JP2007007427A - Compound for golf balls - Google Patents

Abstract

A solid golf ball having a special feeling of a wound golf ball is provided.
A golf ball includes a core, an outer cover layer, and optionally an intermediate layer disposed between the core and outer cover layer. The outer cover layer may comprise a polyurethane or polyurea blend. At least a portion of the golf ball has a formulation that improves the physical and / or performance characteristics (eg, coefficient of restitution) of the golf ball. Preferably, the coefficient of restitution of the core is 0.8 or more.
[Selection figure] None

Description

  The present invention relates generally to golf balls, and specifically to golf ball components (eg, cores) made from polymer compositions having one or more functional additives.

  Conventional golf balls can be divided into two general groups, solid and wound balls. Solid golf balls include one-piece, two-piece (ie, a solid core and cover), and multiple layers (ie, one or more layers of a solid core and / or one or more layers of a cover). A wound golf ball typically includes a solid, hollow, or fluid-filled center surrounded by a tensioned elastic material, and a cover. Solid balls have traditionally been thought to be longer and more durable than wound balls, but lack the special “feel” that the wound structure provides.

  By changing the structure and composition of the ball, manufacturers can vary a wide range of play characteristics that can be optimized for different play capabilities, such as compression, speed, and spin. One component of golf balls that many manufacturers, in particular, continue to improve is the center or core. When hit with a club head, the core becomes the “engine” of the golf ball. In general, the core and / or center of a golf ball is composed of a polymer composition based on polybutadiene. This type of composition can provide a high coefficient of restitution (“CoR”) while at the same time resulting in a low compression, thereby reducing the spin rate of the golf ball and providing a good “feel” Has been modified so that both can be obtained or both. However, this is a difficult task because currently available polymers have physical limitations. Accordingly, there remains a need for new and improved golf ball core compositions.

  The present disclosure is directed to a golf ball having a core and at least one layer disposed about the core. The core is preferably solid. At least one of the core and the layer has a formulation in which the core or the layer is formed from a base polymer, a crosslinking initiator, and at least one additive, wherein the additive is borane, borate, Boronates, borinates, heterocyclic compounds having at least one boron atom as a ring member, boron-containing organic sulfides, sulfur-containing silico compounds, salts of such additives and metal salts of boron complexes, organometallic salts, and non-metals Selected from the group consisting of salt. The additive may be present in an amount of 0.1 phr to 5 phr based on the weight of the base polymer. The blend may further have at least one component selected from the group consisting of metal salts of unsaturated acids having 3 to 8 carbon atoms, fillers, fatty acids and salts thereof. The coefficient of restitution of the core and / or golf ball may be 0.8 or more. Preferably, the additive increases the coefficient of restitution of the core and / or decreases the compression of the core.

Preferably, the additive comprises a BR _3, or BR _3, monoorganosiloxane, diorgano or triorgano compounds, boric acid, sulfur-substituted borate, amine borate esters, boron acids, diboronate, borinic acid, dioxaborolane, dioxaborinane, B (OR) ₃ , B (OR ″) ₃ , R′B (OR) ₂ , YR ″ B (OR) ₂ , Y ′ [R ″ B (OR) ₂ ] ₂ , R ′ ₂ B (OR), A compound having the structure of S _y [(R ″) _z G] ₂ , selected from the group consisting of metal or non-metal salts of such additives, tetraorgano-borane anion R ₄ B ^— , and R and R ′ Are the same or different monovalent radicals having H and up to 40 carbon atoms, optionally containing one or more heteroatoms and optionally 1 Is substituted with a plurality of electron withdrawing groups and R ″ is the same or different divalent radical having up to 20 carbon atoms, optionally containing one or more heteroatoms and optionally one or more electron withdrawing Substituted with a group; Y is selected from thiocyano (-SCN), epoxy, glycidyl, epithio, vinyl, allyl, amine, and AZ groups, A is an oxygen or sulfur atom, Z is H, metal cation, organic Y ′ is a divalent radical selected from polysulfide S _y or polyselenium Se _y ; G is a monovalent or different Si-containing monovalent group selected from the group consisting of metal cations and non-metallic organic cations X is an integer of 0, 1, 2 or 3, y is an integer of 1 to 8, and z is 0 or 1. Preferably, the additive has at least one C—O—B bond, and the carbon in the bond is the second or third carbon.In addition to the boron-containing additive, the formulation further comprises The core may have a diameter of at least 1.5 inches, preferably at least 1.53 inches, and compression of the core may be from 50 to 90, or from 45 to 80, preferably The core may have a center and an outer core layer, wherein the at least one layer has a thickness of 0.05 inches or less and a flexural modulus of 2000 psi to 30000 psi, preferably It may be an outer cover layer formed from polyurethane or polyurea, or an intermediate layer having a thickness of 0.05 inches or less disposed between the core and the outer core layer.

[Definition]

  Unless otherwise specified, numerical values for quantities are “parts by weight”. The term “equivalent” is a value calculated based on the relative amounts of the various components used to produce a given material and is based on the solids content of the given material. The relative amount results in a theoretical weight in grams of a material such as a polymer produced from the components and gives the theoretical number of specific functional groups present in the produced polymer.

  Subscripts such as m, n, x, y, and z refer to the degree of polymerization (ie, the number of linked repeat units) in a general chemical formula as understood by those skilled in the art. In the case of molecularly non-uniform product, this number is an average number and is not limited to an integer. If not zero, it is the average degree of polymerization.

  Here, the term “polymer” refers to oligomers, adducts, homopolymers, random copolymers, pseudo-copolymers, statistical copolymers, alternating copolymers, periodic copolymers, bipolymers, terpolymers, quarter polymers, other forms of polymers, substitutions thereof Derivatives, and mixtures thereof. These polymers are linear, branched, block, graft, monodisperse, polydisperse, regular, irregular, tactic, isotactic, syndiotactic, stereo regular, atactic, stereo block, single It may be single strand, double strand, star, comb, dendritic, and / or ionomeric.

  Here, the term “telechelic” refers to a polymer having at least two terminal-reactive end groups that can proceed further polymerization with reactive end groups. The reactive end groups disclosed herein include, but are not limited to, amine groups, hydroxy groups, isocyanate groups, carboxylic acid groups, thio groups, and combinations thereof.

As indicated herein, low alkoxy is _C1-5, preferably _C1-3 alkyl and alkoxy, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, amyl , Isoamyl, methoxy, ethoxy, isopropoxy, isobutoxy, t-butoxy.

  As indicated herein, halogen includes fluorine, chlorine, bromine, and iodine.

  As indicated herein, linear or branched alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, amyl, isoamyl, n-hexyl, n-heptyl, n-octyl. , Isooctyl, n-nonyl, isononyl, n-dodecyl.

Here pointing manner, substituted alkyl, cyanoalkyl haloalkyl, hydroxyalkyl, alkoxyalkyl, preferably, preferably, for example, beta-cyanoethyl of C _2-6, beta-chloroethyl, beta-hydroxyethyl, beta-methoxyethyl, Contains β-ethoxyethyl. Cycloalkyl includes cyclopentyl, cycloheptyl, cyclohexyl and may have one or more C _1-4 alkyl.

  As indicated herein, aralkyl and alkaryl include methylbenzyl, phenethyl, phenisopropyl, benzyl and may be, for example, ring substituted with halogen, methyl and / or methoxy. This is, for example, p-methylbenzyl, o- or p-chlorobenzyl, o- or p-tolyl, o- or p-chlorophenyl, and o- or p-methoxyphenyl.

  As pointed out here. Heterocyclic radicals include pyrrolidinyl, piperidinyl, pipecolinyl, morpholinyl, thiomorpholinyl, piperazinyl (eg N-methylpiperazinyl).

  As used herein, the term “derivative” refers to a variety of compounds that are chemically derivable from the parent compound and typically has chemical properties and / or reactivity with the parent compound. Share. Where applicable, derivatives of the compounds disclosed herein are not limited thereto, but are substituted derivatives, anhydrides, dimers, oligomers, esters such as amides, halides, oxidations having one or more substituents. Oxides, sulfides, and metal cations (eg, Na, Zn, Ca, Co, Mg, Ni), organometallic cations, and non-metallic cations (eg, quaternary ammonium, quaternary pyridinium, quaternary quinolinium, (organo) phosphonium, Salts with (organo) sulfonium, (organo) oxonium, (organo) iodonium, (organo) azonium).

  Unless otherwise noted, numerical ranges, amounts, values and percentages such as amount of material, reaction time and temperature, ratio of amounts, molecular weight value (here number average molecular weight average “Mn” or Weighted average molecular weight "Mw"), and what the following part of the specification says "about", even if "about" is not explicitly stated before the value, amount, range The rest can be read as it was written before. Accordingly, unless otherwise indicated, the numerical parameters set forth in the following specification and claims are approximations that vary depending on the desired properties to be obtained in accordance with the present disclosure. Although not limiting the application of the doctrine of claims, at a minimum, each numeric parameter should be ascertained based on the number of reported effective figures and should be ascertained through the application of normal rounding techniques. It is.

  Although the numerical ranges and parameters representing the broad scope of the disclosure are approximate, the values shown in the examples are reported as accurately as possible. However, the numerical value naturally includes a predetermined error necessarily resulting from the standard deviation found in each measuring instrument. Further, when numerical ranges for various scopes are shown herein, it should be understood that any combination of these numbers, including the listed values, can be employed.

  For molecular weight, whether Mn or Mw, their values are determined by gel permeation chromatography with polystyrene as the second position, which is well known to those skilled in the art and is described in US Pat. No. 4,739,019. This is described in column 4, line 2-45, for details.

  Here, the term “manufactured from” (“formed from” etc. is also the same. “Formed from” and “formed of” ”) means open, specifically“ comprising ”(including other elements). Is good). As such, a formulation “manufactured from” the listed component list is a formulation that includes at least the listed components and may include other unlisted components when the formulation is formulated.

  Here, the term “cure”, specifically “curable material”, used in relation to the formulation. “Hardened material” means that any crosslinkable component of the formulation is at least partially crosslinked. In certain examples of this disclosure, the crosslinking density or degree of crosslinking of the crosslinkable component may be 5% to 100% of full crosslinking. In other examples, the crosslink density may be 35% to 85% of full crosslinking. In other examples, the crosslink density may be 50% to 85% of full crosslinks. One skilled in the art will recognize that the presence and extent of cross-linking, i.e. cross-linking density, can be determined by various techniques such as dynamic mechanical thermal analysis (DMTA) fields according to ASTM E1640-99.

  As used herein, the term “saturated” or “substantially saturated” means that the compound or material of interest is sufficiently saturated (ie, does not include a double bond, triple bond or aromatic ring structure), or It means that the degree of unsaturation is negligible, for example bromine according to ASTM E234-98 is less than 10, for example 5.

  Here, the term “flexural modulus” or “elastic modulus” refers to the ratio of pressure to strain within the elastic limit of the material (measured in the bending mode), indicating the bending strength of the material, and the tensile modulus. And similar. Flexural modulus is typically reported in pascals (“Pa”) or pounds per square inch (“psi”) and is measured according to ASTM D6272-02.

  As used herein, the term “material hardness” is the indentation hardness of a non-metallic material in the form of a slab or button and is measured with a durometer. The durometer has a spring-loaded indenter, and this indenter places a pushing load on the slab and measures its hardness. Material hardness indirectly affects other material properties such as tensile modulus, resilience, plasticity, compression resistance and elasticity. Standard measurements of material hardness include ASTM D2240-02b. Unless otherwise stated, material hardness is expressed in Shore D units. Material hardness is distinguished from the hardness of the golf ball portion, which is measured directly on the golf ball surface (or other spherical mirror surface). The numerical differences are primarily based on the structure, size, thickness, and material composition underlying the portion of the golf ball component (ie, center, core and / or layer). It will be readily apparent to those skilled in the art that the material hardness and the hardness measured on the ball are neither correlated nor convertible.

  Here, the term “compression”, also known as “ATTI compression” or “PGA compression”, refers to points obtained from a compression tester (Compression Tester, ATTI Engineering Company, Union city, New Jersey), and It is well known in the art as a scale for determining the relative compression of a spherical object. The approximate relationship between Atti compression and Riehle compression is: Atti compression = (160-Riele compression). Compression is a material property (ie, on-ball property) measured on the golf ball structure, not the material itself. The compression measured with this device is also called PGA compression.

Here, the term “coefficient of restitution” or “CoR” of a golf ball or its subassembly is used to describe the rebound velocity of the ball relative to the initial input velocity when the ball is launched from an air gun to a stationary steel plate. Defined as a ratio. The plate achieves an impact surface load of about 100 pounds or 45 Kg. The time intervals T _in and T _out of the ball flight of two spaced ballistic light screens spaced between the air cannon and the steel plate are measured and CoR = T _out / T _in is calculated. The faster the golf ball rebounds, the higher the COR of the ball, the greater the total energy held when hit by the club, and the ball will fly further. Reported initial CoR velocities are about 50 ft / s to about 200 ft / s, and unless otherwise noted are usually understood to be 125 ft / s. Golf balls have different COR for different initial velocities.

  “Mooney” viscosity is the unit employed to measure the plasticity of raw or unvulcanized rubber. The Mooney unit plasticity is equal to the torque applied to the disk in a container that rotates twice per minute, including rubber at a temperature of 100 ° C, measured at any scale. The measurement of Mooney viscosity is specified in ASTM D-1646.

  As used herein and commonly used, the unit “phr” means “parts by weight of the corresponding material per 100 parts of the base polymer or polymer blend”.

[Detailed description]

  The golf ball of the present invention may have any structure, but preferably includes a core and a cover surrounding the core. The core and / or cover may comprise one or more layers, and an intermediate layer may be disposed between the golf ball core and cover. For example, the core of a golf ball has a normal center that is surrounded by an intermediate layer or an outer core layer. An intermediate or outer core layer is disposed between the center and inner cover layers. The core may be a single layer or a plurality of layers. The innermost part of the core may be a solid or a liquid-filled sphere, but is preferably a solid. Along with the core, the intermediate layer or the outer core layer may comprise a plurality of layers. The intermediate layer may be a wound layer made of a tensioned elastomeric material.

  Suitable materials for the solid core or any golf ball layer may be thermoplastic, but preferably may be partially or fully cross-linked (eg thermoset), base polymer (eg rubber, elastomer) or Formulations having a blend of two or more base polymers, a crosslinking initiator or two or more initiators, and optionally one or more additives (eg, cross-linking coagents, fillers, organosulfur compounds) May be included.

