene are those applied in a multi-stage process, such as blocked isocyanates applied in combination with polyepoxides, followed by conventional resorcinol-formaldehyde resins ( RFL dip). Additional useful adhesive resins include combinations of RFL dip and other adhesion promoters such as triallyl cyanurate, resorcinol and formaldehyde, or reaction products of p-chlorophenol, resorcinol and formaldehyde. Yes.

  Adhesive resins suitable for use in the rubber and adhesion promoters described herein include polyurethane resins, epoxy resins, phenol aldehyde resins, polyhydroxyl phenols, aldehyde resins, phenol furfural resins, xylene aldehyde resins, urea formaldehyde resins. , Melamine formaldehyde resin, alkyd resin, polyester resin and the like.

  Typically, in this adhesion promoter system, at least one ester compound according to Formulas I-IV and the adhesive resin are in a weight ratio of about 10 parts ester (i.e., ester) to about 1 part adhesive resin. A ratio of about 10: 1 of each resin) and about 1 part ester to about 10 parts resin by weight (ie, an ester: resin ratio of about 1:10 each). . More preferably, the ester is combined between the adhesive resin, about 4 parts ester to about 1 part adhesive resin by weight, and about 1 part ester to about 4 parts resin. Most preferably, the ratio of ester to adhesive resin in the adhesion promotion system of the present invention is about 1: 1.

  Also, the adhesion promoter described herein may comprise from about 0.1% to about 15% of one or more reactive diluents, based on the total weight of the adhesive resin and ester compound in the composition. May be included in quantity. Reactive diluents for achieving sufficient advantages of the adhesion promoters described herein are (1) glycidyl ethers, (2) diglycidyl ethers, (3) aliphatic linear epoxides, (4 Epoxidized vegetable oils, in particular epoxidized soybean oil, (5) alicyclic epoxides, (6) glycidyl esters, (7) diglycidyl esters.

  These reactive diluents function as solvents to solubilize the rubbers, adhesive resins, and long chain ester compounds described herein, and chemically in the adhesion of the rubber compositions described herein to substrates. Believed to be involved.

  Early work on long chain esters relates to testing of esters in industrial rubber belts containing polyester cords for automotive driveline systems. An important part of the construction of automotive belts is the adhesion of rubber to polyester cord. Polyester cords are used to give the belt strength and life. The polymer selected for the automotive belt is an ethylene / propylene / diene polymer (EPDM). While this polymer is excellent for end use, one of its disadvantages is its low adhesion to many substrates such as polyester cords. The rubber company does not spare any effort to ensure proper adhesion between the EPDM and the polyester cord. At present, they have a resorcinol-formaldehyde resin coating and use a treated cord in which the resin-coated cord is then dipped in an adhesive. The resin treated and adhesive coated cord is then adhered to EPDM during the vulcanization process. This is an expensive process that takes time to achieve rubber-polyester cord adhesion. The adhesion promotion system of the present invention advantageously improves the adhesion of polyester cord to EPDM.

  Other examples of substrates intended for use in the compositions and methods of the present invention include metallic and polymeric layers, films, sheets, fibers, yarns and / or textiles, polyesters and aramid fibers. . Metals used in the present invention include steel, brass coated steel, brass, aluminum, and copper. Adhesion to the glass substrate is also improved. The application of the adhesion promoter of the present invention is particularly directed to steel cords, brass coated steel cords, brass cords, polyester fiber cords, aramid fiber cords, glass cords, fibers and planar metal surfaces. The polymer “cords” or “cords” in this application are intended to include reinforcing elements used in rubber products, and include fibers, continuous fibers, staples, hemp, yarn, fabrics, etc., especially for trucks A cord for use in a structure of a tire dismantle such as a tire.

  The polymeric reinforcing element or cord has a plurality of substantially continuous fibers or single fibers, and is a reinforcing element for glass compositions, polyesters, polyamides, and polymeric rubbers and fibers well known in the art Alternatively, many other materials used to make cord fibers are included. One preferred glass is known as E-glass and "Mechanics of Pneumatic Tires," Clark, National Bureau of Standards Monograph 122, US Dept. of Commerce, November 1971, pages 241-243, 290 and 291. Page). Many yarns or fibers employed in fiber reinforcement elements or cords can vary considerably depending on the end use or service requirements. Similarly, many of the yarns of fibers used to make many reinforcing elements or cords can vary widely. In general, the number of long fibers in a reinforcing element or cord for a customer's tire can vary from about 500 to 3000 and the number of yarns in the reinforcing element can vary from 1 to 10. Preferably, the number of yarns is 1 to 7, and the total number of long fibers is about 2000. A typical example in the glass tire cord industry is known as G-75 (or G-75, 5/0) and has 5 threads per 408 glass fibers. Another typical cord known as G-15 has a single thread containing 2040 glass fibers.

  The adhesion promoters of the present invention can be used in many applications, including adhesion of steel braid hose and engine mount metal hoses to natural and / or synthetic rubber materials.

  The term “vulcanized” as used herein refers to the introduction of a three-dimensional cross-linked structure between rubber molecules. Therefore, in addition to the most common and important sulfur vulcanization, thiuram vulcanization, peroxide vulcanization, quinoid vulcanization, resin vulcanization, metal salt vulcanization, metal oxide vulcanization, polyamine vulcanization, radiation vulcanization , Hexamethylenetetramine vulcanization, urethane cross-linking vulcanization and the like.

  The rubber useful in the compositions described herein can be natural rubber (NR) and / or synthetic rubber. Synthetic rubbers include homopolymers of conjugated diene compounds, such as isoprene, butadiene, chloroprene, etc., such as polyisoprene rubber (IR), polybutadiene rubber (BR), polychloroprene rubber, styrene, acrylonitrile, vinyl pyridine, acrylic acid, etc. Copolymers of the above conjugated diene compounds with vinyl compounds such as methacrylic acid, alkyl acrylates, alkyl methacrylates, such as styrene-butadiene copolymer rubber (SBR), vinylpyridine-butadiene-styrene copolymer rubber, acrylonitrile-butadiene copolymer rubber , Acrylic acid-butadiene copolymer rubber, methacrylic acid-butadiene copolymer rubber, methyl acrylate-butadiene copolymer rubber, methyl methacrylate-butadiene copolymer Mer rubber, acrylonitrile-butadiene-styrene terpolymer, etc., for example, copolymers of ethylene, propylene, isobutylene and other olefins with dienes, such as ethylene-propylene-cyclopentadiene terpolymer, ethylene-propylene-5-ethylidene-2- Norbornene terpolymers and ethylene-propylene-1,4-hexadiene terpolymers, polyalkenamers obtained by ring-opening polymerization of cycloolefins, such as polypentenamers, rubbers obtained by ring-opening polymerization of oxirane rings, such as polyepichlorohydrin rubber And polypropylene oxide rubber, silicon rubber and the like that can be vulcanized with sulfur. Further, halides of the above various rubbers such as chlorinated isobutylene-isoprene copolymer rubber (CI-IIR), brominated isobutylene-isoprene copolymer rubber (Br-IIR), and fluorinated polyethylene are included.

  In particular, the compositions described herein include natural rubber (NR) as well as synthetic rubber, ie styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), polyisoprene rubber (IR), isobutylene-isoprene copolymer rubber, these It is characterized in that high adhesion is imparted to a surface having poor adhesion of vulcanized rubber of a copolymer of a rubber halide (Cl-IIR, Br-IIR) and a non-conjugated diene of an olefin. Of course, the present invention is applicable to other rubbers. All these rubbers contain compounding agents commonly used in rubber compounding, such as fillers such as carbon black, silica, calcium carbonate lignin, softeners such as mineral oil, vegetable oil, etc. before vulcanization. Mixed and then vulcanized.

Vulcanized rubber whose surface has been treated with the adhesion promotion system described herein can be easily bonded to other materials with adhesive resins, especially for metal and polymer, especially cord shapes. To vulcanize the rubber composition, a vulcanizing agent such as sulfur or peroxide vulcanizing agent is dispersed in the composition. Vulcanizing agents are used in amounts ranging from 0.5 to 6.0%, with 1.0 to 4.0% being preferred, based on the weight of natural and / or synthetic rubber in the composition. Representative examples of sulfur vulcanizing agents include elemental sulfur (S ₈ ), amine disulfides, polymeric polysulfides, sulfur-olefin adducts. A preferred sulfur vulcanizing agent is elemental sulfur.

  Other suitable vulcanizing agents include thiurams, quinoids, metal salts, metal oxides, polyamines, vulcanization, radiation, hexamethylenetetramine, urethane crosslinkers and the like. Typical examples of peroxide vulcanizing agents include dibenzoyl peroxide and di (tert-butyl) peroxide.

  Carbon black used in rubber compounding applications that are usually employed can be used as carbon black in the present invention. Typical examples of such carbon black include N110, N121, N220, N231, N234, N242, N293, N299, S315, N326, N330, M332, N339, N343, N347, N351, N358 and N375. It is. The rubber composition described herein can be compounded by a method generally known in the field of rubber compounding. For example, various sulfur vulcanizable or peroxide vulcanizable component rubbers can be variously formulated. Commonly used additives such as sulfur donors, vulcanization aids such as activators and inhibitors, oils, resins including adhesive resins and plasticizers, fillers, pigments, fatty acids, zinc oxide, waxes, Mixed with antioxidants and antiozonants, inhibitors, and processing additives such as peptizers. As known to those skilled in the art, the above additives are selected and commonly used in conventional amounts in conventional tire tread applications. Typical amounts of adhesive resin include about 0.2 to about 10%, usually 1 to 5%, based on the weight of the natural or synthetic rubber.