At least one polymer in the base polymer or base polymer blend may be crosslinkable (eg, having olefin and / or acetylenic unsaturation), including but not limited to natural and synthetic rubbers (various raw or recycled forms) Polyolefins, polyamides, polyesters, fluoropolymers, silicones, ionomers, and mixtures thereof. Rubbers and polyolefins include, but are not limited to, ethylene, propylene, butylene, isobutylene, styrene, and / or dienes (simple dienes, allenes, conjugated dienes such as 1,3-butadiene, 2-methyl-1,3- Butadiene, 2,3-dimethyl-1,3-butadiene, chloroprene, 1,3-pentadiene, 1,5-hexadiene, 1,3-cyclohexadiene, 1,4-pentadiene, 1,4-cyclohexadiene, piperylene) Homopolymers and copolymers (which include terpolymers and other complex copolymers, which may be random, block or graft type) and optionally less than 50% of one or more other unsaturations Monomers such as acetylene Styrene), olefins (such as isobutylene), vinyl (e.g. acrylic acid, methacrylic acid, ethacrylic acid, propyl acrylate, other alkyl acrylate, alkyl esters of C _1-6 of such acids, acrylonitrile, styrene, methyl styrene Vinyl toluene, (vinyl benzene), vinyl esters, unsaturated aldehydes (eg acrolein), unsaturated ketones (eg methyl isopropenyl ketone), unsaturated ethers (eg vinyl ether) and others known to those skilled in the art Non-limiting examples include polydienes such as neoprene, polybutadiene (BR. Cis-1,4-polybutadiene), polyisoprene (cis-1,4-polyisoprene), polyethylene (PE), ethylene- Propylene copolymer ( P), ethylene-butylene copolymer, polystyrene butadiene, polyethylene butadiene, styrene-propylene-diene terpolymer, ethylene-propylene-diene terpolymer (EPDM, specifically ethylene-propylene-dicyclopentadiene terpolymer) butyl rubber (polyisoprene) Isobutylene), styrene-isoprene-butadiene terpolymers, copolymers of conjugated dienes with styrene, acrylonitrile, and / or methacrylates, their fluorinated polymers (eg, fluorinated EP and fluorinated EPDM), and blends of one or more thereof The crosslinkable base polymer may be solid at room temperature.Suitable crosslinkable base polymers are highly linear structures (high cis BR made with Nd catalyst system), Branch of the structure (e.g., high cis BR produced by Co the catalyst system), or may have a structure with an intermediate degree of branching (e.g. high cis BR produced by Ni catalyst system). Suitable polydiene homopolymers or copolymers, eg BR, have a high 1,4-cis content (eg 60% or more, 80% or more, 90% or more, 95% or more, or about 99% or more, eg Nd, High cis BR produced with Co or Ni catalyst system), high 1,4-trans content (eg 45% or more, 55% or more, 65% or more, 75% or more, or 80% or more, or 90% or more For example, high cis BR produced with La, Nd or Ni catalyst systems) and / or low 1,2-vinyl content (eg 15% or less, or 10% or less, or 7% or less, or 5% or less, Or 1% or less). Polydienes such as BR employ various combinations of cis-, trans-, and vinyl isomer structures, such as combinations where the cis-structure content is greater than the trans-structure content and / or the 1,2-vinyl structure content. Where the sum of the cis-, trans- and vinyl isomer content in any given polydiene is 100%. Various polydienes are employed alone or in a blend of two or more thereof to provide golf ball parts of any desired physical or chemical and performance characteristics (between core and cover, portions or layers therein) Can be formulated.

  Polymer blends used for the base polymer include, but are not limited to, those disclosed in US Pat. No. 6,774,187 (the contents of which are incorporated herein by reference), cis-1,4-poly Isoprene rubber, 3,4-polyisoprene rubber, styrene-isoprene-butadiene rubber, styrene-butadiene rubber by emulsion polymerization, styrene-butadiene rubber by solution polymerization, cis-1,4-polybutadiene rubber, and butadiene-acrylonitrile by emulsion polymerization Or styrene-butadiene-acrylonitrile rubber. Styrene-butadiene rubber by emulsion polymerization can improve the processability of the uncured compounded mixture and has a styrene content of 5% to 18%, or 20% to 28%, or 30% to 50%. good. The butadiene-acrylonitrile or styrene-butadiene-acrylonitrile rubber by emulsion polymerization may have an acrylonitrile content of 2% to 40% and 2% to 30%, respectively. Styrene-butadiene rubber by solution polymerization can reduce the hysteresis of the formulation and may have a styrene content of 5% to 50% or 9% to 36%. The cis-1,4-polybutadiene rubber can improve the elasticity and wear resistance of the formulation and may have a cis-1,4 content of at least 90%.

  Other parameters used to determine the appropriate base polymer are Mooney viscosity, solution viscosity, weight and / or number average molecular weight, and polydispersity. In one example, the base polymer or polymer blend may have one or more polymers having a Mooney viscosity of 35 or more, or 50 or more, an intermediate Mooney viscosity range of 40-60, or a high Mooney viscosity of 65 or more. . The base polymer or polymer blend may have one or more polymers having a weighted average molecular weight of 200000 or more, or 250,000 or more, or 300000 or more, or 400000 or more. The base polymer or polymer blend may have one or more polymers with a polydispersity of 2 or less, or 1.8 or less, or 1.5 or less, or 1.35 or less, or 1.2 or less.

  In other alternative examples, the base polymer or polymer blend has a Mooney viscosity of 60 or less, or 50 or less, or 35 or less when only one or more of the additives disclosed herein are employed in the formulation. Or 30 or less, or 25 or less, or 20 or less, or 15 or less. The weight average molecular weight of the polymer may be 250,000 or less, or 200000 or less, or 180000 or less, or 150,000 or less, or 100000 or less, or 85000 or less, or 50000 or less. The polydispersity of the polymer may be greater than 3.5, or 4 or more, or 4.5 or more, or 5 or more, preferably 10 or less, or 8 or less. The vinyl content of the polymer is 8% or more, or 10% or more, or 12% or more, or 15% or more, or 18% or more, or 20% or more, preferably less than 40%, or 35% or less, or 30% or less. It may be. For example, the base polymer or polymer blend can be synthesized using an alkyl lithium or an anionic catalyst system (with or without polar modifiers such as N- or O-containing compounds) and optionally a cup with functional groups. One or more polydienes modified by a ring agent and / or reactive compound may be included.

  The base polymer blend further has one or other elastomer that is crosslinkable or non-crosslinkable, such as diene rubber, a saturated rubber known in the art. Suitable elastomers for use in the base polymer blend include, but are not limited to, those previously disclosed, some or fully hydrogenated versions thereof, polyurethane rubbers, polyurea rubbers, metallocene catalyst polymers, plastomers, and Including multi-olefin polymers, which may be homopolymers, copolymers or terpolymers. The main part of the base polymer blend (eg 50% by weight or more or 80% by weight or more of the base polymer blend) is one or more combinations of two or more crosslinkable polymers, for example polydienes, preferably polybutadiene, The other miscible elastomer is present in an amount less than 50%, or less than 40%, or less than 30%, or less than 25%, or less than 20%, or less than 15%, or less than 10%, or less than 5%. good. In one example, the base polymer blend has less than 20%, or less than 18%, or less than 10% balata. In other examples, the base polymer is substantially free of balata (ie, less than 2%).

  A preferred base rubber is 1,4-polybutadiene having a cis-structure of at least 40%, preferably at least 90%, and most preferably at least about 95%. The Mooney viscosity of the base rubber is preferably greater than about 35, more preferably greater than about 40, and most preferably greater than about 50. Preferably, the molecular weight of the polybutadiene rubber is greater than about 200,000, more preferably greater than or equal to about 275,000, most preferably greater than or equal to about 400,000, and the polydispersity is not greater than about 3, more preferably less than or equal to 2. Examples of desired polybutadiene rubbers are BUNA® CB22 and BUNA® CB23, commercially available from Bayer of Akron, OH, UBE Industries of Tokyo, Japan ) UBEPOL® 360L and UBEPOL® 150L available commercially from CRIFLEX® and CARIFLEX® BCP820 commercially available from Shell of Houston, TX, and CARIFREX ( (Registered trademark) BCP824. If desired, the polybutadiene may be mixed with other elastomers known in the art, such as natural rubber, polyisoprene rubber and / or styrene-butadiene rubber, to modify the properties of the core.

  Cross-linking initiators include any chemical and / or physical means known to those skilled in the art, specifically those that can generate reactive free radicals, such as thermal initiators and photoinitiators. Including. Such initiators include, but are not limited to, compounds such as elemental sulfur or sulfur donors (with or without a promoter), organic peroxides, organometallic peroxides, carbon-carbon initiation Agent, azo compound (eg azobisisobutyronitrile), perester, organic polyoxide, ozone, dioxygen, haloid molecule, polyatomic peroxide, substituted hydrazine, hydrazide, benzophenone, alkoxyamine, nitro compound, nitrate, disulfide, polysulfide And organometallic compounds and radiation means (with or without sensitizer, eg photoinitiator), eg actinic radiation, particle radiation, X-ray radiation, electron beam radiation, super Sonic and heat, or two or more of these compounds and / or physical means Including the combined viewing. Initiator dissociation promoters can be used in combination with various initiators and blends thereof. When one or more initiator compounds are used in the form of the substance alone, the amount of all initiators is 0.1 phr or more, or 0.2 phr or more, or 0.5 phr or more, or 0.8 phr or more, preferably May be 10 phr or less, or 5 phr or less, or 2 phr or less, or 1 phr or less. The weight ratio of any two initiator compounds, when used together, is 0.05: 1 to 50: 1, or 0.1: 1 to 5: 1, or 0.25: 1 to 3: 1, Or 0.5: 1 to 1: 1, or any range in between. When an initiator dissociation promoter is used, the molar ratio of promoter to initiator may be 0.001: 1 to 1: 1, or 0.05: 1 to 1: 1.

  The initiator may be any known polymerization initiator that dissociates during the cure cycle. Suitable initiators are organic peroxide compounds such as peroxyketals (eg 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane. 1,1-bis (t-butylperoxy) cyclododecane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) Propane, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, 2 , 2-bis (t-butylperoxy) octane), dialkyl peroxides (eg, dicumyl peroxide (DC ), Α, α-bis (t-butylperoxy) diisopropylbenzene (DTBP), 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide, di-t-amyl Peroxide, t-butylcumyl peroxide, di (2-methyl-1-phenyl-2-propyl) peroxide, t-butyl-2-methyl-1-phenyl-2-propyl peroxide, 2,5-dimethyl-2, 5-di (t-butylperoxy) hexane-3, di (2-t-butyl-peroxyisopropyl) benzene peroxide), diacyl peroxide (eg, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,3, 5-trimethylhexanoyl peroxide, m-toluoyl benzoyl peroxide, ben Yl peroxide, m-toluoyl peroxide, 2,5-dimethyl-2,5-di (benzoyl peroxide) hexane, acetyl peroxide, propionyl peroxide, octanoyl peroxide, deconoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, t-butyl-peroxymaleic acid), peroxyesters (eg, α, α-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecane Noate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypi Rate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxymaleic acid, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl -2,5-bis (benzoylperoxy) hex , T-butylperoxy-m-toluoyl benzoate, bis (t-butylperoxy) isophthalate, t-butyl-peroxyisopropyl carbonate, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxy -3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate), ketone peroxides (eg methylcyclohexanoate peroxide, methylacetoacetate peroxide, acetylacetone peroxide, methylethylketone peroxide, cyclohexanone peroxide) ), Hydroperoxides (eg, t-hexyl hydroperoxide, t-butyl hydroperoxide, p-menthane hydroperoxide, 1, 1,3,3-tetramethylbutyl hydroperoxide, 2,5-gemethylhexane-2,5-hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide), peroxydicarbonate (e.g., di-n-propyl peroxydicarb) Bonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-2-methoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate), t-butyltrimethylsilyl peroxide, 3,3′4,4′-tetra (t-butylperoxycarbonyl) benzo Enon, and combinations of two or more thereof. DCP is the peroxide most commonly used in golf ball manufacture. DTBP can achieve higher crosslinking efficiency. Other examples include, but are not limited to: VAROX® 231XL and VAROX® DCP-R, commercially available from Elf Atochem of Philadelphia, PA; Chicago; Perkodox® BC and PERKODOX® 14 available commercially from Akzo Nobel of Chicago, IL; and commercially available from Rhein Chemie of Trenton, NJ Possible ELASTOCHEM® DCP-70.

  It is well known that peroxides are available in different forms with different activities. The activity is typically defined by the “active oxygen content”. For example, PERKODOX ™ BC peroxide is 98% active and the amount of active oxygen is 5.80%, while PERKODOX ™ DCP-70 is 70% active and the amount of active oxygen is 4.18%. It is. If the peroxide is in pure form, it is preferably in an amount of at least about 0.25 phr, more preferably in an amount between about 0.35 phr to about 2.5 phr, and most preferably from about 0.5 phr to about 2.5 phr. An amount between 2 phr. Peroxides are also available in concentrated form, which is known to have various activities as described above. In this case, those skilled in the art know that if concentrated peroxide is used in this invention, the concentration suitable for pure peroxide is easily adjusted for concentrated peroxide by dividing by activity. For example, 2 phr of pure peroxide is equivalent to 4 phr of 50% active concentrated peroxide (ie 2 ÷ 0.5 = 4).

  Carbon-carbon initiators include those disclosed in commonly assigned US Patent Application Publication No. 2005-0009992, the contents of which are incorporated herein by reference. The carbon-carbon initiator may be used under the peroxide initiator or as a blend with the peroxide initiator and the weight ratio is in the above range.

  Initiator dissociation promoters can be used in combination with one or more additives (eg, boron-containing compounds) disclosed herein. Useful accelerators include, but are not limited to, iron (III) compounds (eg, iron chloride, iron acetylacetonate, iron naphthenate, iron stearate), copper (II) compounds (eg, copper chloride, copper citrate, copper acetyl). Acetonate, copper citrate), molybdenum compounds (eg, molybdenum (VI) oxide, molybdenum oxide acetylacetonate, and those disclosed herein), manganese compounds (eg, manganese (IV) oxide, manganese naphthenates, and here) ), Cobalt compounds (eg, cobalt naphthenate, cobalt (III) acetylacetonate), tungsten compounds (eg, tungsten (VI) oxide, sodium tungsten, silicotungstic acid, and those disclosed herein), tin Compounds (eg dibutyl (IV) oxide, and include here those disclosed), and a metal alkoxide (e.g., titanium tetrabutoxide, aluminum tributoxide, and those disclosed herein).

Functional additives may have a single function, or two or three or more functionalities, including but not limited to peptizers, plasticizers (physical or cross-linkable), isomerizing agents , Crosslinking aids, free radical mediators (eg sulfur donors), photoinitiators, oxidants, sensitizers, synergizers, flame retardants, impact modifiers, thermal stabilizers, antistatic agents, compatibility agents, foam Agent, reinforcing agent, initiator decomposition accelerator, viscosity imparting agent, polymerization modifier, interfacial treatment agent, colorant, fragrance, processing aid, coupling agent, accelerator, activator, deterioration inhibitor, antioxidant, Swelling agents, dispersants, enhancers (eg CoR), reducing agents (eg compression, crystallinity), extenders, fillers (eg density, elastic modulus), inhibitors, lubricants, retarders (eg curing, scorch), scavenging Agents (eg oxygen, moisture, free radicals), stabilizers (eg Temperature, light, degradation) may have thixotropic, and / or a wetting agent. Preferably, the additive changes the percentage of cis, trans, and / or vinyl in the CoR enhancer (ie, can increase the CoR of the core and / or ball), isomerization mediator (ie, base polymer). it can), T _g shifter (i.e. glass transition temperature of the polymeric material (T _g) curve (as determined by differential scanning calorimetry or dynamic mechanical analyzer) can be shifted in the vertical direction of the temperature) , A degree of crosslinking modifier (ie, one or more types of crosslinking: polymer-polymer crosslinking, coagent-polymer crosslinking, coagent-coagent crosslinking, carbon / carbon crosslinking, ionic crosslinking may be varied) And / or crosslinking profile modifier (ie, the ratio of different crosslinking types) It may be can) be of. An additive may be capable of exerting one or more such functionalities (eg, being a CoR enhancer) without one or more other functionalities (eg, isomerization mediators). Additives may perform various functionalities simultaneously or at different stages of material processing, ball making, storage, and / or use.

の構造を有し、ここで、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４およびＲ_５の少なくとも１つ（例えば、２、３、４、または５）は、同一または異なる電子吸引性基（「ＥＷＧ」）であり、Ｒ_１〜Ｒ_５の残りがある場合には、それらは同一または異なる有機ラジカルまたは水素であり；Ｚは金属カチオン（一価、二価、または多価、例えば、Ｌｉ、Ｎａ、Ｋ、Ｓｃ、Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｔｉ、Ｚｒ、Ｃｒ、Ｍｏ、Ｆｅ、Ｃｏ、Ｒｈ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ｚｎ、Ｃｄ）、有機金属カチオン（ここに開示されているようなもの）、および非金属有機カチオン（例えば、アンモニア、置換アンモニア、トリチル、およびここに開示されているもの）から選ばれたもの、または、ｎが１の場合水素またはハロゲンであってよく（例えばアリールスルフェニルハロゲン）；ｎは１、２またはこれ以上の整数であり、好ましくは６以下である。 One group of suitable additives is

Wherein at least one of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ (eg 2, 3, 4, or 5) is the same or different electron withdrawing group (“ EWG ") and the remainder of R ₁ -R ₅ are the same or different organic radicals or hydrogen; Z is a metal cation (monovalent, divalent, or polyvalent, eg, Li, Na, K, Sc, Be, Mg, Ca, Sr, Ba, Ti, Zr, Cr, Mo, Fe, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, Cd), organometallic cations (here Selected from non-metallic organic cations (eg, ammonia, substituted ammonia, trityl, and those disclosed herein), or hydrogen or halogen when n is 1 May be (example If aryl sulfenyl halide); n is 1, 2 or more integer, preferably 6 or less.

In one embodiment, the EWG is a C _1-12 perhaloalkyl (straight chain containing 1, 2, 3, 4, 5, 6 or more carbon atoms and 1, 2, 3 or more types of halogens). Or branched perhaloalkyl, eg, linear C _2-8 perhaloalkyl, branched C _3-6 perhaloalkyl), C _6-20 (per) haloaryl (6 or more carbon atoms and 1, 2, 3 or more Including those having aromatics with the above types of halogen substituents), C _7-20 (per) _haloaralkyls (including those having 1, 2, 3 or more types of halogen substituents), C _7-20 (per) (including those having two, three or more kinds of halogen substitutions) haloaralkyl, _{C 7-20} (per) Haroarukariru (1, 2, 3 or more Including those having a different halogen substitutions), consisting of a C _{3-20 (per)} halosulfuron Black alkyl (3 or more carbon atoms, three or more types of the halogen-substituted compound ring Preferred are EWGs (including those having a structure), and combinations of two or more of these ("PEWG"). EWG other than perhaloalkyl may be free of halogen substituents, or partially halogenated or perhalogenated. Halogen includes F, Cl and I. Non-limiting examples of such EWG _{is, -CF 3, -CCl 3, -CBr} 3, -CI 3, C 2-8 ( per) _{fluoroalkyl, C 2-8} (per) chloroalkyl, _{C 2 -8} (per) bromoalkyl, C _2-8 (per) iodoalkyl, -C (CF ₃ ), -C (CCl ₃ ), -C (CBr ₃ ), -C (CI ₃ ), (per) fluoro Cycloalkyl, (per) chlorocycloalkyl, (per) bromocycloalkyl, (per) iodocycloalkyl, (per) halophenyl (eg, p-bromophenyl, m-bromophenyl, p-curulophenyl), —C (X _{1) 2 X 2, -CX 1} X 2 H, and _{CX 1 X 2 X 3 (X} 1, X 2 and _{X 3} comprises a different halogen). Preferably, one or more of R ₁ , R ₃ and R ₅ (eg 2 or 3) are the same or different species of EWG as described above. These preferred EWGs are more electron withdrawing than the other EWGs described herein below and are therefore more effective in achieving these desired functionalities.

Other day-restricted EWGs for R ₁ to R ₅ are X (halogen), aldehyde, [(per) halo] alkyl / arylcarbonyl (COR, eg acetyl, trifluoroacetyl, phenylcarbonyl), COOZ ( Carboxylic acid or a salt thereof), COOR ([(per) halo] ester, [(per) halo] alkyl / aryloxycarbonyl such as methoxycarbonyl, ethoxycarbonyl), COX (halocarbonyl), such as 1, 2, 3 SR, SO ₂ NH ₂ (sulfonamide) such as (per) halo (cyclo) alkylthio (eg trifluoromethylthio) having 6 or more carbon atoms and (per) haloarylthio having 6 or more carbon atoms _), SO 2 NHR ([(per) halo sulfonamide), O ₂ NR ₂ ([(per) halo sulfamoyl), SCOR ([(per) halo carbonyl thio, for example acetylthio) [(per) halo amide (e.g. amide, methylamide, phenylamide, ureido), SCONH ₂ (Carbamoylthio), SOR ([(per) halo] alkyl / arylthio, eg, methoxylthio), SO ₂ R ([(per) halo] alkyl / arylsulfonyl, eg, methylsulfonyl, phenylsulfonyl), CN (di Tolyl or cyano), SO ₃ Z (sulfonic acid or salt thereof), SO ₃ R ([(per) halo] sulfonic acid ester), N ⁺ H ₃ , N ⁺ R ₃ , NO ₂ (nitro), and NCS ( Thiocyanato). Where R is the same or different, optionally substituted (eg (per) halogenated), C _1-20 monovalent radical, eg C _1-18 alkyl (including straight-chain and branched) , C _6-15 aryl, C _7-20 aralkyl.

Suitable radicals for the rest of R _{1 to} R ₅ are further H, straight-chain, branched or cyclic monovalent radicals having one or more carbon atoms, alkyl (eg methyl, ethyl, n-propyl, n -Butyl, sec-butyl, n-pentyl, n-hexyl), aryl (eg phenyl, α-naphthyl, β-naphthyl) alkaryl (eg p-methylphenyl), aralkyl (eg benzyl, phenethyl), alkenyl (eg Vinyl), aralkenyl (eg 2-phenylvinyl) alkynyl (eg ethynyl, propargyl, 2-butynyl), aralkynyl (eg phenethynyl), EWG-substituted aryl, [(per) halo] alkenyl (eg -CH = CR ₂ , -CX = _CR 2), [(per) halo] alkynyl (C≡CR), SH (thio), O (Hydroxyl), OR, for example, [(per) halo alkoxy (e.g. trifluoromethoxy, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, isopropoxy, isobutoxy, _{isopentyloxy),} the _{C 3-8} [( Per) halo] cycloalkyloxy (eg, cyclopropyloxy, cyclohexyloxy, cyclohexylmethoxy), C _6-15 [(per) halo] aryloxy (eg, phenyloxy, p-triloxy), C _7-20 [(per) Halo] aralkyloxy (eg, benzyloxy, phenethyloxy, diphenylmethoxy, triphenylmethoxy), C _7-10 [(per) halo] phenylalkyloxy, C _7-10 [(per) halo] alkylphenyloxy, C _{2− 7} [(Pel) Halo] Asilo Xyl (eg acetyloxy, propionyloxy, acryloyloxy, benzoyloxy, C _2-6 [(per) halo] alkenyloxy (eg vinyloxy, 1-propenyloxy, allyloxy), C _2-6 [(per) halo] alkynyloxy ( For example, ethynyloxy, 2-propynyloxy), C _2-7 [(per) halo] alkoxycarbonyloxy (eg meoxycarbonyloxy, ethoxycarbonyloxy), C _7-15 [(per) halo] ary. Roxycarbonyloxy (eg phenoxycarbonyloxy, benzyloxycarbonyloxy), C _1-7 [(per) halo] alkanesulfonyloxy (eg methanesulfonoxy, ethanesulfonoxy) and C _{6 -10} [(per) halo arylsulfonyl Niro carboxymethyl (e.g. benzene Ruhonirokishi), and hydroxyalkyl (e.g., hydroxymethyl).

  Non-limiting examples of groups of additives with preferred EWG are as described above, 2-, 3-, or 4- (trifluoromethyl) thiophenol, 2-, 3-, or 4- (trichloromethyl) Thiophenol, 2-, 3-, or 4- (tribromomethyl) thiophenol, 2-, 3-, or 4- (triiodomethyl) thiophenol, 2,3-, 2,4-, 2,5 -, 2,6-, 3,4- or 3,5-bis (trifluoromethyl) thiophenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-bis (trichloromethyl) thiophenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-bis (tribromomethyl) thiophenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or , 5-bis (triiodomethyl) thiophenol, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-, or 3, 4,5-tris (trifluoromethyl) thiophenol, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-, or 3 , 4,5-tris (trichloromethyl) thiophenol, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-, or 3 , 4,5-tris (tribromomethyl) thiophenol, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-, or 3,4,5-tris (triiodomethyl) thiophenol, and metal salts thereof (for example, salts of Zn, Co, Mg).

ただし、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４およびＲ_５の少なくとも１つと、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９およびＲ_１０の少なくとも１つは、ＰＥＷＧ、−ＳＺ、および−ＯＺから選択された同一または異なるラジカルである。ただし、ＰＥＷＧおよびＺは上述のとおりである；、Ｒ_１〜Ｒ_１０の残りがある場合には、それらは水素および他のＥＷＧおよび有機置換物、例えば上述したものから選択した、同一または異なるラジカルであり；ｎは１、２、３、４またはそれ以上の整数である。一実施例では、Ｒ_１、Ｒ_３およびＲ_５の少なくとも１つ（例えば、２または３）、および／または、Ｒ_６、Ｒ_８およびＲ_１０の少なくとも１つ（例えば、２または３）は、同一または異なるＰＥＷＧである。他の実施例では、Ｒ_１、Ｒ_３およびＲ_５の少なくとも１つ（例えば、２または３）、および／または、Ｒ_６、Ｒ_８およびＲ_１０の少なくとも１つ（例えば、２または３）は、同一または異なる−ＳＺまたは−ＯＺである。このような添加物の非制限的な例は、４，４’−チオビスベンゼンチオール、ビチオノール、ジクロロジフェニルスルフィド、ビス（４−メトキシフェニル）ジスルフィド、ビス（３−メトキシフェニル）ジスルフィド、ビス（２−メトキシフェニル）ジスルフィド、ビス（４−エトキシフェニル）ジスルフィド、ビス（４−イソプロポキシフェニル）ジスルフィド、ビス（４−シクロヘキシロキシフェニル）ジスルフィド、ビス（４−アリロキシフェニル）ジスルフィド、ビス（４−（２−プロピニロキシ）フェニル）ジスルフィド、ビス（４−フェノキシフェニル）ジスルフィド、ビス（４−アセトキシフェニル）ジスルフィド、ビス（４−ベンゾイロキシフェニル）ジスルフィド、ビス（４−メタンスルホニロキシフェニル）ジスルフィド、ビス（４−ベンゼンスルホニロキシフェニル）ジスルフィド、ビス（４−メトキシカルボニロキシフェニル）ジスルフィド、ビス（４−フェノキシカルボニロキシフェニル）ジスルフィド、ビス（４−トリフルオロメチルフェニル）ジスルフィド、ビス（４−トリクロロメチルフェニル）ジスルフィド、ビス（４−トリブロモメチルフェニル）ジスルフィド、および、４，４’−チオビスベンゼンチオール亜鉛およびビチオノールナトリウム塩のような、それらの塩を含む。 Another group of additives has the general structure:

Provided that at least one of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ and at least one of R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are derived from PEWG, -SZ, and -OZ. The same or different selected radicals. However, PEWG and Z are as described above; and when there is remaining R ₁ to R _10, they hydrogen and other EWG and organic substituents such as, for example selected from those described above, the same or different radicals N is an integer of 1, 2, 3, 4 or more. In one example, at least one of R ₁ , R ₃ and R ₅ (eg 2 or 3) and / or at least one of R ₆ , R ₈ and R ₁₀ (eg 2 or 3) is The same or different PEWG. In other embodiments, at least one of R ₁ , R ₃ and R ₅ (eg, 2 or 3) and / or at least one of R ₆ , R ₈ and R ₁₀ (eg, 2 or 3) is , Same or different -SZ or -OZ. Non-limiting examples of such additives include 4,4′-thiobisbenzenethiol, bithionol, dichlorodiphenyl sulfide, bis (4-methoxyphenyl) disulfide, bis (3-methoxyphenyl) disulfide, bis (2 -Methoxyphenyl) disulfide, bis (4-ethoxyphenyl) disulfide, bis (4-isopropoxyphenyl) disulfide, bis (4-cyclohexyloxyphenyl) disulfide, bis (4-allyloxyphenyl) disulfide, bis (4- ( 2-propynyloxy) phenyl) disulfide, bis (4-phenoxyphenyl) disulfide, bis (4-acetoxyphenyl) disulfide, bis (4-benzoyloxyphenyl) disulfide, bis (4-methanesulfonyloxyphenyl) disulfide Bis (4-benzenesulfonyloxyphenyl) disulfide, bis (4-methoxycarbonyloxyphenyl) disulfide, bis (4-phenoxycarbonyloxyphenyl) disulfide, bis (4-trifluoromethylphenyl) disulfide, bis (4-trichloromethylphenyl) disulfide, bis (4-tribromomethylphenyl) disulfide, and their salts, such as 4,4′-thiobisbenzenethiolzinc and bithionol sodium salt.

  Without being bound by any particular theory, if there is one or more EWGs in the aromatic structure, especially in the ortho and / or para positions, SS, SZ, and / or CS It is believed that the electron density along the bond decreases, thus reducing their bond dissociation energy and allowing the bond to dissociate easily. This is especially true under normal curing cycle conditions (eg, with heat and cross-linking initiator). Such bond dissociation leads to the formation of radical intermediates, which may damage the long chain of the base polymer. Specifically, radical intermediates affect the formation of one or more types of crosslinks during curing, resulting in other properties (eg, compression, hardness, bending, etc.) (Modulus) may be increased with or without incidental effects. In addition, radical intermediates (eg, teal radicals) can mediate hydrogen atom transfer reactions, which are believed to at least partially result in cis-trans isomerization.