  Typical amounts of zinc oxide include about 2% to about 5%. Typical amounts of wax include from about 1% to about 5%, based on the weight of natural or synthetic rubber. Often microcrystalline waxes are used. A typical amount of inhibitor is 0.05 to 2%. The amount of peptizer comprises about 0.1 to 1%. Typical peptizers are, for example, pentachlorothiophenol and dibenzamide diphenyl disulfide. All additive percentages are based on the weight of the natural or synthetic rubber.

  Accelerators can be used to control the time and / or temperature required for vulcanization and to improve the properties of the vulcanizate. Vulcanizing agents may be used in a total weight of about 0.5 to about 4%, preferably about 0.8 to about 1.5%, based on the weight of the natural or synthetic rubber. Suitable types of accelerators that can be used are amines, disulfides, guanidines, thiazoles, thiurams, sulfenamides, dithiocarbamic acids and xanthates. If included in the rubber composition, the primary accelerator is preferably sulfenamide. If a second accelerator is used, it is preferred that the second accelerator is guanidine or thiuram. When an adhesion promoter system comprising a long chain ester and an adhesive resin is used as a wire coat or bead coat, i.e., a tire, a typical adhesion promoter system does not contain an organocobalt compound and It can be used by replacing all or a part with one that functions as a wire adhesion promoter. When used in part, known organocobalt compounds can be included to promote adhesion of rubber to metal in the field. Accordingly, suitable organocobalt compounds that can be employed in combination with the non-organocobalt adhesion promotion systems containing long chain esters described herein include fatty acid cobalt salts such as stearic acid, palmitic acid, oleic acid, linoleic acid, carbon Cobalt salts of aliphatic or cycloaliphatic carboxylic acids having 6 to 30 atoms, cobalt chloride, cobalt naphthenate, carboxylated cobalt, and commercially from the Shepherd Chemical Company (Cincirmati, Ohio) under the name “Comend A” Available organic-cobalt-boron complexes are included.

  Comend A is believed to have the following structure:

ここで、各Ｒは、同じ又は異なっており、炭素原子９から１２個を有するアルキル基であり、Ｂは、Ｃ₄〜Ｃ₂₄の直鎖又は分岐の飽和又は不飽和の炭化水素鎖である。

Here, each R is the same or different and is an alkyl group having 9 to 12 carbon atoms, and B is a C _{4 to} C ₂₄ linear or branched saturated or unsaturated hydrocarbon chain. .

  The amount of organocobalt compound that can be employed depends on the particular nature of the selected organocobalt compound, particularly the amount of cobalt metal present in the compound. Since the amount of cobalt metal varies considerably in the cobalt metal suitable for use, it is appropriate and convenient to base the amount of organic cobalt compound utilized on the amount of cobalt metal desired in the final compound. Thus, if an organocobalt compound is included in the rubber composition, the amount of organocobalt compound present in the stock composition is about 0. 0 by weight of organocobalt metal based on the total weight of rubber in the composition. Should be provided from 01% to about 0.35% and provided from about 0.03% to about 0.2% by weight of the organocobalt metal, based on the total weight of rubber in the composition. Is preferred.

  The adhesion promoters described herein are particularly effective in compositions where the rubber is both natural or synthetic cis-polyisoprene and in mixtures containing at least 25% by weight of cis-polyisoprene with other rubbers. When mixed, it is preferred to contain cis-polyisoprene at least 40% by weight, more preferably 60% by weight. Examples of other rubbers that can be mixed with cis-polyisoprene include poly-1,3-butadiene, copolymers of 1,3-butadiene and other monomers such as styrene, acrylonitrile, isobutylene and methyl methacrylate, ethylene / propylene / diene Terpolymers and halogen-containing rubbers such as chlorobutyl, bromobutyl and chloroprene rubbers.

  The amount of sulfur in the composition is typically 2 to 8 parts, for example 3 to 6 based on 100 parts by weight of rubber, but less or more, for example 1 to 7 or 8 on the same basis. Part.

  Additional examples of vulcanization accelerators that can be used in the rubbers described herein are thiazole-based accelerators such as 2-mercaptobenzothiazole, bis (2-benzothiazolyl) disulfide, 2- (2 ′, 4′-dinitrophenyl-thio) benzothiazole, benzothiazole-2-sulfenamides such as N-isopropylbenzothiazole-2-sulfenamide, N-tert-butyl-benzothiazole-2-sulfenamide, N-cyclohexylbenzo-thiazole-2-sulfenamide, and 2- (morpholinothio) benzothiazole, and thiocarbamylsulfenamides such as N, N-dimethyl-N ′, N′-dicyclohexylthiocarbamoyl- Sulfenamide and N- (morpholinothiocarbonyl Thio) -morpholine. Accelerators can be used alone or as a mixture. In the compositions described here, these vulcanization accelerators are usually used in an amount of 0.3 to 2 parts, for example 0.3 to 1.5 parts per 100 parts by weight of rubber, preferably It is used at 0.4 to 1.0 part, more preferably 0.5 to 0.8 part.

  The adhesion promoter described herein promotes the bond between rubber and brass, for example, between rubber and brass coated steel. Typical brass contains 60-70% by weight, especially 63-68% by weight of copper component, the optimal percentage depending on the specific conditions under which the bond is formed. The brass coat on the brass coat steel is preferably, for example, 0.05 to 1 micrometer, preferably 0.07 to 0.7 micrometers, for example 0.15 to 0.4 micrometers.

  The long chain ester additive / resin combination described herein (i.e., adhesion promoter system) is particularly useful for bonding rubber to steel cords where conventional adhesion pretreatment is not very effective. The rubber also effectively adheres to alloys including copper and zinc and one or more small amounts of other metals such as cobalt, nickel or iron.

  Cobalt compounds are used as adhesion promoters for adhesion of rubber to zinc, such as adhesion of rubber to zinc-coated steel cords (which are widely used in the manufacture of conveyor belts). Examples of such compounds are cobalt naphthalene and the cobalt-boron complex described in GB 2,022,089A.

  Vulcanization of the rubber composition described herein is carried out at normal temperatures ranging from about 100 ° C to 200 ° C. Preferably, the vulcanization is performed in the range of about 110 ° C to 180 ° C. Any of the usual vulcanization processes such as heating by pressing or stamping, superheated steam or hot air by heating with a salt bath can be used.

  If the rubber composition is vulcanized at a temperature of 100 ° C. to 200 ° C., the rubber composition can be used for various purposes. For example, vulcanized rubber compositions can be used in the form of tires, belts, hoses, engine mounts, gaskets, and air springs. Speaking of tires, it can be used for various tire components. Such tires can be constructed, shaped, extruded and cured by various methods known and well known to those skilled in the art. When rubber compositions are used in tires, they are used for wire coats, bead coats, threads, tops, sidewalls and combinations thereof. As can be seen from the above, the tire may be a customer tire, an aircraft tire, a truck tire or the like. A preferred tire is a customer tire. Also, the tire can be radial or biased, but radial is preferred.

  The invention is better understood by reference to the following examples, unless otherwise indicated, parts and percentages are by weight.

  In the first part of this project, compounds are mixed with conventional EPDM formulations and tested for adhesion.

メラミン−ホルムアルデヒド樹脂は、タイヤ工業の分野で接着促進剤として知られている。ゴム−コード間の接着に対するニーズは、上述のように、一般的にメチレンドナー／アクセプター樹脂システムの存在を必要とする。典型的なシステムは、ドナーとしてのヘキサキスメトキシメチルメラミン(HMMM)と、アクセプターとしての（レゾルシノールのような）ノボラック樹脂とからなる。

Melamine-formaldehyde resins are known as adhesion promoters in the tire industry. The need for rubber-cord adhesion generally requires the presence of a methylene donor / acceptor resin system, as described above. A typical system consists of hexakismethoxymethylmelamine (HMMM) as a donor and a novolac resin (such as resorcinol) as an acceptor.

Results The table below shows the results of adhesion to polyester cords in Examples 1-5.

対照（実施例３）は、メラミンホルムアルデヒド樹脂及びLord Corporation (Cary, North Carolina)から購入した接着剤で前処理したポリエステルコードを有するＥＰＤＭである。実施例１，２４及び５で使用したポリエステルコードは、メラミンホルムアルデヒド樹脂で処理したが接着剤では処理していない。実施例１及び２は、単にメラミンホルムアルデヒド樹脂を含み、対照コンパウンドと基本的に等しい接着力を与え、これは、使用あれているコードが接着剤でコートされていないので有意義である。実施例４及び５は、樹脂とここに記載したエステルとの組み合わせを含み、予期しない接着性の増大を示している。実施例４及び５に対する接着力は、対照及び樹脂のみの実施例（３〜５）に比較して、少なくとも１００％の増大である。

The control (Example 3) is an EPDM with a polyester cord pretreated with melamine formaldehyde resin and an adhesive purchased from Lord Corporation (Cary, North Carolina). The polyester cords used in Examples 1, 24 and 5 were treated with melamine formaldehyde resin but not with an adhesive. Examples 1 and 2 simply contain melamine formaldehyde resin and give essentially the same adhesion as the control compound, which is significant because the cords used are not coated with adhesive. Examples 4 and 5 contain a combination of resin and the esters described herein and show an unexpected increase in adhesion. The adhesion to Examples 4 and 5 is at least 100% increase compared to the control and resin-only examples (3-5).