ただし、Ｒ_１、Ｒ_２、Ｒ_４およびＲ_５の少なくとも１つは、−ＯＺ、好ましくは、−ＳＺ、であり、Ｚは上述のとおりであり；Ｒ_１〜Ｒ_５の残りがある場合には、それらは水素およびＷＧおよび有機置換物、例えば上述したものから選択した、同一または異なるラジカルであり；ＺがＨまたはハロゲンのときｎは１であり、またＺがカチオンのときにはｎは１〜６の整数である。一実施例では、Ｒ_１およびＲ_５の少なくとも１つは−ＳＺである。他の例では、Ｒ_３も−ＳＺである。代替的にはＲ_３は−ＳＺ以外の有機基である。このような添加物の非制限的な例は、オルト−ジチオールおよびオルト−ポリチオール、例えば、１，２−ジチオールベンゼン、３，４−ジチオールトルエン、３，４，５，６−テトラクロロ−１，２−ジチオールベンゼン、１，２，４，５−テトラチオールベンゼン、１，２−ベンゼンジチオール亜鉛塩、３，４−トルエンジチオール亜鉛塩、３，４，５，６−テトラクロロ−１，２−ベンゼンジチオール亜鉛塩、１，２，４，５−ベンゼンテトラチオール二亜鉛塩、２，２’−チオビス（４，６−ジクロロフェノール）二ナトリウム塩を含む。 Another group of additives has the general structure:

Provided that at least one of R ₁ , R ₂ , R ₄ and R ₅ is —OZ, preferably —SZ, and Z is as described above; when there is a remainder of R _{1 to} R ₅ Are the same or different radicals selected from hydrogen and WG and organic substituents such as those described above; n is 1 when Z is H or halogen, and n is 1 to 1 when Z is a cation. It is an integer of 6. In one example, at least one of R ₁ and R ₅ is —SZ. In other examples, R ₃ is also -SZ. Alternatively, R ₃ is an organic group other than -SZ. Non-limiting examples of such additives include ortho-dithiol and ortho-polythiol, such as 1,2-dithiolbenzene, 3,4-dithioltoluene, 3,4,5,6-tetrachloro-1, 2-dithiolbenzene, 1,2,4,5-tetrathiolbenzene, 1,2-benzenedithiol zinc salt, 3,4-toluenedithiol zinc salt, 3,4,5,6-tetrachloro-1,2- Benzene dithiol zinc salt, 1,2,4,5-benzenetetrathiol dizinc salt, 2,2′-thiobis (4,6-dichlorophenol) disodium salt.

  Other suitable additives that are organic sulfur compounds are organic sulfides and their metal salts, and metal salts of aromatic ortho-thiols. Suitable organic sulfur compounds are: 1,3-dithiolane, 2,4,5-trithiolane, and oligomers thereof; 1,3,4,6-tetrathiapentalene-2,5-dione; 2-thiobarbituric acid 2,2′-dithiobis (pyridine-N-oxide); 2,2′-thiobis (4,6-dichlorophenol) disodium salt; 2,2 ′-(2,5-thiophenediyl) bis [5- tert-butylbenzoxazole]; 3-mercaptopropionic acid zinc salt; 3- (phenylthio) acrylic acid; 3,5-dichlorobenzenesulfonyl chloride; 4-thiouracil; 4,4′-bis (diphenylsulfonium) diphenyl sulfide hexa Fluoroantimony salt; 4,4′-thiobisbenzenethiol dizinc salt; 6-amino-1,3,5-triazine-2, 8,8'-quinonyl disulfide; acryloxythiol; acryloxythiol zinc salt; ammonium pyrrolidine carbothioate; benzene-1,2-dicarbodithioic acid; benzene-1,2-dicarbothioic acid; benzenedisulfonyl chloride Benzenesulfonic acid sodium salt; benzenesulfonamide; benzenesulfonic acid; benzoyl sulfide; benzo [c] thiophene-1,3-dione; benzo [c] thiophene-1,3-dithione; benzyl N, N-dimethyldithiocarbamate Bis (3-triethoxysilylpropyl) tetrasulfide; bis (4-acryloxybenzene) disulfide; bis (phenylsulfonyl) methane; butadiene sulfide; di-p-toluenesulfonamide; di-p- Di-p-tolyl disulfoxide; di-p-tolylsulfinyl sulfone; di- (4-acryloxyphenyl) disulfide; diisopropylxanthogen disulfide; dimethyl sulfite; diphenyl- (4-phenylsulfanyl-phenyl) -sulfonium Hexafluoroantimonate (V); diphenyl disulfone; diphenyl dichlorosulfide; diphenyl sulfone; diphenyl sulfoxide; formamidine disulfide dihydrochloride; glyoxal sodium bisulfite additive compound, hydrate; manganese ethylene bis (dithiocarbamate); methane sulfone N-chloro-p-toluenesulfonamide, sodium salt; N- (cyclohexylthio) phthalimide; N- (phenylthio) E) phthalimide; N, N′-sulfonylbisaniline; p-toluenesulfonic acid sodium salt; p-toluenesulfonamide; p-toluenesulfonylhydrazide; pentafluorobenzenesulfenyl chloride; phenothiazine; phenoxathiin; Poly (p-phenylene ether-sulfone); poly (phenylene sulfide); s-trithiane; sulfanilamide; sulfanilic acid; sulfolane; sulfothioquinoline; tetraalkyl thiuram disulfide; tetraamyl thiuram disulfide; Tetrathiafulvalene; thianthrene; thiobis (triphenylsulfonium hexafluorophosphate); thionine acetate; Thionine chloride; thiophthalic acid; thiophthalic anhydride; thiosemicarbazide; thiourea; thioxanthen-9-one; toluene-3,4-dithiol zinc salt; triphenylsulfonium tetrafluoroborate; triphenylsulfur chloride; Mercaptopyridine-N-oxide; zinc 2-mercaptotolimidazole; zinc benzenesulfinate dihydrate; zinc di-n-butyldithiocarbamate; zinc dimethyldithiocarbamate; zinc di (acrylthioic acid); Includes zinc p-toluenesulfonate and (4-phenylthiophenyl) diphenylsulfonium triflate.

ただし、ｎは１、２、４または６の整数、ｍは１〜３の整数、χは１〜６の整数であり、置換物Ｒ_１〜Ｒ_４は、上述したような、Ｈ、ＳおよびＥＷＧから選択した同一または異なるラジカルである。具体的な非制限的な例は、１，２−ベンゼンジチオール亜鉛塩；３，４−トルエンジチオール亜鉛塩；３，４，５，６−テトラクロロ−１，２−ベンゼンジチオール亜鉛塩、および１，２，４，５−ベンゼンテトラチオール二亜鉛塩を含む。 Suitable metal salts of aromatic ortho-thiols include those having the following general structural formula:

Where n is an integer of 1, 2, 4 or 6, m is an integer of 1 to 3, χ is an integer of 1 to 6, and the substituents R _{1 to} R ₄ are H, S and The same or different radicals selected from EWG. Specific non-limiting examples include 1,2-benzenedithiol zinc salt; 3,4-toluenedithiol zinc salt; 3,4,5,6-tetrachloro-1,2-benzenedithiol zinc salt, and 1 2,4,5-benzenetetrathiol dizinc salt.

  Other suitable additive groups include organic sulfur compounds (ie, having no sulfur-carbon covalent bonds, but covalent and / or ionic bonds between sulfur and non-carbon atoms such as O, N, P, Si, etc. Sulfur-containing compounds), non-metallic inorganic sulfur compounds (preferably non-metallic inorganic sulfides), inorganic thiols, metal sulfides, and derivatives thereof. Non-limiting examples of carbon-containing inorganic sulfur compounds include ammonium diethyl dithiophosphate; dithiophosphate diethyl ester; piperidine tetrathiotungstate, and glycol sulfite. Non-limiting examples of carbon-containing inorganic sulfides include: zinc di-n-butyldithiophosphate; bis (triphenyltin) sulfide; bis (diphenylphosphine) disulfide; diphenyltin sulfide; triphenylantimony sulfide; triphenylphosphine sulfide; 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide (Ravensson reagent, Lawesson's Reagent), and dithiobispentamethylcyclotrisiloxane. Non-limiting examples of suitable non-metallic inorganic sulfides include nitrogen sulfide; phosphorus pentasulfide; phosphorus trisulfide; iodo sulfide; iodo disulfide; polythiazyl or tetrathioic acid. Non-limiting examples of inorganic thiols include dithiophosphate diethyl ester; tetrathiotungstic acid; thiostannic acid; sodium hydrosulfide. Non-limiting examples of metal Phy include sodium polysulfide; barium sulfide; antimony (V) sulfide; and ammonium tetrathiomolybdate. Non-limiting examples of non-metallic inorganic sulfur compounds include sulfamide; sulfonyl dihydrazine; sulfur iodide, and ammonium thiosulfate.

  Other groups of suitable additives include halogenated hydrocarbons such as halogenated alkanes or halogenated alkenes, or halogenated alkynes, or aromatic-containing halogenated alkanes, which have EWG on the aromatic ring Including aromatic-containing halogenated aromatics. A non-limiting example of a suitable halogenated alkane is 1-bromooctadecane. Non-limiting examples of aromatic-containing halogenated alkanes include ortho, meta, or para-xylylene dibromide, or chlorotriphenylmethane.

  Other groups of suitable additives include inorganic halides (ie, having at least one covalent and / or ionic bond between halogen atoms and non-carbon atoms such as O, N, P, Si and metals, A halogen-containing compound which may or may not have a covalent bond between halogen and carbon, and includes carbon-containing inorganic halides. Non-limiting examples of inorganic halides are: zinc chloride; zinc iodide; iodosulfide; ruthenium (III) chloride hydrate; selenium oxychloride; sulfur iodide; tellurium dichloride; titanium (IV) chloride; ) Chloride; diphospharous tetraiodide; and hexachlorocyclotriphosphazene. Non-limiting examples of carbon-containing inorganic halides include bicyclo [2.2.1] hepta-2,5-diene-rhodium (I) chloride dimer; bis (cyclopentadienyl) zircon chloride; bis (cyclopenta Diphenyl) zircon chloride hydride; cyclopentadienyl titanium (IV) trichloride; diphenyliodonium iodide; diphenylselenium dichloride; diphenyldichlorosulfide; diphenyltin dichloride; N-bromosuccinimide; p-xylylenebis (triphenylphosphonium bromide); Pentafluorobenzenesulfenyl chloride; phenylselenyl bromide; polymer-bound selenium bromide; tellurium dichloride complex with thiourea (1: 2); tetraethylammonium bromide; triphenyl Rhenium chloride; triphenyl sulfur chloride; 1,2-phenylene phosphorous chloride; 3,5-dichlorobenzenesulfonyl chloride; dicyclopentadienyl titanium dichloride; orimethylphenylammonium iodide; tosyl chloride; trichloroisocyanic acid; Including benzene disulfonyl chloride; trichloromelamine; chlorotrimethylsilane; and diphenylphosphine chloride.

ただし、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９およびＲ_１０は、上述したようなＨ、ＥＷＧ、−ＳＺ、および−ＯＺから選択した同一または異なるラジカルである。一実施例では、Ｒ_１、Ｒ_３およびＲ_５の少なくとも１つ（例えば、２または３）、および／または、Ｒ_６、Ｒ_８およびＲ_１０の少なくとも１つ（例えば、２または３）は、同一または異なる、上述のようなＥＷＧである。他の実施例では、添加物はハロゲン化芳香族エーテルである。芳香族エーテルの非制限的な例は、１，３−ジフェノキシベンゼンである。ハロゲン化芳香族エーテルの非制限的な例は、４−ブロモフェニルエーテル；ペンタブロモフェニルエーテル；ペンタクロロフェニルエーテル、またはペンタルルオロフェニルエーテルを含む。 Another group of suitable additives are aromatic ethers (ie, compounds having at least one end ether bonded to an aromatic structure. Preferably, the aromatic structure is substituted with one or more of the above-described EWGs. More preferably, EWG is a halogen and / or a halogenated structure such as PEWG) and is a compound having the following general structural formula:

Provided that R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ were selected from H, EWG, —SZ, and —OZ as described above. The same or different radicals. In one example, at least one of R ₁ , R ₃ and R ₅ (eg 2 or 3) and / or at least one of R ₆ , R ₈ and R ₁₀ (eg 2 or 3) is Same or different EWG as described above. In other embodiments, the additive is a halogenated aromatic ether. A non-limiting example of an aromatic ether is 1,3-diphenoxybenzene. Non-limiting examples of halogenated aromatic ethers include 4-bromophenyl ether; pentabromophenyl ether; pentachlorophenyl ether, or pentarluorophenyl ether.

  Another group of suitable additives are acids or their derivatives. These include stannic acid, aliphatic sulfonic acids and salts thereof, halogenated aliphatic sulfonic acids and salts thereof, aromatic sulfonic acids and salts thereof, halogenated aromatic sulfonic acids and salts thereof, aromatic sulfinic acids and salts thereof , Halogenated aromatic sulfinic acid and its salt, inorganic sulfate, inorganic persulfate, inorganic sulfite, inorganic bissulfite, tetrathioic acid and its salt, inorganic thiosulfate, sulfamic acid and its salt, sulfanilic acid and its salt , Aromatic thiophthalate and its derivatives, thioaromatic acid, thiobarbituric acid, pyrrololidine carbodithioic acid and its salt, iodic acid and its salt, inorganic tetrathioic acid and its salt, aliphatic dithiophosphoric acid and its salt, aromatic Dithiocarbamic acid and its salts, aromatic carboxylic acids And salts thereof, halogenated aromatic carboxylic acids, halogenated carboxylic acids and salts thereof, and sulfuric acid and salts thereof. Non-limiting examples of stannic acid include metastannic acid, thiostannic acid, and chlorostannic acid. Non-limiting examples of aromatic sulfonic acids and salts thereof include methane sulfonic acid, or sodium mean sulfonate. Non-limiting examples of aliphatic sulfonic acids and salts thereof include trifluoromethane sulfonic acid; potassium salt of chloromethane sulfone, and zinc triflate. Non-limiting examples of aromatic sulfonic acids and salts thereof include benzene sulfonic acid; p-toluene sulfonic acid; or zinc tosylate. Non-limiting examples of suitable halogenated aromatic sulfonic acids and salts thereof include dichlorobenzene sulfonic acid and ammonium fluorobenzene sulfonate. Non-limiting examples of suitable aromatic sulfinic acids and salts thereof include benzenesulfinic acid; zinc benzenesulfinate; or sodium toluenesulfinate. Examples of suitable halogenated aromatic sulfinic acids and salts thereof include pentachlorobenzene sulfinic acid and zinc trichlorotoluene sulfinate. Non-limiting examples of suitable inorganic sulfides include calcium sulfide and ammonium sulfide. Non-limiting examples of inorganic persulfides include potassium persulfide and ammonium persulfide. Non-limiting examples of inorganic sulfites include sodium sulfite; ammonium sulfite; or potassium metabisulphite. Non-limiting examples of inorganic bisulfite include sodium bisulfite and zinc bisulfite. Non-limiting examples of tetrathioic acid and its salts include tetrathioic acid; sodium tetrathionate; and zinc tetrathionate. Non-limiting examples of inorganic thiosulfates include ammonium thiosulfate; barium thiosulfate; or calcium thiosulfate. Non-limiting examples of suitable sulfamic acids and salts thereof include sulfamic acid; ammonium sulfamate; and nickel sulfamate. Non-limiting examples of suitable sulfanilic acids and salts thereof include sulfanilic acid, sodium sulfanilate; and zinc sulfanilate. Non-limiting examples of aromatic thiophthalates and derivatives thereof include thiophthalic acid and thiophthalic anhydride. Non-limiting examples of thioaromatic acids include (3-phenylthio) acrylic acid and chlorophenylthioacetic acid. Non-limiting examples of thiobarbituric acid include 2-thiobarbituric acid. Non-limiting examples of pyrrololidine carbodithioic acid and its salts include 1-pyrrolidinecarbodithioic acid and ammonium pyrroluridine carbodithioate. Non-limiting examples of iodic acid and its salts include iodic acid; sodium iodate; and zinc iodate. Non-limiting examples of inorganic tetrathioacids and salts thereof include tetrathiotungstic acid; ammonium tetrathiotungstate, or piperidine tetrathiotungstate. Non-limiting examples of suitable aliphatic dithiophosphoric acids and salts thereof include dimethyldithiophosphoric acid and zinc di-n-butyldithiophosphate. Non-limiting examples of aromatic dithiophosphoric acid and its salts include diphenyldithiophosphoric acid and zinc diphenyldithiophosphate. Non-limiting examples of aliphatic dithiocarbamic acid and its salts are: dimethyldithiocarbamate; manganese ethylene bis (dithiocarbamate); manganese zinc ethylene bis (dithiocarbamate); disodium ethylenebis (dithiocarbamate); and zinc dibutyldithiocarbamate including. Non-limiting examples of aromatic dithiocarbamic acids or salts thereof include zinc ethylphenyldithiocarbamate. Non-limiting examples of aromatic carboxylic acids and salts thereof include benzoic acid; trimellitic acid; 4-hydrazinobenzoyl acid; phthalic acid; 4-hydrazinobenzoyl acid; phthalic acid; or zinc benzoate. Non-limiting examples of halogenated aromatic carboxylic acids and salts thereof include chlorobenzoic acid and zinc penachlorobenzoate. Non-limiting examples of halogenated carboxylic acids and salts thereof include trichloroacetic acid; trifluoroacetic acid; or sodium chloroacetate. Non-limiting examples of sulfate amides include sulfamide.

  Another group of additives suitable for enhancing CoR or reducing compression are organic selenium compounds, which include organic selenides (eg, diselenides and higher order polyselenides), organosernyl halides. , Aromatic seleno compounds (eg, aromatic selenides, (di) arylseleno compounds), and derivatives thereof, preferably including aromatic selenides, more preferably one or more disclosed herein. And those having an aromatic structure substituted with EWG, most preferably a halogenated aromatic selenide. A non-limiting example of an organic selenium compound is benzene selenol. A non-limiting example of an organic selenide compound is tetramethyltetraselenafulvalene. Non-limiting examples of aromatic selenides include diphenyl diselenide; phenyl selenide; and ditolyl diselenide. Non-limiting examples of halogenated aromatic selenides include pentachlorophenyl diselenide; pentafluorophenyl diselenide; and 4-bromophenyl diselenide.

  Another group of suitable additives are inorganic selenium compounds, which may or may not contain carbon atoms (ie selenium-containing compounds are selenium and non-carbon atoms such as O, N, P, Si And at least one covalent and / or ionic bond between the metal and the like, but no selenium-carbon covalent bond). Non-limiting examples of inorganic selenium compounds include selenium dioxide and selenium dichloride. A non-limiting example of a carbon-containing inorganic selenium compound is triphenylphosphine selenide.

  Another group of suitable additives are organic tellurium compounds, which include organic tellurides (eg, ditelluride), organotelluryl halides, and aromatic tellurium compounds (eg, (di) aryl telluro compounds), preferably Includes aromatic tellurides, more preferably those having an aromatic structure substituted with one or more EWGs disclosed herein, most preferably halogenated aromatic tellurides. Non-limiting examples of organic tellurium compounds include diphenyl ditelluride; phenyl telluride; and ditolyl ditelluride. Non-limiting examples of halogenated aromatic tellurides include pentachlorophenyl ditelluride; pentafluorophenyl ditelluride; and 4-bromophenyl ditelluride.

  Another group of suitable additives are inorganic tellurium compounds, which may contain less or more carbon atoms (ie tellurium containing compounds are tellurium and non-carbon atoms such as O, N, P, Si and Having at least one covalent and / or ionic bond with metals etc., but no tellurium-carbon covalent bond). Non-limiting examples of inorganic tellurium compounds include tellurium dioxide and tellurium dichloride. Non-limiting examples of carbon-containing inorganic tellurium compounds include triphenylphosphine tellurium and tellurium dichloride complexes with thiourea.

  Another group of suitable additives are organometallic coordination compounds, including unsaturated organometallic coordination compounds, which may be cyclic or acyclic. Non-limiting examples of cyclic organometallic coordination compounds include bicyclo [2.2.1] hepta-2,5-diene-rhodium (I) chloride dimer; (bicyclo [2.2.1] hepta-2 , 5-diene) dichlororuthenium (II) polymer; -rhodium (I) chloride dimer; bis (cyclopentadienyl) zirconium dichloride; bis (cyclopentadienyl) zirconium dichloride hydride; and cyclopentadienyl titanium (IV) Contains trichloride. Non-limiting examples of acyclic organometallic coordination compounds are 2,6,10-dodecatriene-1,12-diylnickel trifluoroacetic acid; 2,6,10-dodecatriene-1,12-diylnickel Fluoroacetate, and bis (π-allylnickel trifluoroacetate).

  Another group of suitable additives are aromatic iodonium compounds (eg, aromatic iodonium salts), preferably aromatic iodonium halides, optionally substituted with one or more of the above-described EWG aromatic structures. Have Non-limiting examples of aromatic iodonium compounds are: diphenyliodonium iodide; diphenyliodonium bromide; diphenyl chloride; diphenyliodonium nitrate; diphenyliodonium acetate; diphenyliodonium perchlorate; diphenyliodonium 9,10-dimethoxyanthracene-2-sulfonate Diphenyliodonium hexafluorophosphate; diphenyliodonium purfluoro-1-butanesulfonate; diphenyliodonium p-toluenesulfinate; diphenyliodonium triflate; and diphenyliodonium-2-carboxylate monohydrate.

  Another group of suitable additives are thiocyanate salts. Non-limiting examples of thiocyanate salts include ammonium thiocyanate and sodium thiocyanate.

  Another group of suitable additives are benzofurazan, including but not limited to benzofuroxane; benzofurazan dioxide; and benzofurazan.

  Another group of suitable additives is Verkade's Superbase, including but not limited to trimethylphosphatolane; and triisopropylphosphatolane.

  Another group of suitable additives are acyl halides. Non-limiting examples of acyl halides include oxalyl chloride; benzoyl chloride; and pentafluorobenzoyl chloride.

  Other suitable additives include iodine; chlorosulfonated polyethylene rubber; poly (4-vinylpyridinium dichromate) crosslinked with 2% DVB; tetraphenyltin; titanium isopropoxide; xanthone; and tris ( Triphenylphosphine) ruthenium hydrochloride.

  Other suitable groups are amino acids and derivatives thereof (eg aliphatic amino acids, aromatic amino acids, halogenated amino acids, amides thereof (eg corresponding cyclic amides, if any, addition products of hydroxyl-containing compounds), The peptide (eg, with one or more other amino acids, including polypeptides), conjugates (eg, S-conjugated, Se-conjugated, Te-conjugated, sulfide, diselenide, ditelluride, selenyl sulfide, telluryl) Sulfides, tereryl selenides), esters thereof (eg, alkyls such as methyl and ethyl, cycloalkyls, aryls), salts thereof (metal cations, organometallic cations, and non-metal cations, examples of which are disclosed herein) And those having amine and acid groups Is a variety of isomers].

  Non-limiting examples of sulfoamino acids include cysteine, S-alkyl (alkene) cysteine (eg S-methylcysteine, S-ethylcysteine, S-propylcysteine, S-butylcysteine, St-butylcysteine, S- Allylcysteine), γ-glutamyl-S-allylcysteine (eg, γ-glutamyl-S-methylcysteine, γ-glutamyl-S-propylcysteine, γ-glutamyl-S-allylcysteine), S-alkyl (alkene) cysteine Sulfoxides (eg, methine, ethyne, propyne, S-butylcysteine sulfoxide, alliin, asoallyin, S- (methylthiomethyl) cysteine sulfoxide), S-arylcysteine (eg, S-benzylcysteine, S-phenylcysteine), Rogenated sulfoamino acids (for example, S- (p-chlorobenzyl) cysteine, S- (p-bromophenyl) mercapturic acid, trifluoromethionine), pettibellin, 2-hydroxyethylcysteine, hydroxyethiin, S-allyl Mercaptocysteine, S-allylsulfonylalanine, N-acetyl-cysteine (mercapturic acid), penicillamine, (3,3-dimethylcysteine), S- [2- (4-pyridyl) ethyl)] cysteine, S- ( Carboxymethyl) cysteine, S-nitrosoglutathione, S-nitroso-N-acetyl-penicillamine, S-benzylcysteine, p-nitroanilide, S- [N- (3-phenylpropyl) (thiocarbamoyl)] cysteine, S- [N-benzyl (thiocarbamoyl)] Stain, S-tritylcysteine, S- (t-butylthio) cysteine, cysteine-S-sulfate, cysteine-glutathione disulfide, cysteinesulfinic acid, N, S- (dibenzyloxycarbonyl) cysteine, S- (acetamidomethyl) cysteine, S- (p-methoxybenzyl) cysteine, S- (p-methylbenzyl) cysteine, S- (t-butylthio) cysteine, N- (2-nitrophenylsulfenyl) alanine, N- (2-nitrophenylsulfenyl) ) Phenylalanine, methionine, methionine sulfoxide, methionine sulfone, methionine sulfoximine, methyl methionine, glycylmethionine, methionyl methionine, N- (2,4-dinitrophenyl) methionine, N- (2,4-dinito Phenyl) methionine sulfone, N-benzoylmethionine, N- (benzyloxycarbonyl) methionine, N-formylmethionine, N-phthaloylmethionine, ethionine, ethionine sulfoxide, ethionine sulfone, ethionine sulfoximine, prothionine, prothionine Sulfoximine, butionine, butionine sulfoxide, butionine sulfone, butionine sulfoximine, glutathione, S-hexylglutathione, S-nitrosoglutathione, diglutathione, lanthionine, pentionine, cysteinylglycine, glutamylcysteine, glutamylcystay Nilglycine, S-adenosylmethionine, homocystin, homocysteine, S- (2-amino-2-carboxylethyl) homocysteine, S-adeno Cysteine of lehomocysteine, homocysteine thiolactone, homocysteine sulfinic acid, homocysteic acid, S-phenylhomocysteine, N-acetyl-methionine, pentachloroaniline malcapturic acid, malonocysteine, pentachlorothiophenol (PCTP) Conjugates by PCTP, conjugation by malonocysteine, PCTP by pyruvate, PCTP by acetate, PCTP by S-glycoside, PCTP by glutamylcysteine, S- (pentachlorophenyl) cysteine , Cysteic acid, cysteine sulfinic acid, cysteic acid monohydrate, methionine sulfone, methionine sulfoxide, propionine, 4-amino-2-methylthio-5-thiazolecal Boronic acid, [14C, 15N] -2-amino-6- (methylthio) caproic acid, 1-amino-3- (methylthio) propyl phosphoric acid, 1-amino-3- (methylthio) propylphosphinic acid, (4- Amino-2-methyl-5-pyrimidinylmethylthio) acetic acid, 4- (2′-carboxy-2′-hydroxy-ethylthio) -2-peperidinecarboxylic acid, aminomercaptobenoic acid (eg, 3-amino-2- Mercaptobenzoic acid, 4-amino-3-mercaptobenzoic acid) and derivatives thereof (eg, those disclosed in US Pat. No. 5,847,147). This content is incorporated herein by reference), 2-aminohexanoic acid, 4-amino-2- (ethylthio) -5-pyrimidinecarboxylic acid, 2-amino-5- (2-propylthio) -1-pentanoic acid, 2-amino-3-mercapto-3-methylbutanoic acid, 2-mercapto-4methyl-5-thiazoleacetic acid, α-amino-β-mercapto-β, β-pentamethylenepropionic acid, 6-amino-2-mercapto- 5-methylpyrimidine-4-carboxylic acid, and derivatives thereof.

  Non-limiting examples of selenoamino acids include selenocysteine, Se-alkyl (alkene) selenocysteine (eg, Se-methylselenocysteine, Se-propylselenocysteine, Se-allylselenocysteine, Se-propenylselenocysteine, Se-2 -Methyl-2-propenylselenocysteine), γ-glutamyl-Se-alkyl (alkene) selenocysteine (eg, γ-glutamyl-Se-methylselenocysteine, γ-glutamyl-Se-propylselenocysteine, γ-glutamyl-Se) -Allylselenocysteine), Se-alkyl (alkene) selenocysteine selenoxide (eg Se-proponylselenocysteine selenoxide), Se-propynylselenocysteine, Se-arylselenocysteine (eg For example, Se-benzylselenocysteine, Se-phenylselenocysteine), Se-phenylselenohomocysteine, halogenated selenoamino acids (eg, Se- (p-chlorobenzyl) selenocysteine), Se-allylselenocysteine, (Se, Se-dimethylselenocysteine), Se- (carboxylmethyl) selenocysteine, selenoglutathione, selenodiglutathione, selenocysteine-cysteine selenyl sulfide, selenocysteine-glutathione selenyl sulfide, selenocysteine selenol, selenocysteine selenoic acid, seleno Cysteine selenoic acid, Se- (p-methoxybenzyl) selenocysteine, Se- (p-methylbenzyl) selenocysteine, Se-n-butylselenocysteine, Se- (p -Methoxybenzyl) selenocysteine, selenocystine, selenocystamine, sulfoselenocystine, N-tert-butoxycarbonyl-selenocystine, selenocystine-Se-methylselenocysteine, selenocystathionine, cystine selenotrisulfide, selenocysteic acid, selenomethionine Selenoxide, selenomethionine selenone, Se-methylselenomethionine, Se-adenosylselenone methionine, selenoethionine, γ-glutamyl-selenoethionine, selenoglutathione, selenodiglutathione, selenolanthionine, γ-glutamyl-selenocysteinylglycine di Selenide, selenohomocystine, selenohomocysteine, Se-adenosylselenohomocysteine, selenogamma-aminobutyric acid, and And seleninoalanine.

  Non-limiting examples of telluroamino acids include tellurocysteine, tellurocystine, telluromethionine, aromatic telluroamino acids (eg, Te-phenyl tellurohomocysteine, Te-phenyl tellurohomocystine), and halogenated telluroamino acids.