  These results show that the resin / ester combination results in a significant increase in adhesion between EPDM and polyester cord compared to the control compound and the compound containing resin only.

  Prescription and collected data for Examples 1-5 are shown in Table I.

接着促進剤
第２部
ＥＰＤＭゴムのポリエステルコードへの改善された接着性を示した第１部の結果に基づいて、樹脂／エステルの組み合わせを、金属コード接着に使用される標準の天然ゴムコンパウンドにおいて評価した。

Adhesion promoter Part 2 Based on the results of Part 1 showing improved adhesion of EPDM rubber to polyester cords, resin / ester combinations can be used in standard natural rubber compounds used for metal cord bonding. evaluated.

  The compounds tested in this study varied the ester content with a constant resin content. Table II below shows the initial, air oven degradation and humidification degradation adhesion results, and in Examples 6-12, the weight parts of resin and ester are shown in parentheses.

初期のワイヤコードの接着の結果は、樹脂／エステルの組み合わせを含む処方より僅かに高い接着性を有する標準的な処方を示している。樹脂／エステルの組み合わせを含む処方は、樹脂／エステルの８／４の組み合わせを除いて全てよく似た結果となっている。現時点では、この処方が低い初期接着性を有する理由は分かっていない。

The initial wire cord adhesion results show a standard formulation with slightly higher adhesion than the formulation containing the resin / ester combination. Formulations containing resin / ester combinations all gave very similar results except for the 8/4 resin / ester combination. At present, it is not known why this formulation has low initial adhesion.

  The result of humidification degradation is interesting in that Examples 9, 11 and 12 have the highest level of force and the lowest rate of change from the beginning. This formulation has the highest recorded force and the least change from the initial adhesion. This indicates that increasing the amount of curing agent, along with the resin / ester combination, improves post-degradation adhesion. Except for Example 8 (Resin 8 / Ester 8), all resin / ester compounds showed less change in force recorded than the standard compound.

  The formulations for Examples 6-12 are shown in Table III.

イオウ加硫天然ゴム処方における樹脂／エステルの組み合わせの使用は、標準の天然ゴム処方に比較して、加熱劣化及び加湿劣化後のワイヤコードの接着性を改善することができる。

The use of a resin / ester combination in a sulfur vulcanized natural rubber formulation can improve the adhesion of the wire cord after heat and humidity degradation as compared to a standard natural rubber formulation.

  To demonstrate that the improved cure system of Example 12 was not only involved in increasing the adhesion performance of Example 12, an additional formulation, Example 13, was tested. The difference between Examples 6 and 13 is that Example 13 contains a 50% increase in cure system additives (sulfur and Vulkacit). Table IV provides comparative data showing that an increase in the curing system of the “control compound” (ie, the prior art formulation of Example 6) does not lead to an adhesive effect. Thus, these data confirm that the increase in adhesion in Example 12 is not simply due to an increase in the additive of the curing system, i.e., this increase is due to an adhesion promoter.

接着促進剤
第３部
次に、天然ゴム−金属間結合が、ここに記載した添加されているエステルの効果を決定するために評価された。これは、エンジンマウント、ブレーキ、ホースなどの自動車部品に対して大きな潜在能力を示している。

Adhesion Promoter Part 3 The natural rubber-metal bond was then evaluated to determine the effect of the added ester described herein. This shows great potential for automotive parts such as engine mounts, brakes and hoses.

  Initial considerations focused on long chain esters in natural rubber and their effect on metal adhesion (Table V-Examples 14-17). The data shows that the adhesion promoters described herein improve adhesion to brass in sulfur-vulcanized formulations. The use of the resin / ester combination did not improve adhesion to the ester only compound.

テーブルＶ−実施例１４〜１７ＶＩは、イオウ加硫システムが樹脂のみを含有する処方（実施例１８）、本開示の長鎖エステルと組み合わされた場合（実施例２０）及び樹脂もエステルのない場合（実施例１９）に使用された場合のデータを与えている。これらのデータから、長鎖エステルと接着樹脂とを含む接着促進システムは、対照の処方及び樹脂を含み本開示のエステルを含まない処方と比較したとき、最良であり、優れた接着性の結果を与えることを示している。

Table V—Examples 14-17VI show formulations where the sulfur vulcanization system contains resin only (Example 18), when combined with the long chain ester of the present disclosure (Example 20), and when the resin is also ester-free. Data when used in Example 19 is given. From these data, an adhesion promoting system comprising a long chain ester and an adhesive resin is the best when compared to a control formulation and a formulation containing the resin and no ester of the present disclosure, with excellent adhesion results. It shows giving.

次に、ここに記載した長鎖エステルの効果をゴム−金属結合のためのＥＰＤＭゴム処方において評価した。また、この加硫システムは、イオウシステムに対する過酸化物の効果を決定するために評価した。このイオウ処方は機能せず、従って、これらの処方は採用されない。過酸化物加硫処方は、エステル単独と樹脂／エステルの組み合わせの使用により変化させた。テーブルVIIの下のデータ（実施例２１〜２３）は、ＥＰＤＭにおける真鍮、アルミニウム及びスティールコードについての接着性の結果をリストしている。

The effects of the long chain esters described herein were then evaluated in an EPDM rubber formulation for rubber-metal bonding. This vulcanization system was also evaluated to determine the effect of peroxide on the sulfur system. This sulfur formulation does not work and therefore these formulations are not employed. The peroxide vulcanization formulation was varied by the use of an ester alone and a resin / ester combination. Data below Table VII (Examples 21-23) lists adhesion results for brass, aluminum and steel cord in EPDM.

樹脂／エステルを含んだ処方は、エステルだけの処方と対照より著しく大きな接着性を有している。スティールの接着性の結果は、エステルを有する処方は幾分かの接着性を与えるが、樹脂／エステルの組み合わせが予想外に良好である。対照の処方はスティールへの接着性は有していない。何れの処方もアルミニウムに対する接着性はない。

The resin / ester containing formulation has significantly greater adhesion than the ester only formulation and the control. Steel adhesion results indicate that formulations with esters give some adhesion, but the resin / ester combination is unexpectedly good. The control formulation has no adhesion to steel. None of the formulations is adhesive to aluminum.

  Prescription data for Examples 21-23 are shown in Table VIII.

表ＩＸは、テーブルVIIIのデータを補足する比較データを提供している。実施例２４は樹脂を含むが、ここに記載した長鎖エステルは含んでいない。テーブルＩＸのデータから明らかなように、実施例２４はＥＰＤＭと金属基材との間の接着を促進することはない。

Table IX provides comparative data that supplements the data in Table VIII. Example 24 includes a resin but does not include the long chain ester described herein. As is apparent from the data in Table IX, Example 24 does not promote adhesion between the EPDM and the metal substrate.

  Table IX also contains the recipe for changing the ester. A standard ester according to the present disclosure, UBS O20602, is used in the formulation of Examples 25 and 26. In Example 25, the saturated ester additive is not combined with the adhesive resin disclosed herein and does not promote adhesion between the EPDM and the metal substrate. However, in Example 26, the saturated ester is combined with the adhesive resin to provide excellent adhesion between the metal substrate and EPDM, more specifically between steel and EPDM.

ＥＰＤＭゴムの金属への結合
更なるエステルが、接着樹脂と組み合わされたときのそれらの効果を決定するために評価された。評価されたエステルは、以下のとおりである。

Additional esters of EPDM rubber to metal were evaluated to determine their effect when combined with an adhesive resin. Estimated esters are as follows.

Plasthall DOS-saturated diester based on 2-ethylhexyl alcohol and sebacic acid
RX-13577… Unsaturated monoester based on tridecyl alcohol and tall oil fatty acid
RX-13824: Unsaturated dimerate ester based on tridecyl alcohol and C ₃₆ dimer acid. This ester is similar to RX-13804 using the same dimer acid, but RX-13804 reacts with 2-ethylhexyl alcohol (di-2-ethylhexyl dimerate).

  The results show that the compound with DOS / resin provides good adhesion to brass and steel. RX-13577 / resin compound has good adhesion to brass and steel, and the force value against steel is higher than any of the ester / resin combinations. This data indicates that the higher level of unsaturation provides greater adhesion because RX-13577 has more unsaturated sites by weight than RX-13804 and RX-13824. Yes. Some of the other data that helps support the above is steel adhesion data for ester-only compounds. The RX-13577 compound had only one measurable adhesion, whereas DOS and RX-13824 did not have adhesion values.

  The data is described in Tables 27-27 of Table X.

ポリエステルコードに対する塩素化ポリエチレンゴム
より詳細に、ＲＸ−１３８４５は、コード及び繊維についてゴム接着を評価した。ＲＸ−１３８４５は３６重量％のＲＸ−１３０４と、３６重量％のＣｙｒｅｚ ＣＲＡ−１３８ Ｒｅｓｉｎ（室温で液体）と、２８％の基材（合成カルシウムシリケート）からなる接着システムである。ＲＸ−１３８４５は、予め加熱したＣｙｒｅｚ ＣＲＡ−１３８ Ｒｅｓｉｎの液体を、ミキシングボウルに入れた乾燥したキャリア（基材）に加えることにより調製される。これらの材料は低速で３分間混合される。これらの材料は更に３分間混合される。ＲＸ−１３８４５は、液体を粉体として取り扱われることを可能とする。活性な接着促進剤が遊離し、活性な成分が基材から遊離するので、ＲＸ−１３８４５のゴムコンパウンドへの混和は、接着促進剤があたかもそれがそのままの材料としてゴムに取り入れられているのと同じような方法で機能するのを可能とする。

More specifically, RX-13845 evaluated rubber adhesion on cords and fibers. RX-13845 is an adhesive system consisting of 36% by weight RX-1304, 36% by weight Cyrez CRA-138 Resin (liquid at room temperature) and 28% substrate (synthetic calcium silicate). RX-13845 is prepared by adding a preheated Cyrez CRA-138 Resin liquid to a dry carrier (substrate) in a mixing bowl. These materials are mixed for 3 minutes at low speed. These materials are mixed for an additional 3 minutes. RX-13845 allows the liquid to be handled as a powder. Since the active adhesion promoter is liberated and the active ingredients are liberated from the substrate, the incorporation of RX-13845 into the rubber compound is as if the adhesion promoter is incorporated into the rubber as it is. It makes it possible to function in a similar way.

  The results show a significant improvement in the adhesion of untreated nylon, isocyanate-treated nylon, isocyanate-treated aramid fibers, and untreated polyester fibers to chlorinated polyethylene polymers. The data is described in Examples 34-38 of Table XI.

コード接着性の測定方法
エステルについて、接着樹脂と組み合わされたときのそれらのゴムへのコードの接着の影響を決定するために評価が行われた。以下は、天然及び人工の繊維及び紡績糸を含む強化繊維の種々のゴムコンパウンド及びエラストマーへの接着の相対的なストリップピールを決定するための方法である。この方法は、５００又はそれ以上のデニールの工業的な重量繊維に通常使用されている。最も普通に採用される典型的なエラストマー及びコンパウンドは、天然ゴム、スチレン−ブタジエンゴム、オレフィンの非共役ジエン類とのコポリマー（ＥＰＤＭ）、ポリクロロプレンゴム（ＣＲ）、アクリロニトリル−ブタジエンエラストマー（ＮＢＲ）、クロロスルホネート化ポリエチレンエラストマー（ＣＳＭ）、ポリイソプレンゴム、イソブチレン−イソプレンコポリマーゴム、クロル化イソブチレン−イソプレンコポリマーゴム、臭素化イソブチレン−イソプレンコポリマーゴム、ポリビニルクロライド、ウレタン、及びこれらの混合物であるが、この技術は、広範囲の材料に対する繊維の接着性を測定するために改良され得る。

Method for Measuring Cord Adhesion Esters were evaluated to determine the effect of cord adhesion to their rubber when combined with an adhesive resin. The following is a method for determining the relative strip peel of the adhesion of reinforcing fibers, including natural and artificial fibers and spun yarns, to various rubber compounds and elastomers. This method is commonly used for industrial heavy fibers of 500 or more denier. Typical elastomers and compounds most commonly employed are natural rubber, styrene-butadiene rubber, copolymers of olefins with non-conjugated dienes (EPDM), polychloroprene rubber (CR), acrylonitrile-butadiene elastomer (NBR), Chlorosulfonated polyethylene elastomer (CSM), polyisoprene rubber, isobutylene-isoprene copolymer rubber, chlorinated isobutylene-isoprene copolymer rubber, brominated isobutylene-isoprene copolymer rubber, polyvinyl chloride, urethane, and mixtures thereof. Can be improved to measure fiber adhesion to a wide range of materials.

  The adhesion test described here was performed in accordance with ASTM D4393-85 “Stripping of adhesive cords or fibers to rubber compounds”.

  Typically, 1 inch x 5 inch fiber / rubber composite strips were made for testing. The fiber was placed on a tape backing using a rotatable cylinder. The tape backing was affixed to a rolled elastomer or rubber compound under high temperature and high pressure from a hydraulic press (ie, under vulcanization, extrusion or other conditions) to form a cord or fiber reinforced composite. The composite material was cut into stripes for adhesion measurement (for example, by separation load value, appearance, etc.).

Method Place the ASTM 429 mold in a pressure press (temperature between 250 ° F and 400 ° F, capable of pressing about 125 tons) and cure the vulcanization temperature (curing of the specific rubber compound that uses the temperature. Temperature) of ± 2 ° F. The pressure was maintained for about 30 minutes within that particular temperature range.

  Three strips of 3 inch wide masking tape (a suitable masking tape is # 515 Masking Tape, Anchor Continental, Inc. Columbia, SC) wrapped around a rotatable cylinder with the adhesive side outward It was. The three strips were stacked to provide a tape backing with a total width of about 7 inches. Six 1 inch wide fiber samples were wound on the tape backing. Samples of similar or different yarns can be wound on each tape backing. However, each fiber or cord should be wrapped so that there are no fiber overlaps and no gaps between adjacent fibers. Typically, three strips of each fiber were made and tested.

  The fibers were secured with 1 inch wide masking tape and the strips were marked A, B, C, D, E and F. Six wound samples were removed from the cylinder by cutting across the cylinder.

  A 5 inch x 7 inch unvulcanized compound rubber to be tested was cut to a specific thickness (0.250 ± 0.20 inch). The surface of the mold that would contact the fiber assembly was cleaned with n-pentane.

  The preheated mold was removed from the press. The fiber sample was placed on the bottom of the mold plate with the masking tape backing side down and the fibers facing up. A 1 inch by 7 inch aluminum foil is placed on the back edge of the fiber sample so that the fiber is perpendicular to the aluminum foil and its length covers an aluminum foil strip. Each strip is in a specific position on the press. The cleaned 5 inch x 7 inch unvulcanized rubber plate is then placed on top of the fiber assembly. A preheated top mold plate is placed on top of the sample to form a sandwich for the top plate, rubber compound, aluminum foil, yarn sample, tape, and bottom plate. The sandwich is then placed in a preheated pressure press and a pressure of about 125 tons is applied. The pressure and temperature are maintained for a predetermined time (vulcanization time).

  After the vulcanization time has elapsed, the mold assembly is removed from the press. It is important not to disturb the fiber composite while separating the pad from the mold plate. Typically, the pad is placed in cold water to speed up the cooling process. The pad is cooled to room temperature before marking the pad for verification.

  The adhesive pad is laid for an extended period (preparation period), ie overnight, and cut into 1 inch by 5 inch strips for adhesion testing. As much aluminum foil strip as possible was removed to provide an initiating separation between the fiber sample and the rubber compound. If it is very difficult to remove, the foil may be left intact. After conditioning, each 5 inch x 7 inch rubber cut is cut into a 1 inch x 5 inch strip with only one fiber to be tested.

  Each 1 inch by 5 inch adhesive composite was tested using an Instron 4201 stretcher / compressor (Instron Corporation, Canton, Mass.) According to the 08 method of the Instron Series IX Materials Testing® software.

ここに記載したその組成物、方法及び物品の重要な特徴に従えば、一又はそれ以上の長鎖エステルのメラミン−又はフェノール−含有接着樹脂と結合させた組み合わせ（この組み合わせは「接着促進剤」又は「接着促進剤システム」と称される）は、（１）両方の成分を一又はそれ以上の可溶性有機溶剤に溶解させることにより、又は（２）エステル及び樹脂成分を一又はそれ以上の乳化剤を用いて水にエマルジョン化することにより、エステル／樹脂接着促進剤の液状の提供により液体で使用され得る。水ベースのエマルジョンは、エマルジョン中の最良の分散のためには、ＨＬＢ値約４から約５の値を有しているべきである。液状の形状では、接着促進剤は多くの利点を有し、特に、エラストマーの基材への接着のための液状エステル／樹脂接着促進剤を用いることにより、エラストマーの組成を変更することなく、金属又は高分子基材などの基材をコートする能力を備えている。他の利点として、（１）比較的高濃度、例えば５０〜９０重量％の接着促進剤を含み、エラストマー組成物への添加又は基材へのコーティングに際して希釈され得る接着促進剤の濃縮されたマスターバッチを調製する能力；（２）液状接着促進剤の長鎖エステル部分の合成の間、液状接着促進剤の樹脂成分を溶解させるための溶媒として、過剰なアルコール即ち２−エチルヘキサノールを含み得ること、がある。エステルの合成の間に過剰なアルコールを使用することは、過剰なアルコールによってその反応がより早く進むため、エステル合成において特に有利である。過剰のアルコールが樹脂を安定化させるのに有用であるので、過剰なアルコールは、多くを除去することなく合成されたエステルに残しても良く、又はエステル濃縮又は精製ステップで過剰なアルコールの多く又は幾分かが残っても良い。

In accordance with important features of the compositions, methods and articles described herein, a combination of one or more long chain ester melamine- or phenol-containing adhesive resins (this combination is an “adhesion promoter”) Or referred to as an “adhesion promoter system”) (1) by dissolving both components in one or more soluble organic solvents, or (2) one and more emulsifiers in the ester and resin components Can be used in liquids by providing a liquid form of an ester / resin adhesion promoter by emulsifying in water. The water based emulsion should have an HLB value of about 4 to about 5 for best dispersion in the emulsion. In liquid form, adhesion promoters have many advantages, especially by using liquid ester / resin adhesion promoters for adhesion of elastomers to substrates without changing the composition of the elastomer. Alternatively, it has the ability to coat a substrate such as a polymer substrate. Other advantages include: (1) a concentrated master of adhesion promoter that includes a relatively high concentration, eg, 50-90% by weight, of an adhesion promoter and can be diluted upon addition to an elastomeric composition or coating to a substrate. Ability to prepare batches; (2) During the synthesis of the long chain ester portion of the liquid adhesion promoter, may contain excess alcohol, ie 2-ethylhexanol, as a solvent to dissolve the resin component of the liquid adhesion promoter. There is. The use of excess alcohol during ester synthesis is particularly advantageous in ester synthesis because the reaction proceeds faster due to excess alcohol. Since excess alcohol is useful to stabilize the resin, excess alcohol may be left in the synthesized ester without removing much, or much of the excess alcohol in the ester concentration or purification step or Some may be left.