Another group of additives are boron-containing compounds, which may be substituted or unsubstituted (eg, non-halogenated or non- (per) halogenated) and are not limited thereto. , borane (e.g., BR _3, or a BR _3, first organic, diorgano, and third organic borane compound), and boric acid, such as borates (B _{(oR) 3,} sulfur-substituted borates and Amine borate esters B (OR ″) ₃ N), boronates (boronates such as R′B (OR) ₂ , functional boronates YR ″ B (OR) ₂ and diboronates Y ′ [R ″ B ( _{oR) 2]} containing _2), containing boric acid, such as borinate (R _'2 B (oR)), dioxaborolan, dioxaborinane, and these metal and non-metal salts (fourth organic borane anion _R 4 B ^- the free Wherein R and R ′ are H and a straight chain having up to 40 (eg, 1-20, 1-10, 1-8, 1-6 or 1-3) carbon atoms. Chain, branched and / or cyclic radicals (eg alkyl (alkenyl), aryl, aralkyl (aralkenyl), alkaryl (alkene aryl), eg alkyl (alkenyl) phenyl, cycloalkyl (alkenyl), alkyl (alkenyl) cyclo The same or different monovalent radicals selected from alkyl (alkenyl), cycloalkyl (alkenyl) alkyl (alkenyl), and combinations thereof) and additionally one or more heteroatoms (eg O, N, S , P, Si) and additionally substituted with one or more of the above-mentioned EWGs; R ″ is 20 or less Straight chain carbon atoms, branched and / or cyclic radical _(e.g., alkylene _{C 1-15} or _{C 1-3 (alkenylene),} the _{C 6-10} (alkyl) _arylene, a _{C 6-10} (alkyl) The same or different divalent radicals selected from cycloalkylene (alkenylene), and combinations thereof, additionally containing one or more heteroatoms and additionally substituted with one or more EWG as described above Y is a functional group selected from AZ, thiocyano (—SCN), epoxy, glycidyl, epithio, vinyl, allyl, and amine (first or second) as described above; Y ′ is a polysulfide S _y or a divalent radical selected from polyselenides Se _y, y is an integer from 1, 2, 3, 4, and 8. Preferably, the one or more carbons that honor the C—O—B bond are the second and / or third carbons and sterically hinder the hydrolysis. Boron-containing compounds may or may not be used with amine-based compounds such as those disclosed herein.

Non-limiting examples of borane include triphenylphosphine borane, dibutoxyvinyl borane, decaborane, morpholine borane, dichlorophenyl borane, dibromophenyl borane, tris (2,4,6-trimethylphenyl) borane. Borane salts include metal salts (eg, with Na, Li, K, Mg, Zn, Co, Ca cations) and non-metallic salts (eg, quaternary ammonium, quaternary pyridinium, quaternary quinolinium, ( (Organo) phosphonium, (organo) sulfonium, (organo) oxonium, (organo) iodonium, (organo) azonium, for example, tetrabutylammonium, tetramethylammonium, tetraethylammonium, tributylamine, triethanolamine, methylpyridinium, ethylpyridinium, Butylpyridinium, methylquinolinium, ethylquinolinium, butylquinolinium) and having an anion of R ₄ B ⁻ . At least one R in the anion may be an aryl, aralkyl, or alkaryl group, optionally with one or more substituents (eg, descriptive EWG, linear or branched C _1-6 alkyl, EWG or non- EWG substituted alkyl, phenyl, EWG or non-EWG substituted phenyl). The remaining R in the anion are the same or different groups selected from alkyl (alkenyl), aryl, aralkyl, alkaryl (alkene aryl), cycloalkyl (alkenyl) alkyl (alkenyl), optionally as described above One or more substitutions. Non-limiting examples of anions include one aryl group (eg, trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, trialkyl (p-fluorophenyl) boron, trialkyl (3,5-bistrifluoromethyl). ) Phenyl boron, trialkyl [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, trialkyl (p-nitrophenyl) boron, Trialkyl (m-nitrophenyl) boron, trialkyl (p-butylphenyl) boron, trialkyl (m-butylphenyl) boron, trialkyl (p-butyloxyphenyl) boron, trialkyl (m-butyloxyphenyl) Boron, trialkyl (p-octyloxyphenyl) boron, trialkyl (M-octyloxyphenyl) boron) and two aryl groups (eg dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, dialkyldi (3,5-bistrifluoromethyl) ) Phenyl boron, dialkyldi [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyldi (p-nitrophenyl) boron, dialkyldi (M-nitrophenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi (p- Octyl Oki Phenyl) boron, dialkyldi (m-octyloxyphenyl) boron); three aryl groups (eg monoalkyltriphenylboron, monoalkyltris (p-chlorophenyl) boron, monoalkyltris (p-fluorophenyl) ) Boron, monoalkyltris (3,5-bistrifluoromethyl) phenylboron, monoalkyltris [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2- Propyl) phenyl] boron, monoalkyltris (p-nitrophenyl) boron, monoalkyltris (m-nitrophenyl) boron, monoalkyltris (p-butylphenyl) boron, monoalkyltris (m-butylphenyl) boron, Monoalkyltris (p-butyloxyphenyl) ) Boron, monoalkyltris (m-butyloxyphenyl) boron, monoalkyltris (p-octyloxyphenyl) boron, monoalkyltris (m-octyloxyphenyl) boron) and four aryl groups (eg , Tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl) phenylboron, tetrakis [3,5-bis (1,1,1,3 , 3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis (m-nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis ( m-butylphenyl) boron, tetrakis p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis (p-octyloxyphenyl) boron, tetrakis (m-octyloxyphenyl) boron), where the alkyl group is Linear or branched C _1-20 alkyl (eg, n-butyl, n-octyl, n-dodecyl) or a salt thereof (eg, sodium tetraphenylboron).

  Non-limiting examples of borates include alkyl borates (e.g., trimethyl borate, triethyl borate, tris (2-chloroethyl) borate, tris (2-aminoethyl) borate, tri ( n-propyl) borate, triisopropylborate, tri (n-butyl) borate, triisobutylborate, tri (sec-butyl) borate, tri (t-butyl) borate, Tri (n-pentyl) borate, trihexylborate, tris (4-methyl-2-pentyl) borate, tris (2-ethylhexyl) borate, trioctylborate, tris (1- Methylheptyl) borate, tris (2-methylheptyl) borate, tris (2,6-dimethyl-4-heptyl) borate, tridecylborate, tridodecylborate, triocta Sylborate, tris (2-dimethylaminoethyl) borate) and cycloalkylborate (e.g., tricyclohexylborate, tri (2-cyclohexylcyclohexyl) borate, di (n-butyl) [ 2,6-di (t-butyl) -4-methylphenyl] borate); and (alkyl) arylborate (eg, triphenylborate, tri (o-tolyl) borate, tri (m , P-cresyl) borate, tri (o-chlorophenyl) borate, tri (nonylphenyl) borate, dihydrogen nonylphenylborate); alkenylboric acid (eg triallylborate); Cyclic esters of acids (eg glycerol borate, triethylamine glycerol borate, monoethanolamine glycerol borate, triethanol Luamine glycerol borate (boratrane), tripropanolamine borate, triisopropanolamine borate, and alkanolamines, alkane polyols, and cycloalkane polyols such as propane-1,3-diol, phenylethane-1 , 2-diol, ethyl-2,4-dimethylpentane-2,4-diol and 2-ethyl-2hydroxymethyl-1,3-propanediol); amine borates (eg, boro-tetra-n -Propylate, tri (n-propyl) borate, and those disclosed herein) and / or borane (eg, dimethylamine borane, pyridine borane, trimethylamine borane, triethylamine borane), trimethylamine-N-ethamidoborane, [bis (2- Chloroethyl) amino] bis (o-hydroxyphenoxy) borane, tris [bis2-chloroethyl) amino] borane, ethylenediaminebisborane, t-butylamineborane, hexamethylenetetramineborane, N, N-dimethylbenzylamineborane, tetrakis (dimethyl) Including addition compounds with (amino) diborane (eg tertiary alkyl primary amines, as disclosed herein).

  Non-limiting examples of boronates and boronic acids include 4-borono-benzoic acid, 3-ethoxycarbonylphenylboronic acid, 3-soproxycarbonylphenylboronic acid, m-nitrophenylboronic acid, p-bromophenylboronic acid, p-chlorophenylboronic acid, m- or p-benzenediboronic acid, nonylboronic acid, o-phenylene-benzeneboronic acid, 2,2'-stilbeneboronic acid, p-bromophenylboronic acid, p-tolylboronic acid, phenylboron Acid, 1-naphthaleneboronic acid, 1-hexaneboronic acid, 1-naphthaleneboronic acid, 1-propaneboronic acid, 1-pentaneboronic acid, ferroceneboronic acid, 1-naphthaleneboronic acid, (2-phenylthioethenyl) Dibutylboronic acid, 2-mesityleneboronic acid, 2,2′-dimethoxybifu Nyl-5-boronic acid, 1-naphthaleneboronic acid, 2-chloro-4-fluorophenylboronic acid, 2-chloro-4-trifluoromethylphenylboronic acid, 2-chloro-4-iodophenylboronic acid, 2- Methoxyphenylboronic acid, 2- (methylthio) phenylboronic acid, 2-naphthaleneboronic acid, 2-thiopheneboronic acid, tolylboronic acid, 3-carboxylphenylboronic acid, 3-chlorophenylboronic acid, 3-chloro-4-fluorophenyl Boronic acid, 3-fluorophenylboronic acid, 3-methoxyphenylboronic acid, 3- (methylthio) phenylboronic acid, 3-tolylboronic acid, 3- (trifluoromethyl) phenylboronic acid, 4-biphenylboronic acid, 4- Bromophenylboronic acid, 4-bromo-2,3-difluorophenylbo Acid, 4-carboxylphenylboronic acid, 4-chlorophenylboronic acid, 4-cyanophenylboronic acid, 4-fluorophenylboronic acid, 4-fluoro-3-methylphenylboronic acid, 4-methoxyphenylboronic acid, 4- (Methylthio) phenylboronic acid, 4-tolylboronic acid, 4- (trifluoromethoxy) phenylboronic acid, 5-fluoro-2-methylphenylboronic acid, 5-indolylboronic acid, 2,4-dichlorophenylboronic acid, 2 , 4-Difluorophenylboronic acid, 2,4-dimethylphenylboronic acid, 3,4-dichlorophenylboronic acid, 3,4-difluorophenylboronic acid, 3,4-dimethylphenylboronic acid, 3,5-bis (tri Fluoromethyl) phenylboronic acid, 3,5-dichlorophenylboronic acid, 3,5 -Difluorophenyl boronic acid, including 3,4,5-trifluorophenyl boronic acid.

  Non-limiting examples of heterocyclic compounds having at least one boron atom as a ring member include dioxaborol (eg, catecholborane (1,3,2-benzodioxaborol), 2- (5,6-dichlorophenyl) ) -1,3,2-benzodioxaborole, 2- (5,6-dichloro-4-methylthiophenyl) -1,3,2-benzodioxaborole, 2,4,5-triphenyl- 1,3,2-dioxaborole); and dioxyborolane (eg, 2-methoxy-1,3,2-benzodioxaborolane, 2-isopropoxy-4,4,5,5, -tetramethyl-1,3) , 2-dioxaborolane, 4-hydroxymethyl-1,3,2-dioxaborolane-ol, (2-isopropoxy-1,3,2-dioxaborane-4-yl) methanol, [2- (4- Droxymethyl-1,3,2-dioxaborolan-2-yloxy) -1,3,2-dioxaborolan-4-yl] methanol, bispinacolatobiborate, 2-bis (2-chloroethyl) amino-1,3,2 -Dioxaborolane, [2-1,3,2-dioxaborolane-2-yloxy) ethyl] dimethylamine, [2- (2,4,6,9-tetraoxa-5-bora-spiro [4,4] nonane, 2 , 7-di (t-butylaminomethyl) -2,4,6,9-tetraoxa-5-bora-spiro [4,4] nonane) and dioxaborinane (for example, tripropylene glycol biborate, dibutylene glycol bibo) Rate, tributylene glycol biborate, hexylene glycol biborate, trihexylene glycol biborate, 1,2-di Xabolinan, 2-butyl-1,3,2-dioxaborinane, 1,3,2-dioxaborinan-2-ol, 4-methyl-1,3,2-dioxaborinan-2-ol, 4,4,6-trimethyl- 1,3,2-dioxaborinan-2-ol, 2-isopropoxy-1,3,2-dioxaborinane, 2-isopropoxy-4-methyl-1,3,2-dioxaborinane, 2-isopropoxy-4,4 , 6-Trimethyl-1,3,2-dioxaborinane, 2-bis (2-chloroethyl) amino-1,3,2-dioxaborinane, [2- (1,3,2-dioxaborinan-2-yloxy) ethyl] dimethyl Amines, [2- (4-methyl-1,3,2-dioxaborinan-2-yloxy) ethyl] dimethylamine, [2- (4,4,6-trimethyl- 1,3,2-dioxaborinan-2-yloxy) ethyl] dimethylamine, 2,2′-bis (5,5-dimethyl-1,3,2-dioxaborinane), 2,2′-oxybis (1,3,3) 2-dioxaborinane), 2,2′-oxybis (4,4,6-trimethyl-1,3,2-dioxaborinane), 2,2 ′-(methyltrimethylenedioxy) bis (4-methyl-1,3) , 2-dioxaborinane), 5-methyl-5-propyl-2- (p-tolyl) -1,3,2-dioxaborinane, 2-hydroxy-4,4,6-trimethyl-1,3,2-dioxaborinane) Or dithiaborolane (eg 2-methyl-dithiaborolane, 2-methylthio-dithiaborolane, 2-chloro-dithiaborolane) or dithiaborinane (eg 2-chloro-1,3, -Dithiaborinane, 2-bis (2-chloroethyl) amino-1,3,2-dithiaborinane); and boroxine (for example, boroxine, tributylboroxine, trimethoxyboroxine, triphenylboroxine, tris (cyclohexyloxy) boroxine) And borazine (eg, borazine, trimethylborazine, 2,4,6-trichloroborazine, 2,4,6-trimethyl-1,3,5-triphenylborazine).

  Other boron-containing compounds include boron-containing organosulfides (eg, B-nonyl-bis (octylphenol) sulfide), borinates (eg, o- (2-aminoethyl) diphenylborinate), and metal salts of boron complexes and Non-metallic salts (eg, dipentylammonium tetrafluoroborate, dibutylammonium tetrafluoroborate, sodium tetraisopropoxyborate, trityltetrafluoroborate, ammonium boron fluoride, cetyltrimethylammonium borohydride, methyltrioctylammonium borohydride, tetraethylammonium borohydride Sodium borofluoride, tetrapropylammonium tetrafluoroborate, triphenylsulfonium tetrafluoroborate Chromatography, diphenyl iodonium tetrafluoroborate, tri (p- tolyl) sulfonium tetrafluoroborate, rubidium tetrafluoroborate, mono -N- butyl ammonium tetrafluoroborate, sodium tetramethoxyborate, sodium borohydride F script sulphonate).

Another group of additives are Si-containing compounds, including but not limited to, those having the structure R _x SiR ′ _4-x or S _y [(R ″) _z G] ₂ Where R is the same or selected from H, halogen (eg F, Cl, Br, I), linear or branched C _1-8 or C _2-4 alkyl, aryl, aralkyl, and vinyl; Different monovalent radicals; R ′ is halogen, hydroxyl, linear or branched C _1-8 or C _2-4 oxyalkyl, C _{5-10 oxycycloalkyl} , oxyaryl, oxyarylalkyl, And the same or different monovalent radicals selected from oxyvinyl; R ″ is the same or different divalent radicals, preferably linear or branched C _1-18 A divalent hydrocarbon, for example C _1-18 or C _2-4 alkylene, optionally having one or more heteroatoms (eg O, N, S); G is the same or different Si Containing monovalent radicals, for example, substituted or unsubstituted (cyclo) (poly) (alkyl) siloxanes, or silyl groups of —Si (R _x ) (R ′ _3-x ), wherein R And R ′ is as described above, x is an integer of 0, 1, 2, or 3, y is an integer of 1, 2, 3, or 4, and is an integer up to 8, and z is 0 or 1. .

  Non-limiting examples of oxyalkyl silanes include tetramethoxy silane, tetraethoxy silane, tetraisopropoxy silane, tetrabutoxy silane, tetraoctyl silane, methyl trimethoxy silane, methyl triethoxy silane, methyl triisopropoxy silane, ethyl tri Methoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trimethoxysilane, triethoxy Silane, Triisopropoxysilane, Fluorotrimethoxysilane, Fluorotriethoxysilane, Dimethyldimethoxysilane, Dimethyldiethoxysilane, Diethyl Dimethoxysilane, diethyl diethoxysilane, dimethoxysilane, diethoxy silane, difluoro dimethyl Toshiki silane, difluoro diethyl Toshiki silane, trifluoromethyl trimethoxysilane, and includes trifluoromethyl triethoxysilane.

  Non-limiting examples of halogenated silanes include trichlorosilane, tribromosilane, fluorotrichlorosilane, methyltribromosilane, ethyltrichlorosilane, chlorotrimethylsilane, fluorotrimethylsilane, vinyltrichlorosilane, and phenyltrichlorosilane .

  Non-limiting examples of sulfur-containing silico compounds include dithiobis (pentamethylcyclotrisiloxane), 3,3′-bis (trimethoxysilylpropyl) disulfide, 3,3′-bis (triethoxysilylpropyl) disulfide, 3,3′-bis (triethoxysilylpropyl) tetrasulfide, 3,3′-bis (triethoxysilylpropyl) tetrasulfide, 3,3′-bis (triethoxysilylpropyl) octasulfide, 3,3′- Bis (trimethoxysilylpropyl) tetrasulfide, 2,2′-bis (triethoxysilylethyl) tetrasulfide, 3,3′-bis (trimethoxysilylpropyl) trisulfide, 3,3′-bis (triethoxysilyl) Propyl) trisulfide, 3,3′-bis (tributoxysilyl) Propyl) disulfide, 3,3′-bis (trimethoxysilylpropyl) hexasulfide, 3,3′-bis (trimethoxysilylpropyl) octasulfide, 3,3′-bis (trioctoxysilylpropyl) tetrasulfide, 3,3′-bis (trihexoxysilylpropyl) disulfide, 3,3′-bis (tri-2 ″ -ethylhexoxysilylpropyl) trisulfide, 3,3′-bis (triisooctoxysilylpropyl) Tetrasulfide, 3,3′-bis (tri-t-butoxysilylpropyl) disulfide, 2,2′-bis (methoxydiethoxysilylethyl) tetrasulfide, 2,2′-bis (tripropoxysilylethyl) pentasulfide 3,3′-bis (tricyclohexoxysilylpropyl) tetra Rufide, 3,3′-bis (tricyclopentoxysilylpropyl) trisulfide, 2,2′-bis (tri-2 ″ -methylcyclohexoxysilylethyl) tetrasulfide, bis (trimethoxysilylmethyl) tetrasulfide, 3-methoxyethoxypropoxysilylpropyl-3'-diethoxybutoxysilylpropyl-tetrasulfide, 2,2'-bis (dimethylmethoxysilylethyl) disulfide, 2,2'-bis (dimethyl-sec-butoxysilylethyl) tri Sulfide, 3,3′-bis (methylethylbutoxysilylpropyl) tetrasulfide, 3,3′-bis (di-t-butylmethoxysilylpropyl) tetrasulfide, 2,2′-bis (phenylmethylmethoxysilylethyl) Trisulfide, 3,3'- Bis (diphenylisopropoxysilylpropyl) tetrasulfide, 3,3′-bis (diphenyldichlorohexoxysilylpropyl) disulfide, 3,3′-bis (dimethyl-ethylmercapto-silylpropyl) tetrasulfide, 2,2′- Bis (methyldimethoxysilylethyl) trisulfide, 2,2′-bis (methyl-ethoxypropoxysilylethyl) tetrasulfide, 3,3′-bis (diethylmethoxysilylpropyl) tetrasulfide, 3,3′-bis (methyl) -Di-sec-butoxysilylpropyl) disulfide, 3,3'-bis (propyldiethoxysilylpropyl) disulfide, 3,3'-bis (butyldimethoxysilylpropyl) trisulfide, 3,3'-bis (phenyldimethoxy) Silylpropyl Tetrasulfide, 3-phenylethoxybutoxysilylpropyl-3′-trimethoxysilylpropyl-tetrasulfide, 4,4′-bis (trimethoxysilylbutyl) tetrasulfide, 6,6′-bis (triethoxysilylhexyl) tetra Sulfide, 12,12′-bis (triisopropoxysilyldodecyl) disulfide, 18,18′-bis (trimethoxysilyloctadecyl) tetrasulfide, 18,18′-bis (tripropoxysilyloctadecyl) tetrasulfide, 4,4 '-Bis (trimethoxysilyl-butan-2-yl) tetrasulfide, 4,4'-bis (trimethoxysilylchloroxylene) tetrasulfide, 5,5'-bis (methyldimethoxysilylphenyl) trisulfide, 3 , 3'-bis Trimethoxysilyl-2-methylpropyl) tetrasulfide, including 3,3'-bis (phenyl dimethoxy silyl-2-methylpropyl) disulfide.

  Another group of additives is 1, 2, 3 or more unsaturated moieties (eg, vinyl, allyl, isopropenyl, each having at least one easily removable hydrogen at the α-position of the unsaturated bond. Group, acryloyl group, methacryloyl group, acrylamide group, methacrylamide group) and a crosslinkable and / or polymerizable compound. Such additives may be acid or non-acid, sulfur-free, may contain one or more heteroatoms (eg, O, N, S, P, Si), aliphatic, alicyclic, Or may be aromatic, mono-, di-, poly-ester, mono-, di-, poly-amide, mono-, di-, poly-ester amide, bismaleimide, organic salts thereof (for example, cation ( Organic) ammonium), and their metal salts (eg, cations Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ti, Zr, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ir, Cu, Zn, Cd, Al), and liquid vinyl polydiene.

  Acid crosslinkable and / or polymerizable compounds may have one or more acid moieties selected from, but not limited to, carboxyl groups, sulfonico groups, sulfinico groups, phosphono groups, phosphinico groups, and acid anhydride radicals. Acrylic acid, methacrylic acid, ethacrylic acid, propylacrylic acid, other alkyl acrylic acids, mono-, poly-unsaturated fatty acids, unsaturated polyacids described in US patent application Ser. No. 10 / 895,537, and their anhydrides And the contents of that patent document are incorporated herein by reference. Non-limiting examples of acid organosulfur compounds and acid organophosphorus compounds include vinyl sulfonic acid, vinyl phosphonic acid.

および

（ｘ、ｙおよびｚは０、１、２、・・・高々１０の独立の整数であり、かつ、ｘ＋ｙ＋ｚの平均数が１以上、または３．５以上である）
および、これらの２以上の組み合わせを含む。Ａの非制限的な例は、−ＣＯＯＨ、−ＣＨ（ＣＯＯＨ）_２、−Ｓ０_３Ｈ、−ＯＰＯ_３Ｈ_２，＝Ｏ_２ＰＯ_２Ｈ、すなわち

−ＯＰ（Ｏ_２Ｈ）ＯＰｈ、すなわち、

−Ｃ_８Ｈ_４Ｏ_３、すなわち、

−Ｃ_６Ｈ_３（ＣＯＯＨ）_２、すなわち、

およびこれらの２以上の組み合わせを含む。 One group of acid crosslinkable and / or polymerizable compounds has the structure [X (L) _p R] _m [(L) _q A] _n . Wherein X is the same or different divalent radicals that are crosslinkable and / or polymerizable; L is the same or different divalent radical, preferably —COO— or —CONH—; R Are the same or different radicals having a valence of 2, 3 or 4 up to 6 and having 1 to 30 carbon atoms, optionally having ether, ester and / or amide linkages, and A being the same Or different monovalent or divalent radicals; m and n are integers independently selected from 1, 2, 3, 4 to at most 8, and m + n is 2, 3, or 4 to at most 10 P is the same or different number selected from 0 or 1; q is the same or different number selected from 0 or 1. Non-limiting examples of X are C _2-10 alkenes of the same or different numbers selected from linear, branched, or cyclic 0 or 1, such as vinyl, allyl, asoallyl, propenyl, and Contains isopropenyl. Non-limiting examples of R are —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₆ —, — (CH ₂ ) ₈ —, — (CH ₂ ) ₁₀ -,-(CH ₂ ) ₂₀ -,-(CH ₂ ) ₂ O (CH ₂ ) ₂ -,-(CH ₂ ) ₂ O [O (CH ₂ ) ₂ ] ₂ -,-(CH ₂ ) _{2 OCO (CH 2) 2 COO (} CH 2) 3 -,

and

(X, y and z are 0, 1, 2,... At most 10 independent integers, and the average number of x + y + z is 1 or more, or 3.5 or more)
And combinations of two or more thereof. Non-limiting examples of _{A, -COOH, -CH (COOH) 2} , -S0 3 H, -OPO 3 H 2, = O 2 PO 2 H, i.e.

-OP _(O 2 H) OPh, i.e.,

-C ₈ H ₄ O _3, i.e.,

_{-C 6 H 3 (COOH) 2} , i.e.,

And combinations of two or more thereof.

および、これらの２以上の組み合わせ（例えば、Ｐ含有酸化合物およびカルボキシル含有酸化合物の組み合わせ）を含む。 Non-limiting examples of acid compounds in the above structures are CH ₂ ═C (R) CONH (CH ₂ ) ₂ COOH, CH ₂ ═C (R) CONH (CH ₂ ) ₁₀ (COOH) ₂ , CH _{2 = CHC 6 H 4 CH 2 COOH} , CH 2 = C (R) COO (CH 2) 8 CH (COOH) 2, CH 2 = C (R) COO (CH 2) 10 CH (COOH) 2, CH 2 = _{CHC 6 H 4 COOH, CH 2} = C (R) CONH (CH 2) 2 OPO 3 H 2, CH 2 = C (R) COO (CH 2) 12 CH (COOH) 2, CH 2 = CHC 6 H 4 _{(CH 2) 2 COOH, CH} 2 = C (R) COO (CH 2) 2 OCNC 6 H 3 (COOH) 2, CH 2 = C (R) COO (CH 2) 2 OPO 3 H 2, CH 2 = CHC ₆ H _{SO 3 H, CH 2 = C} (R) COO (CH 2) 2 OCOC 8 H 4 O 3, CH 2 = C (R) COO (CH 2) 2 OP (O 2 H) OPh, CH 2 = CHC 6 _{H 4 CH 2 SO 3 H,} [CH 2 = C (R) COO (CH 2) 2 O] 2 CHOCOC 6 H 3 (COOH) 2, [CH 2 = C (R) COO (CH 2) 2 O] _{3 COCOC 6 H 3 (COOH)} 2, CH 2 = C (R) COO (CH 2) 2 OCO (CH 2) 2 COOCH 2 CH [CH 2 OCOC (R) = CH 2] OCOC 6 H 3 (COOH) _{2, [CH 2 = C (} R) COOCH 2 CH [OCOC 6 H 3 (COOH)] CH 2 OCH 2] 2, CH 2 = C (R) CONH (CH 3) 2 CH 2 SO 3 H, [CH ₂ = C (R) C _{O (CH 2) 2 O]} 2 C [CH 2 OCOC 6 H 3 (COOH) 2] 2, CH 2 = C (R) COOC (CH 3) 2 CH 2 SO 3 H, [CH 2 = C (R _{) COO (CH 2) 2 O} ] 2 PO 2 H, CH 2 = C (R) CONH (CH 2) 2 SO 3 H, CH 2 = C (R) COO (CH 2) 10 SO 3 H, CH 2 _{= C (R) COO (CH} 2) 2 SO 3 H, CH 2 = C (R) COO (CH 2) 6 SO 3 H, CH 2 = C (R), CH 2 = C (R) COOC 6 H ₄ SO ₃ H, and

And combinations of two or more thereof (for example, a combination of a P-containing acid compound and a carboxyl-containing acid compound).

  The above-mentioned salts of acid compounds are another group of crosslinkable and / or polymerizable compounds. Suitable cations of such salts herein include any and all of those disclosed herein, including, for example, metal cations and amino-based cations. The metal cation can be derived by reacting an acid compound with a monovalent and / or divalent metal oxide. Other salts can, for example, react divalent metal oxides with a) monobasic unsaturated carboxylic acids, such as acrylic acid and / or methacrylic acid, and / or b) mono- or polyunsaturation. And reaction products reacted with dibasic and / or polybasic carboxylic acids, and / or their anhydrides, such as those described in US Pat. No. 6,656,483. The contents of this patent document are incorporated herein by reference. Non-limiting examples include zinc diacrylthioic acid.

The acid compounds disclosed herein can be concentrated with polyamines (foamable polyamides), polyols (foamable polyesters), or amino alcohols (foamable ester amides) to make them suitable for use in the formulations disclosed herein. Acid multifunctional crosslinkable and / or polymerized compounds can be produced. Non-limiting examples of unsaturated carboxylic acid condensates include ethylene glycol diacrylate (methacrylate), diethylene glycol diacrylate (methacrylate), triethylene glycol diacrylate (methacrylate), tetraethylene glycol diacrylate (methacrylate), nonaethylene glycol Diacrylate (methacrylate), polyethylene glycol diacrylate (methacrylate), propylene glycol diacrylate (methacrylate), dipropylene glycol diacrylate (methacrylate), tripropylene glycol diacrylate (methacrylate), neopentyl glycol diacrylate (methacrylate), 1 , 4-Butanediol diacrylate (methacrylate), 1,6-hexa Diol diacrylate (methacrylate), 1,9-nonanediol diacrylate (methacrylate), trimethylpropane diacrylate (methacrylate), trimethylolpropane triacrylate (methacrylate), glyceryl diacrylate (methacrylate), glyceryl triacrylate (methacrylate), Pentaerythritol diacrylate (methacrylate), pentaerythritol triacrylate (methacrylate), pentaerythritol tetraacrylate (methacrylate), urethane diacrylate (methacrylate), epoxy acrylate (methacrylate), bisphenol A diglycidyl ether diacrylate, allyl diacrylate (methacrylate) ), 2,2′-bis [4-acryl Yl (methacryloyl) oxyethoxyphenyl] propane, 2,2′-bis [4-acryloyl (methacryloyl) oxyethoxyethoxyphenyl] propane, 2,2′-bis {4- [3-acryloyl (methacryloyl) oxy-2- Hydroxypropoxy] phenyl} propane.
Non-limiting examples of bismaleimides include N, N′-m-phenylene dimaleimide (HVA-2 available from Dupont). Non-limiting examples of allyl esters include triallyl cyanurate (Akrosorb 19203 available from Akrochem, Akron, Ohio), triallyl isocyanurate (Akrosorb 19251 available from Akrochem), and triallyl trimerate ( TATM available from Sartomer, Exton, Pennsylvania). Non-limiting examples of mono- or polyunsaturated polycarboxylic acids and derivatives thereof include citraconic acid, itaconic acid, fumaric acid, maleic acid, mesaconic acid, aconitic acid, maleic anhydride, itconic anhydride, citraconic anhydride, Polyacrylic (methacrylic) acid, polyitaconic acid, copolymers of acrylic (methacrylic) acid and maleic acid, copolymers of acrylic (methacrylic) acid and styrene, and C ₆ or longer chain fatty acids such as hexadecene diacid, octadecene di Acids, vinyl-tetradecenedioic acid, eicosdienic diacid, dimethyl-eicosdienic diacid, 8-vinyl-10-octadecenedioic acid, their anhydrides, methyl, ethyl, and other linear or branched alkyl esters thereof, These amides, these ester amides, Including these mixtures.