  Liquid adhesion promoters are substrates such as organic liquids or fibers such as metals, polymer layers, films, or textiles, whether or not emulsified and solubilized in water-based emulsions. It can be added to an elastomeric composition for adhesion to, or used to pre-treat such as a metal or a substrate such as a polymer layer, film, or textile substrate. In other embodiments, a substrate such as a polymer sheet, film, fiber, yarn and / or fiber, such as nylon, glass, aramid, polyester, etc. is bonded to the adhesion promoter system ( It may be pretreated with a resin component (known in the art as “isocyanate pretreatment”). The resin treated substrate can then be treated with the ester component of an adhesion promoter system for improved adhesion of the elastomer to the substrate. The resin-treated substrate is ester-treated by any method, preferably by dipping or coating the resin-treated substrate with an organic solution of ester or a water-based emulsion containing the ester. obtain. Alternatively, an ester can be added to the elastomer so that it contacts and adheres to the resin treated substrate, or a combination of ester and resin (adhesion promoter system) can be applied as a coating, in this case contacting the elastomer It is preferable to dry in advance. As previously disclosed, the adhesion promoter system can be added directly to the elastomeric composition.

  Versions of the organic solutions (RX-13928, hereinafter referred to as “solutions”) and water-based emulsions (RX-13937, hereinafter referred to as “emulsions”) of the liquid adhesion promoter disclosed herein have been tested against various elastomers. It was done. The organic solution version is tested by (1) adding the organic solution directly to the elastomeric composition and (2) pretreating the substrate with the ester / resin adhesion promoter composition. The water-based emulsion was only tested by pretreating the substrate prior to elastomer adhesion. The data is shown in the following tables XIII to XV. In Tables XIII to XV below, substrates pretreated with a liquid adhesion promoter composition (either organic solution or water-based emulsion) were oven dried at 65 ° C. for 30 hours before applying the elastomer. .

以下のテーブルXVIは、接着促進剤の液状溶液におけるエステル及び樹脂の両方を溶解し得る溶媒の選択において使用するためのメラミン（Ｒｅｓｉｍｅｎｅ３５２０）及びＲＸ−１３８０４（ジ−２−エチルヘキシルダイメレート）の溶媒溶解性の要約である。溶解性は溶媒対ダイメレート／メラミンの１：１混合物のみにおいて決定した。もし両方のサンプルが溶媒に溶解したら、その溶液に、ダイメレート＋溶媒対メラミン＋溶媒の１：１で再び混合した。サンプルは、組成物が１３重量％又はそれより大きい％溶媒レベルである限り、ダイメレートエステル及びメラミンの両方の完全な溶解性を与える。

Table XVI below shows solvent dissolution of melamine (Resimene 3520) and RX-13804 (di-2-ethylhexyl dimerate) for use in selecting a solvent that can dissolve both the ester and resin in a liquid solution of the adhesion promoter. It is a gender summary. Solubility was determined only in a 1: 1 mixture of solvent to dimerate / melamine. If both samples were dissolved in the solvent, the solution was mixed again with 1: 1 of dimerate + solvent to melamine + solvent. The sample gives complete solubility of both dimerate ester and melamine as long as the composition is at 13% by weight or higher% solvent level.

水ベースキャリアにおける接着促進剤のエステル及び／又は樹脂成分を均一に乳化するために、安定なエマルジョンの形成を可能とする適切な乳化／分散剤が使用される。エステル類は非常に低い極性を有し、樹脂類は非常の高い極性を有しているので、もしエステル及び樹脂の両方を水ベースキャリアに乳化するなら、乳化剤の組み合わせが、均一で安定な水へのエマルジョンを提供するのに必要である。水ベースエマルジョンは、最良の乳化のために、約４から約５の親水性／疎水性バランス（ＨＬＢ）を有しているべきである。ダイメレートエステル及び接着樹脂の均一で安定な水ベースエマルジョンを特に効果的に与える乳化剤の組み合わせは、以下のエマルジョン調製ガイドに示すように、アニオン性金属ステアレート、例えばエステルに対してはステアリン酸カリウム、接着樹脂に対してはノニオン性のソルビタンオレエートである。

In order to uniformly emulsify the ester and / or resin component of the adhesion promoter in the water-based carrier, a suitable emulsifying / dispersing agent that enables the formation of a stable emulsion is used. Since esters have very low polarity and resins have very high polarity, if both the ester and resin are emulsified in a water-based carrier, the combination of emulsifiers will result in a uniform and stable water. Necessary to provide an emulsion of The water-based emulsion should have a hydrophilic / hydrophobic balance (HLB) of about 4 to about 5 for best emulsification. The emulsifier combination that provides a particularly stable water-based emulsion of dimerate ester and adhesive resin is particularly effective for anionic metal stearates such as potassium stearate, as shown in the emulsion preparation guide below. It is nonionic sorbitan oleate for adhesive resin.

本発明に従えば、接着樹脂を可溶化するのに使用される有機溶媒に加えて、ここに記載したゴム組成物に一又はそれ以上の反応性の有機溶媒（希釈剤）を添加し、又はその樹脂溶媒の一部若しくは全部を置き換えることは、ゴム組成物の基材への接着性を予期せぬ程度にまで増大させ、ここでの基材は、例えばポリマーコード、金属コード、ポリマー繊維及び金属であり、特にタイヤ、ホース、コンベヤベルト、トランスミッションベルト等のコード強化ゴム製品の製造におけるコードである。

According to the present invention, in addition to the organic solvent used to solubilize the adhesive resin, one or more reactive organic solvents (diluents) are added to the rubber composition described herein, or Replacing part or all of the resin solvent increases the adhesion of the rubber composition to the substrate to an unexpected extent, where the substrate can be, for example, a polymer cord, a metal cord, a polymer fiber, and It is a metal, and in particular, a cord in manufacturing cord reinforced rubber products such as tires, hoses, conveyor belts, transmission belts and the like.

  Examples of reactive diluents include (1) glycidyl ethers, (2) diglycidyl ethers, (3) aliphatic linear epoxides, (4) epoxidized vegetable oils, especially epoxidized soybean oil, (5) Alicyclic epoxides, (6) glycidyl esters, and (7) diglycidyl esters are included.

  (1) Glycidyl ethers generally have the following formula:

ここで、Ｒは、アルキル（メチル，エチル，ブチル，イソブチル，等)，一又はそれ以上のオレフィン性結合を含むアルキル、又はアリール（フェニル，トルイル，ベンジル等)であり、これらは、エピクロロヒドリンのメタノール，エタノール，イソプロパノール，ｎ−ブタノール，１−オクタノール，２−エチルヘキサノール，ｎ−デカノール，イソオクタノール，イソデカノール，オレイルアルコール，ベンジルアルコール，又は他のアルコールとの反応生成物を含み、アルコール類の混合物、例えばｎ−オクチル及びｎ−デシルの混合物も含まれる。

Where R is alkyl (methyl, ethyl, butyl, isobutyl, etc.), alkyl containing one or more olefinic bonds, or aryl (phenyl, toluyl, benzyl, etc.), which is epichlorohydride Contains reaction products of phosphorus with methanol, ethanol, isopropanol, n-butanol, 1-octanol, 2-ethylhexanol, n-decanol, isooctanol, isodecanol, oleyl alcohol, benzyl alcohol, or other alcohols, and alcohols Also included are mixtures of n-octyl and n-decyl.

  Examples include 2-ethylhexyl glycidyl ether, allyl glycidyl ether, dodecyl glycidyl ether, decyl glycidyl ether, iso-butyl glycidyl ether, n-butyl glycidyl ether, naphthyl glycidyl ether, tridecyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl Glycidyl ether, C8-C10 aliphatic glycidyl ether, p-tertiary butylphenyl glycidyl ether, nonylphenyl glycidyl ether, and phenyl glycidyl ether are included.

  (2) Diglycidyl ethers generally have the following formula:

ここで、Ｒは、直鎖又は分岐の脂肪族部分であり、例えば、（ＣＨ₂）_nここでｎは２〜１０、又は−ＣＨ₂−ＣＨ（ＣＨ₃）ＣＨ₂−又は−ＣＨ₂−Ｃ（ＣＨ₃）₂−ＣＨ₂−等である。エピクロロヒドリンのジオール又はジオールの混合物との反応生成物があり、ここでジオール又はジオールは、例えば、エチレングリコール，プロピレングリコール，１，４−ブチレングリコール，１，３−ブチレングリコール，１，６−ヘキサンジオール，２−メチル−１，３−プロパンジオール，２，２−ジメチル−１，３−プロパンジオール，又はこれらの混合物である。Ｒはまた、芳香族部分であり得、グリコールとビスフェノールＡ及びビスフェノールＦのような共通のビスフェノール類との反応生成物であるエポキシ構造を結果として生ずる。

Here, R is a linear or branched aliphatic moiety, for example, (CH ₂ ) _n, where n is 2 to 10, or —CH ₂ —CH (CH ₃ ) CH ₂ — or —CH ₂ —. C (CH ₃ ) ₂ —CH ₂ — and the like. There are reaction products of epichlorohydrin with diols or mixtures of diols, where diols or diols are, for example, ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,6. -Hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, or a mixture thereof. R can also be an aromatic moiety, resulting in an epoxy structure that is the reaction product of glycol and common bisphenols such as bisphenol A and bisphenol F.

  Examples include 1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, Polyethylene glycol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, castor oil triglycidyl ether, propoxylated glycerin triglycidyl ether, and sorbitol polyglycidyl ether are included.

  (3) The aliphatic linear epoxide generally has the following formula:

例示には、以下と同様に、ポリプロピレンオキサイド、ブチレンオキサイドが含まれる。

Examples include polypropylene oxide and butylene oxide as in the following.

（４）エポキシ化大豆油、エポキシ化アマニ油、エポキシ化サフラワーオイル、エポキシ化コーン油、エポキシ化綿実油、エポキシ化菜種油、エポキシ化ピーナッツ油、及びグリセリンのＣ₁₈不飽和エステルのエポキシ化により誘導される他の同様の種類のものである。

(4) induction epoxidized soybean oil, epoxidized linseed oil, epoxidized safflower oil, epoxidized corn oil, epoxidized cottonseed oil, epoxidized rapeseed oil, epoxidized peanut oil, and the epoxidation of C ₁₈ unsaturated esters of glycerol Are of other similar types.

  (5) 1,2-cyclohexene dioxide, 1,2-cyclopentene oxide, 1,2,3,4-diepoxybutene, vinylcyclohexene dioxide, etc., and sold by Shell 0il under the brand name of EPON (R) These products are alicyclic epoxides, exemplified below.

（６）グリシジルエステル類は、一般的に以下の式を有している。

(6) Glycidyl esters generally have the following formula:

ここで、Ｒは、−(ＣＨ₂)_n−ＣＨ₃（ｎ＝１−９）等の直鎖脂肪族であり、又はＣＨ₂ＣＨ(ＣＨ₃)₂ 及び−ＣＨ(ＣＨ₂ＣＨ₃)(ＣＨ₂)₄ＣＨ₃等の分岐脂肪族である。Ｒはまた、一又はそれ以上のオレフィン性の結合を有する直鎖の脂肪族であり得る。Ｒはまた、芳香族、即ち、−フェニル、−トルイルであり得る。これらのグリシジルエステルは、グリシドールとカルボン酸との反応生成物であり、酢酸，プロピオン酸，イソ酪酸，２−エチルヘキサン酸，安息香酸，トルイル酸（種々の異性体あり），オレイン酸，リノール酸，リノレン酸や、カルボン酸の混合物である。

Here, R is a linear aliphatic group such as — (CH ₂ ) _n —CH ₃ (n = 1-9), or CH ₂ CH (CH ₃ ) ₂ and —CH (CH ₂ CH ₃ ) ( It is a branched aliphatic group such as CH ₂ ) ₄ CH ₃ . R may also be a straight chain aliphatic having one or more olefinic bonds. R may also be aromatic, i.e. -phenyl, -toluyl. These glycidyl esters are reaction products of glycidol and carboxylic acid, and are acetic acid, propionic acid, isobutyric acid, 2-ethylhexanoic acid, benzoic acid, toluic acid (with various isomers), oleic acid, linoleic acid , Linolenic acid or a mixture of carboxylic acids.

  Examples include glycidyl neodecanoate, glycidyl acetate, glycidyl butyrate, glycidyl propionate, glycidyl valerate, glycidyl caproate, glycidyl caproate, glycidyl caprate, glycidyl caprylate, glycidyl laurate, and linol Glycidyl esters of acid or linolenic acid are included.

  Diglycidyl esters generally have the following formula:

ここで、Ｒは、直鎖脂肪族−（ＣＨ₂）_n（ｎ＝１〜８）、又は分岐の脂肪族、又は脂肪族／脂環族の混合物、又は一又はそれ以上のオレフィン性結合を有する脂環族である。Ｒはまた、芳香族であり得る。これらのグリシジルエステルは、グリシドールのジカルボン酸との反応生成物であり、ジカルボン酸の例は、マロン酸，グルタル酸，アジピン酸，アゼライン酸，セバシン酸，無水フタル酸，イソフタル酸，テレフタル酸，及び一又はそれ以上のダイマー酸類である。

Where R is a linear aliphatic — (CH ₂ ) _n (n = 1-8), a branched aliphatic, or a mixture of aliphatic / alicyclic, or one or more olefinic bonds. It has alicyclic. R can also be aromatic. These glycidyl esters are the reaction products of glycidol with dicarboxylic acids, examples of which are malonic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and One or more dimer acids.

Claims (48)

Rubber selected from the group consisting of natural rubber, synthetic rubber and combinations thereof;
(1) an adhesive resin in an amount of from about 0.1% to about 15% by weight based on the weight of the rubber in the composition; and (2) a sufficient amount of rubber for vulcanizing the rubber. (3) a reactive diluent in an amount of about 0.5 wt% to about 50 wt%, based on the total weight of the adhesive resin plus the esters of formulas I to IV, (4) formulas I, II, III And water-based emulsions containing IV, IV or a combination of two or more of these esters, in an amount of about 0.1% to about 15% by weight of ester based on the weight of rubber in the composition A vulcanized rubber composition comprising a liquid adhesion promoter selected from the group consisting of:

Here, R ¹ is a C _{3 to} C ₂₄ alkyl radical, which is linear or branched, saturated or unsaturated having 1 to 3 carbon-carbon double bonds, and R ² is C _{3 to} C ₂₄ saturated fatty acid residues, or unsaturated fatty acid residues having 1 to 6 carbon-carbon double bonds,

Here, n = 3 to 24, R ³ and R ⁴ are the same or different, and are a C _{6 to} C ₂₄ alkyl radical having a linear or branched saturated or 1 to 3 carbon-carbon double bond. Is unsaturated and

Where R ⁵ and R ⁷ are the same or different and are C ₃ -C ₂₄ hydrocarbon chains, straight or branched saturated or unsaturated having 1 to 6 carbon-carbon double bonds. Yes,
R ⁶ and R ⁸ are the same or different and are C ₃ -C ₂₄ alkyl radicals, linear or branched saturated or unsaturated having 1 to 3 carbon-carbon double bonds;
R ¹⁰ and R ¹¹ are the same or different and are linear or branched with a C _{3 to} C ₂₄ saturated hydrocarbon chain, or linear or branched with an unsaturated C _{3 to} C ₂₄ hydrocarbon chain. 1 to 6 carbon-carbon double bonds,

Here, R ¹² , R ¹⁴ and R ¹⁸ are the same or different, and are C _{3 to} C ₂₄ hydrocarbon chains having straight-chain or branched saturated or 1 to 6 carbon-carbon double bonds. Unsaturated
R ¹³ , R ¹⁵ and R ¹⁹ are the same or different and are C ₃ -C ₂₄ alkyl radicals, linear or branched saturated or unsaturated having 1 to 3 carbon-carbon double bonds;
R ¹⁶ , R ¹⁷ and R ²⁰ are the same or different and are linear or branched with a C _{3 to} C ₂₄ saturated hydrocarbon chain, or linear with an unsaturated C _{3 to} C ₂₄ hydrocarbon chain, or It is branched and has 1 to 6 carbon-carbon double bonds. The rubber composition of claim 1, wherein the ester is selected from the group consisting of Formulas I, II, III, IV and combinations of two or more of these esters:

Here, R ¹ is a C _{3 to} C ₁₈ alkyl radical, which is a linear or branched saturated or unsaturated group having 1 to 3 carbon-carbon double bonds, and R ² is C _{8 to} C ₁₈ saturated fatty acid residues, or unsaturated fatty acid residues having 1 to 3 carbon-carbon double bonds,

Here, n = 6 to 18, R ³ and R ⁴ are the same or different, and are a C _{6 to} C ₁₈ alkyl radical having a linear or branched saturated or 1 to 3 carbon-carbon double bond. Is unsaturated and

Wherein R ⁵ and R ⁷ are the same or different and are C ₆ -C ₂₄ hydrocarbon chains having straight or branched saturated or 1 to 3 carbon-carbon double bonds,
R ⁶ and R ⁸ are the same or different and are C ₃ -C ₁₈ alkyl radicals, linear or branched saturated or unsaturated having 1 to 3 carbon-carbon double bonds;
R ¹⁰ and R ¹¹ are the same or different and are linear or branched with a C _{3 to} C ₁₈ saturated hydrocarbon chain, or are linear or branched with an unsaturated hydrocarbon chain and are 1 to 3 Having a carbon-carbon double bond,

R ¹² , R ¹⁴ and R ¹⁸ are the same or different and are a C _{8 to} C ₁₈ hydrocarbon chain having straight or branched saturated or 1 to 3 carbon-carbon double bonds;
R ¹³ , R ¹⁵ and R ¹⁹ are the same or different and are C ₆ -C ₁₈ alkyl radicals, linear or branched saturated or unsaturated having 1 to 3 carbon-carbon double bonds;
R ¹⁶ , R ¹⁷ and R ²⁰ are the same or different and are linear or branched with a C _{6 to} C ₁₈ saturated hydrocarbon chain, or linear with an unsaturated C _{6 to} C ₁₈ hydrocarbon chain, or Branched and having 1 to 3 carbon-carbon double bonds,
The reactive diluent includes (1) glycidyl ether, (2) diglycidyl ether, (3) aliphatic linear epoxide, (4) epoxidized vegetable oil, (5) alicyclic epoxy, (6) glycidyl ester, (7) a monomer selected from the group consisting of diglycidyl esters, and any combination thereof, from about 5 wt% to about 40 wt% based on the total weight of the adhesive resin plus the esters of Formulas I-IV A rubber composition present in the composition.   The rubber composition according to claim 1, wherein the adhesive resin is a condensation product of a methylene acceptor and a methylene donor.   4. The rubber composition according to claim 3, wherein the adhesive resin is phenol-formaldehyde, melamine-formaldehyde; naphthol-formaldehyde; polyepoxide; triallyl cyanurate, resorcinol and formaldehyde, p-chlorophenol, resorcinol. And a reaction product of formaldehyde; a rubber composition selected from the group consisting of styrene, butadiene and 2-vinylpyridine; and mixtures thereof.   The rubber composition according to claim 4, wherein the phenol-formaldehyde resin is resorcinol-formaldehyde.   The rubber composition according to claim 1, wherein the adhesive resin is selected from the group consisting of melamine, acetoguanamine, benzoguanamine, cyclohexylguanamine and glycoluril, and oligomers of these monomers, and each unit of the monomer or the oligomer. A rubber composition that is substituted with a vinyl-terminated radical at an average of two or more positions above and does not contain resorcinol.   The rubber composition according to claim 6, wherein at least one of the adhesive resins is further substituted with a radical having a carbamoylmethyl or amidomethyl group at an average of two or more positions. 7. The rubber composition according to claim 6, wherein the adhesive resin is selected from compounds of the following formula and positional isomers thereof:

Here, in each polymerization unit of each monomer and the oligomer, Y is selected from methyl, phenyl, and cyclohexyl, and on average, at least two Rs are —CH ₂ —R ¹ , and any one of the remaining Rs is H and at least 2R ¹ is a radical selected from:
^{_{CH 2 = C (R 2)}} -C (O) -O-,
^{_{CH 2 = C (R 2)}} -C (O) -Z,
^{_{CH 2 = C (R 2)}} -C (O) -NH-, and ^{_{CH 2 = C (R 2)}} -CH 2 -O-,
Where R ² is hydrogen or C ₁ -C ₁₈ alkyl, Z is a radical selected from:
-O- -O-CH ₂ -CH _{2,
-C-CH 2 -CH (CH 3} ) -O-,
—O—CH ₂ —CH ₂ —CH ₂ O—, and —O—CH (C ₂ H ₅ ) —O—, and any remaining R ¹ radicals are selected from:
-O-R ³
—NH—C (O) —OR ⁴ , and —NH—C (O) —R ⁴ , and where R ³ is hydrogen or R ⁴ and R ⁴ is C ₁ -C ₁₈ alkyl, fatty A cyclic, hydroxyalkyl, alkoxyalkyl or aromatic radical, wherein in said oligomer P is from 2 to about 10, L is methylene or the following radicals —CH ₂ —O—CH ₂ —
A rubber composition. The rubber composition according to claim 8, wherein at least one R ^{1 on} average in each monomer or each oligomerized unit of the adhesive resin is
—NH—C (O) —OR ⁴
Wherein R ⁴ is as defined in claim 8. The rubber composition according to claim 9, wherein the adhesive resin is the following compound:

Where P is from 2 to about 10, L is methylene or the radical —CH ₂ —O—CH ₂ —, and R is
At least two R are —CH ₂ —R ¹ , any of the remaining R is H, and at least 2R ¹ is a radical selected from:
^{_{CH 2 = C (R 2)}} -C (O) -O-,
^{_{CH 2 = C (R 2)}} -C (O) -Z,
^{_{CH 2 = C (R 2)}} -C (O) -NH-, and ^{_{CH 2 = C (R 2)}} -CH 2 -O-,
Where R ² is hydrogen or C ₁ -C ₁₈ alkyl, Z is a radical selected from:
-O- -O-CH ₂ -CH _{2,
-C-CH 2 -CH (CH 3} ) -O-,
—O—CH ₂ —CH ₂ —CH ₂ O—, and —O—CH (C ₂ H ₅ ) —O—, and any remaining R ¹ radicals are selected from:
-O-R ³
—NH—C (O) —OR ⁴ , and —NH—C (O) —R ⁴ , and where R ³ is hydrogen or R ⁴ and R ⁴ is C ₁ -C ₁₈ alkyl, fatty A rubber composition which is a cyclic, hydroxyalkyl, alkoxyalkyl or aromatic radical. 11. The rubber composition according to claim 10, wherein, in the formula of the adhesive resin, at least one R radical on average in each monomer or each oligomerized unit,
—CH ₂ —NH—C (O) —OR ⁴
Where R ⁴ is a C ₁ -C ₁₈ alkyl, alicyclic, hydroxyalkyl, alkoxyalkyl or aromatic radical. The rubber composition according to claim 10, wherein on average at least two R radicals are selected from:
_{CH 2 = C (CH 3)} -C (O) O-C 3 H 6 -O-CH 2 -
And _{CH 2 = CH 2 -C (O} ) O-C 2 H 4 -O-CH 2 -
At least one R radical is selected from:
_{CH 2 -NH-C (O)} -O-CH 3
And _{CH 2 -NH-C (O)} -O-C 3 H 7
Rubber composition.   9. A rubber composition according to claim 8, wherein the melamine, acetoguanamine, benzoguanamine, cyclohexylguanamine and glycoluril and their oligomers are hydroxymethylated and alkoxymethylated (the alkoxy group has 1 to 5 carbon atoms). A rubber composition further comprising an additional additive selected from selected derivatives.   The rubber composition according to claim 6, wherein the adhesive resin is melamine or a derivative of an oligomer of melamine.   The rubber composition according to claim 6, wherein the adhesive resin is acetoguanamine or a derivative of an oligomer of acetoguanamine.   The rubber composition according to claim 6, wherein the adhesive resin is benzoguanamine or a derivative of an oligomer of benzoguanamine.   The rubber composition according to claim 6, wherein the adhesive resin is cyclohexylguanamine or a derivative of an oligomer of cyclohexylguanamine. The rubber composition according to claim 1, wherein the adhesive resin is a self-condensed alkylated triazine resin selected from the group consisting of the following (i), (ii) and (iii):
(i) a self-condensed alkylated triazine resin having an imino or methylol functional group and represented by the following formula (I):

(ii) the oligomer of (i), or
(iii) a mixture of (i) and (ii),
Where Z is —N (R) (CH ₂ OR ¹ ), aryl having 6 to 10 carbon atoms, alkyl or acetyl group having 1 to 20 carbon atoms,
Each R is independently hydrogen or —CH ₂ OR ¹ ;
Each R ¹ is independently hydrogen or an alkyl group having 1 to 12 carbon atoms;
Under the condition that at least one R is hydrogen or —CH ₂ OH and at least one R ¹ is selected from an alkyl group;
A rubber composition wherein the rubber composition is substantially free of methylene acceptor co-reactant.   The rubber composition according to claim 18, wherein at least one R group of the alkylated triazine resin is hydrogen. The rubber composition according to claim 19, wherein at least one R ¹ group of the alkylated triazine resin is a lower alkyl group having 6 to 10 carbon atoms.   The rubber composition according to claim 20, wherein the adhesive resin is a derivative of melamine, benzoguanamine, cyclohexylguanamine, acetoguanamine or an oligomer thereof. A rubber composition according to claim 20 wherein Z is _{-N (R) (CH 2 OR} 1), the rubber composition.   The rubber composition according to claim 4, wherein the phenol-formaldehyde resin is resorcinol-formaldehyde; and the melamine-formaldehyde resin is N- (substituted oxymethyl) melamine-formaldehyde. A rubber composition according to claim 1, wherein the ester, the formula has a II, 3 carbons, saturated or 1 linear or branched with sebacic acid with C ₆ -C ₂₄ alcohol - carbon double A rubber composition comprising a saturated diester formed by reaction with an unsaturated one having a bond. 25. A rubber composition according to claim 24, wherein the alcohol is 2-ethylhexyl alcohol and the ester has the following formula:

The rubber composition according to claim 1, wherein the ester is a C ₃₆ dimer acid and a C ₃ -C ₁₈ alcohol saturated with linear or branched or 1 to 3 carbon-carbon double bonds. A rubber composition which is an unsaturated diester formed by reaction with a saturated one.   27. The rubber composition according to claim 26, wherein the alcohol is 2-ethylhexyl alcohol.   27. The rubber composition according to claim 26, wherein the alcohol is tridecyl alcohol.   27. The rubber composition according to claim 26, wherein the alcohol is oleyl alcohol. The rubber composition according to claim 1, wherein the ester contains the following dimer acid reacted with a C _{3 to} C ₂₄ alcohol.

The rubber composition according to claim 1, wherein the ester contains the following dimer acid reacted with a C _{3 to} C ₂₄ alcohol.

The rubber composition according to claim 1, wherein the ester contains the following dimer acid reacted with a C _{3 to} C ₂₄ alcohol.

A rubber composition according to claim 1, wherein the ester, C ₃ -C ₂₄ alcohols, the reaction products of tricarboxylic acid of the following formula, the rubber composition.

  The rubber composition according to claim 1, wherein the ester is a combination of compounds of formulas I, II, III and IV. A rubber composition according to claim 34, wherein the ester, C ₃ -C ₂₄ saturated or one linear or branched alcohol 3 carbon - ones of unsaturated carbon double bonds, CAS # A rubber composition which is a reaction product with a dimer acid having 61788-89-4.   36. The rubber composition according to claim 35, wherein the alcohol is 2-ethylhexyl alcohol.   36. The rubber composition according to claim 35, wherein the alcohol is tridecyl alcohol.   36. The rubber composition according to claim 35, wherein the alcohol is oleyl alcohol. The rubber composition according to claim 1, wherein R ² , R ⁵ , R ⁷ , R ¹² , and R ¹⁴ are fatty acid residues derived from animal or plant fatty acids.   40. The rubber composition according to claim 39, wherein the fatty acid is butter, lard, tallow, grease, herring, menhaden, pilchard, sardine, babas, castor, coconut, corn, cottonseed, jojoba, flaxseed, sei deer, olive A rubber composition selected from the group consisting of: palm, palm kernel, peanut, rapeseed, safflower, soy, sunflower, tall, kiri, and mixtures thereof.   41. The rubber composition according to claim 40, wherein the fatty acid residue is hexanoic acid; octanoic acid; decanoic acid; dodecanoic acid; 9-dodecenoic acid; tetradecanoic acid; 9-tetradecenoic acid; 9-octadecenoic acid; 9-octadecenoic acid, 12-hydroxy; 9,12-octadecadienoic acid; 9,12,15-octadecatrienoic acid; 9,11,13-octadecatrienoic acid; , 11,13-octadecatrienoic acid, 4-oxo; octadecatetraenoic acid; eicosanoic acid; 11-eicosenoic acid; eicosadienoic acid; eicosatrienoic acid; 5,8,11,14-eicosatetraenoic acid; Eicosapentaenoic acid; docosanic acid; 13-docosenoic acid; docosatetraenoic acid; 4,8,12,15,19-docosapenta Phosphate; docosahexaenoic acid; tetracosenoic acid; is selected from and 4,8,12,15,18,21- tetracosadione group consisting of hexa-enoic acid, a rubber composition. A method for increasing the adhesion of a rubber composition comprising natural rubber or synthetic rubber, a vulcanizing agent for the rubber, and an adhesive resin to a base material, wherein a reactive diluent is added to the rubber composition. A liquid comprising Formula I, II, III, IV and mixtures thereof, added in an amount of about 0.5 wt% to about 50 wt% based on the total weight of the adhesive resin plus the esters of Formulas I-IV Adding an ester additive in an amount of from about 0.1% to about 15% by weight based on the weight of the rubber;

Here, R ¹ is a C _{3 to} C ₂₄ alkyl radical, which is linear or branched, saturated or unsaturated having 1 to 3 carbon-carbon double bonds, and R ² is C _{3 to} C ₂₄ saturated fatty acid residues, or unsaturated fatty acid residues having 1 to 6 carbon-carbon double bonds,

Here, n = 3 to 24, R ³ and R ⁴ are the same or different and are a C _{6 to} C ₂₄ alkyl radical, linear or branched,

Where R ⁵ and R ⁷ are the same or different and are C ₃ -C ₂₄ hydrocarbon chains, straight or branched saturated or unsaturated having 1 to 6 carbon-carbon double bonds. Yes,
R ⁶ and R ⁸ are the same or different and are a C _{3 to} C ₂₄ alkyl radical, linear or branched,
R ¹⁰ and R ¹¹ are the same or different and are linear or branched with a C _{3 to} C ₂₄ saturated hydrocarbon chain, or linear or branched with an unsaturated C _{3 to} C ₂₄ hydrocarbon chain. 1 to 6 carbon-carbon double bonds,

Here, R ¹² , R ¹⁴ and R ¹⁸ are the same or different, and are C _{3 to} C ₂₄ hydrocarbon chains having straight-chain or branched saturated or 1 to 6 carbon-carbon double bonds. Unsaturated
R ¹³ , R ¹⁵ and R ¹⁹ are the same or different and are C ₃ -C ₂₄ alkyl radicals, linear or branched saturated or unsaturated having 1 to 3 carbon-carbon double bonds;
R ¹⁶ , R ¹⁷ and R ²⁰ are the same or different and are linear or branched with a C _{3 to} C ₂₄ saturated hydrocarbon chain, or linear with an unsaturated C _{3 to} C ₂₄ hydrocarbon chain, or Branched and having 1 to 6 carbon-carbon double bonds,
Placing the composition under conditions sufficient to vulcanize the rubber in the composition such that the reactive diluent enhances adhesion between the rubber and the substrate;
The method that involves.   43. The method of claim 42, wherein the substrate is a plurality of cords and the reactive diluent is (1) glycidyl ether, (2) diglycidyl ether, (3) aliphatic linear epoxide, ( 4) a monomer selected from the group consisting of epoxidized vegetable oils, (5) alicyclic epoxies, (6) glycidyl esters, (7) diglycidyl esters, and any combinations thereof, adhesive resin plus formulas I to I The method is present in the composition from about 5% to about 40% by weight, based on the total weight of the ester of IV.   43. The method of claim 42, wherein the substrate is a polymer sheet or fiber and the reactive diluent is (1) glycidyl ether, (2) diglycidyl ether, (3) aliphatic linear epoxide. , (4) epoxidized vegetable oil, (5) alicyclic epoxy, (6) glycidyl ester, (7) diglycidyl ester, and a monomer selected from any combination thereof, adhesive resin plus type A process wherein from about 5% to about 40% by weight of the ester of I to IV is present in the composition, based on the total weight.   43. The method of claim 42, wherein the substrate is a planar metal stock material and the reactive diluent is (1) glycidyl ether, (2) diglycidyl ether, (3) aliphatic linear epoxide. , (4) epoxidized vegetable oil, (5) alicyclic epoxy, (6) glycidyl ester, (7) diglycidyl ester, and a monomer selected from any combination thereof, adhesive resin plus type A process wherein from about 5% to about 40% by weight of the ester of I to IV is present in the composition, based on the total weight. A method for increasing the adhesion of a rubber composition containing a vulcanizing agent for rubber to a substrate, the means selected from the group consisting of the following means: (1) Adhesive resin component, reactivity Applying a liquid adhesion promoter containing a diluent component and an ester component to the substrate before contacting the substrate with the rubber composition; (2) a solvent solution containing a reactive diluent; Or a water-based emulsion containing a reactive diluent of an ester component and a liquid adhesion promoter containing the reactive diluent prior to contacting the substrate alone and before contacting the substrate with the rubber composition Contacting the base material alone with a solvent solution or a water-based emulsion containing a reactive diluent of an adhesive resin component and a liquid adhesion promoter; (3) Liquid adhesion of the base material coated with the adhesive resin Contains the ester component of the accelerator Applying a reactive diluent of the adhesive resin component and the liquid adhesion promoter to the substrate prior to contacting the rubber composition comprising a solvent solution or a water-based emulsion; (4) a group to which the ester is applied. Applying an ester component of the liquid adhesion promoter to a substrate before contacting the adhesive resin with a rubber composition comprising a solvent solution or water-based emulsion containing the adhesive resin component and a reactive diluent component. Where the ester component of the adhesion promoter is selected from the group consisting of Formulas I, II, III, IV, and any combination thereof:

Here, R ¹ is a C _{3 to} C ₂₄ alkyl radical, which is linear or branched, saturated or unsaturated having 1 to 3 carbon-carbon double bonds, and R ² is C _{3 to} C ₂₄ saturated fatty acid residues, or unsaturated fatty acid residues having 1 to 6 carbon-carbon double bonds,

Here, n = 3 to 24, R ³ and R ⁴ are the same or different, and are a C _{6 to} C ₂₄ alkyl radical having a linear or branched saturated or 1 to 3 carbon-carbon double bond. Is unsaturated and

Wherein R ⁵ and R ⁷ are the same or different and are C ₃ -C ₂₄ hydrocarbon chains having straight or branched saturated or 1-6 carbon-carbon double bonds,
R ⁶ and R ⁸ are the same or different and are C ₃ -C ₂₄ alkyl radicals, linear or branched saturated or unsaturated having 1 to 3 carbon-carbon double bonds;
R ¹⁰ and R ¹¹ are the same or different and are linear or branched with a C _{3 to} C ₂₄ saturated hydrocarbon chain, or linear or branched with an unsaturated C _{3 to} C ₂₄ hydrocarbon chain. 1 to 6 carbon-carbon double bonds,

R ¹² , R ¹⁴ and R ¹⁸ are the same or different and are C _{3 to} C ₂₄ hydrocarbon chains having straight or branched saturated or 1 to 6 carbon-carbon double bonds;
R ¹³ , R ¹⁵ and R ¹⁹ are the same or different and are C ₃ -C ₂₄ alkyl radicals, linear or branched saturated or unsaturated having 1 to 3 carbon-carbon double bonds;
R ¹⁶ , R ¹⁷ and R ²⁰ are the same or different and are linear or branched with a C _{3 to} C ₂₄ saturated hydrocarbon chain, or linear with an unsaturated C _{3 to} C ₂₄ hydrocarbon chain, or Branched and having 1 to 6 carbon-carbon double bonds,
Means for placing the composition under conditions sufficient to vulcanize the rubber in the composition such that the reactive diluent enhances adhesion between the rubber and the substrate;
The method that involves.   47. The method of claim 46, wherein the amount of the adhesive resin component contained in the rubber composition or applied to the substrate is from about 0.1% by weight based on the weight of rubber in the composition. About 15% by weight, and the amount of the ester component contained in the rubber composition or applied to the substrate is about 0.1% to about 15% by weight based on the weight of rubber in the composition. Wherein the amount of the reactive diluent contained in the rubber composition or applied to the substrate is from about 0.5% to about 50% based on receipt of the total of the adhesive resin component plus ester component. The method is by weight percent. The cord-reinforced product having a plurality of cords selected from the group consisting of polymer cords, metal cords, glass cords, and combinations thereof, and bonded to the rubber composition according to claim 1.