  Liquid vinyl polydienes are liquid at room temperature, for example, liquid vinyl polybutadiene homopolymers and copolymers (eg, having a vinyl-1,2 content of at least 60%, or at least 65%), low to moderate May have a molecular weight of from about 1000 to about 5000, such as from about 1800 to about 4000, or from about 2000 to about 3500. The liquid vinyl polydiene has a content of 90% vinyl-1,2 and a high vinyl polybutadiene with a molecular weight of about 3200, a content of 70% vinyl-1,2 and a molecular weight of about 2400. High vinyl polybutadiene, having a content of 70% vinyl-1,2, and having a molecular weight of about 3200 high vinyl poly (butadiene-styrene) butadiene, and other liquid vinyl polymers disclosed herein.

を含み、ここで、Ｒ”は、ＨまたはＣ_１−６のアルキルであり、さらに、

を含む。そのような有機硫黄の非制限的な例は、上記の構造のチオエーテルおよびポリスルフィド、および、アクリルオキシ−４−チオフェノール、亜鉛アクリルオキシチオフェノール、ビス（４−アクリルオキシベンゼン）ジスルフィド、ジアリルジスルフィド、ジアリルトリスルフィド、メチルアリルスルフィド、ペンタクロロフェニルビニルスルフィド、ペンタクロロフェニルビニルスルホキシド、テトラクロロ（ビニルチオ）を含む。他の例は、１または複数の上述の有機硫黄構造を有してもよい。ただし、置換物Ｒ_１〜Ｒ_５（好ましくはＲ_２、Ｒ_３および／またはＲ_４）の少なくとも１つ、および／または、置換物Ｒ_６〜Ｒ_１０（好ましくはＲ_７、Ｒ_８および／またはＲ_９）の少なくとも１つが、それぞれ、少なくとも１つの上述の架橋可能および／または重合可能なラジカルＸを有する。 Another group of crosslinkable and / or polymerizable compounds are ethylenically unsaturated organosulfur compounds, which may or may not have one or more heterocyclic structures. Not including compounds having a mercapto group and its tautomers, such as thiouracil, triazinedithione, and mercaptothiazole. The general structure of such organic sulfur may include [X (Y) _w R (R _s ) _x ] _y (S) _z . Wherein X is the same or different monovalent crosslinkable and / or polymerizable radical; Y is selected from —COO—, —CH ₂ O—, and —C ₆ H ₄ CH ₂ O—. Are the same or different divalent radicals; R is the same or different divalent; R _s is the same or different sulfur-containing radical; w is 0 or 1; x is 0 or 1 Y is 1 or 2; z is 0 or 1; x + z = 1. Non-limiting examples of X include linear, branched or cyclic C _2-10 alkenes such as vinyl, allyl, isoallyl, propenyl, and isopropenyl. Non-limiting examples of _{R, -CH 2 C 6 H 4 CH} 2 -, - (CH 2) 2 O (CH 2) 2 -, - C 6 H 4 CH 2 -, - (CH 2) x Si _{(CH 3) 2 OSi (CH} 3) 2 (CH 2) y - containing. Wherein x and y are the same or different integers of 1 to 5, C _1-12 saturated hydrocarbons (eg, linear, branched, and / or cyclic alkenes, specifically — (CH ₂ ) _{6 -, - (CH 2)} 10 -, - (CH 2) 11 -, - CH 2 - [] - CH 2 -. a where [] is a benzene ring). Non-limiting examples of R _s are -S-,

Wherein R ″ is H or C _1-6 alkyl, and

including. Non-limiting examples of such organic sulfur include thioethers and polysulfides of the above structure, and acryloxy-4-thiophenol, zinc acryloxythiophenol, bis (4-acryloxybenzene) disulfide, diallyl disulfide, Contains diallyl trisulfide, methyl allyl sulfide, pentachlorophenyl vinyl sulfide, pentachlorophenyl vinyl sulfoxide, tetrachloro (vinylthio). Other examples may have one or more of the aforementioned organic sulfur structures. Provided that at least one of the substituents R _{1 to} R ₅ (preferably R ₂ , R ₃ and / or R ₄ ) and / or the substituents R _{6 to} R ₁₀ (preferably R ₇ , R ₈ and / or At least one of R ₉ ) each has at least one of the aforementioned crosslinkable and / or polymerizable radicals X.

Aromatic crosslinkable and / or polymerizable compounds further include those having the diaryl ether structure described above, wherein the substituents R _{1 to} R ₅ (preferably R ₂ , R ₃ and / or R _4). ) And / or at least one of the substituents R _{6 to} R ₁₀ (preferably R ₇ , R ₈ and / or R ₉ ), respectively, is at least one of the aforementioned crosslinkable and / or polymerizable Furthermore, cinnamon alcohol, cinnamic aldehyde, methoxycinnamic aldehyde, cinnamon methyl ether, cinnamon ethyl ether, cinnamon allyl ether, cinnamon phenyl ether, cinnamon benzyl ether, cinnamon naphthyl ether, cinnamon methyl ketone, cinnamon ethyl ketone, cinnamon allyl ketone , Cinnamon phenyl ketone, cinnamon benzyl ketone, katsura Acetate, cinnamon propionate, cinnamon butyrate, cinnamon benzoate, methyl cinnamate, methyl methyl cinnamate, ethyl cinnamate, naphthyl cinnamate, cinnamon methyl carbonate, cinnamon phenyl carbonate, allylbenzene, allyl phenyl ether, allyl Contains benzoate and allyl phenyl acetate.

  Non-limiting examples of other crosslinkable and / or polymerizable compounds include styrene, α-methylstyrene, and derivatives thereof (eg, p-chlorostyrene, p-hydroxystyrene, divinyl-benzene), fumarate esters (Eg monomethyl fumarate, diethyl fumarate, diphenyl fumarate), allyl esters (eg diallyl phthalate, diallyl terephthalate, diallyl carbonate, allyl diglycol carbonate), epoxies (eg diglycerol polyglycidyl ether, pentaerythritol) Polyglycidyl ether, 1,4-bis (2,3-epoxyproxyperfluoroisopropyl) cyclohexane, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resor Diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid glycidyl ether, o-phthalic acid glycidyl ether, dibromophenyl glycidyl ether, 1,2,7,8-diepoxyoctane, 4,4′-bis (2,3-epoxyproxyperfluoroisopropyl) diphenyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclo-hexanecarboxylate 3,4-epoxycyclohexyloxysilane, ethylene glycol-bis (3,4-epoxycyclohexanecarboxylate)), oxetane (for example, 3-ethyl-3-hydroxymethyl) Tyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (naphthoxymethyl) oxetane, di [1-ethyl (3-oxetynyl)] methyl ether, 3-ethyl-3- (2 -Ethylhexyl-oxymethyl) oxetane, 1,4-bis {[(3-ethyl-3-oxetynyl) methoxy] methyl} benzene), vinyl ether (eg vinyl 2-chloroethyl ether, vinyl n-butyl ether, triethylene glycol) Vinyl ether, 1,4-cyclohexanedimethanol divinyl ether, trimethylolethane trivinyl ether, vinyl glycidyl ether) and silanes (eg, γ-methacryloxypropyltrimethoxysilane, ε-methacryloxyoctyltrimethoxysilane, Niltrimethoxysilane, as described in the Applicant's US patent application 10/120012, ie, as described in US Patent Application Publication 2003/0004013). The contents of that patent application are incorporated herein by reference.

  In one example, the additive acts at least as a crosslinking coagent and comprises a metal salt, for example a zinc salt of an unsaturated acid having 3 to 8 carbon atoms, such as acrylic acid or methacrylic acid, or a manganese salt. Examples include, but are not limited to, one or more metal salts of diacrylate, dimethacrylate, and monomethacrylate, where the metal is magnesium, calcium, zinc, aluminum, sodium, lithium, or nickel . Preferred acrylates include zinc acrylate, zinc diacrylate, zinc methacrylate, zinc dimethacrylate and mixtures thereof. The cross-linked coagent is typically present in an amount greater than about 10 phr, preferably from about 20 to about 40 phr, more preferably from about 25 to about 35 phr.

  In other examples, the additive serves to increase the CoR of the core and / or golf ball and includes hypervalent iodine (eg, diphenyliodonium iodine), Se-containing compounds (eg, diphenyldiselenide), Sn-containing Including compounds (eg, diphenyl dichloride), and sulfonamides (eg, sulfamide). Some of these additives (eg, hypervalent iodine, Sn-containing compounds, and sulfonamides) may be used in amounts equal to or greater than the crosslinking initiator (eg, peroxide), and the weight ratio of additive to crosslinking initiator is 1: 1 or more, preferably 1.5: 1 or more, more preferably 2: 1 to 10: 1, and most preferably 2: 1 to 6: 1. Alternatively, such additives are used in amounts of 0.1 phr or more, preferably 0.5 phr to 10 phr, most preferably 1.5 phr to 3 phr. Other additives (eg, Se-containing compounds) may be used in lesser amounts than the crosslinking initiator (eg, peroxide), and the weight ratio of additive to crosslinking initiator is 0.5: 1 or less, preferably 0.05: 1 to 0.3: 1, more preferably 0.1: 1 to 0.2: 1. Alternatively, such additives are used in amounts of 0.5 phr or less, preferably 0.1 phr to 0.3 phr, more preferably 0.15 phr to 0.3 phr.

  Also useful for the core are isocyanate-containing compounds such as monomeric compounds such as p-toluenesulfonyl isocyanate (PTSI from VanDeMark, Lockport, NY), and polymeric methylene diphenyl diisocyanate (Pow MDI from Dow Chemical), oxazolidine Oxazolane orthoformate (eg trimethyl and triethyl orthoformate), orthoacetate (eg trimethyl and triethylorthoacetate), vinyl silane, a solution-converting polybutadiene as described in US patent application Ser. , Metal mercaptothiazoles described in US patent applications 10/437386 and 10/437387 and And polymer compounds such as metal mercaptobenzothiazoles, the contents of which are incorporated herein by reference.

  Another group of additives are fillers, tungsten, zinc oxide, barium sulfate, silica, calcium carbonate, zinc carbonate, metals, metal oxides and their salts, liglind (typically ground to about 30 mesh particles) Reusable core materials), high Mooney viscosity rubber riglind, and other materials. Fillers added to one or more parts of a golf ball typically include materials such as processing aids or compounds that affect fluid or mixing properties, density adjusting fillers, shear strength or reinforcing fillers, and the like. May be included. The filler may be inorganic, and various metals or metal oxides such as tin oxide, barium sulfate, zinc sulfate, calcium carbonate, barium carbonate, clay, tungsten, tungsten carbide, various silicas (eg, quartz, silica) Silica-alumina, silica-titania, silica-zirconia, silica-magnesia, silica-calcia, silica-barium oxide, silica-strontium oxide, silica-titania-sodium oxide, silica-titania-potassium oxide), titania, zirconia, Including alumina, and mixtures thereof. The filler may include various foaming or expanding agents, which can be easily selected by those skilled in the art. The filler may comprise polymer, ceramic, metal microspheres, may be solid or hollow, and may be filled or unfilled. Organic fillers are polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-trimethylol propane methacrylate copolymer, polyvinyl chloride, polystyrene, polyethylene chloride, nylon, polysulfone, polyethersulfone, And polycarbonate. Fillers can typically be added to one or more portions of the golf ball to adjust its density to meet uniform golf ball standards. A filler may be used to adjust the weight of the additional layer for the center or at least one special ball. For example, lightweight balls are popular with low swing speed players.

  The additives disclosed herein may be used alone or in combination with two or more additives. Using two or more additives selected from different groups, a single or more than one desired utility can be achieved alone or in harmony. The amount of each additive in the composition may be adjusted to optimize the desired utility. In one example, on a weight basis, the amount is 0.1 phr to 5 phr of the base rubber in the formulation.

  The above-described formulations can be used for any structure of one or more golf ball parts, eg, inner center, inner core layer, intermediate core layer, outer core layer, intermediate layer, inner cover layer, intermediate It can be used for cover layers, outer cover layers, etc. and their equivalents. In one example, a polybutadiene-based formulation can be used to form a golf ball outer cover layer that is durable and resistant to cuts and scratches. Such an outer cover layer may itself constitute the entire golf ball cover layer (ie, a single cover layer), forming a multilayer cover with one or more inner cover layers and / or intermediate cover layers. May be. The thickness of the outer cover layer is 0.001 inch to 0.125 inch, preferably 0.005 inch to 0.1 inch, more preferably 0.01 inch to 0.05 inch, most preferably It may be from 0.015 inch to 0.04 inch, for example 0.035 inch. The outer cover layer may have a low flexural modulus of 50000 psi or less, preferably 1000 psi to 30000 psi, more preferably 2000 psi to 250,000 psi. The Shore D hardness of the outer cover layer may be 20 to 60, preferably 25 to 55, more preferably 30 to 55, and most preferably 40 to 55.

In one example, a golf ball layer (e.g., core, intermediate layer) is: a) 100 parts by weight of one polybutadiene, or a blend of two or more polybutadienes, preferably the high cis amount disclosed herein; b) 3 phr or less , Preferably 0.1 phr to 2 phr, more preferably 1 phr or less, more preferably 0.8 phr or less, more preferably 0.5 phr or less; c) 3 phr or less, preferably 0.1 phr to 2 phr, More preferably 1.1 phr or less of aryl thiol, preferably selected from CoPFTP, CoPCTP, CoPBTP, ZnPFTP, ZnPBTP, or a combination of two or more thereof; optionally d) 20 phr or more, preferably 25 phr or more, More preferably 30 phr Above, more preferably 35 phr or more, for example 40 phr, of a bridging coagent, preferably a metal salt of an unsaturated carboxylic acid, such as ZDA, ZDMA or combinations thereof; optionally e) a metal oxide, preferably ZnO, and Optionally f) with filler, preferably barite (BaSO ₄ ). Such a formulation forms at least a portion of a golf ball having a diameter of 1.5 inches or more, preferably 1.54 inches or more, more preferably 1.545 inches or more, and most preferably 1.55 inches or more. Good. The core Atti compression may be 40 to 90, preferably 45 to 85, more preferably 50 to 80, even more preferably 50 to 75, even more preferably 50 to 60, most preferably 55 to 60; The compression may be 25 or less. The CoR of the core may be 0.75 or more, preferably 0.77 or more, 0.79 or more, more preferably 0.8 or more, 0.81 or more. The thickness of the outer core layer may be 0.5 inches or less, preferably 0.3 inches or less, more preferably 0.25 inches to 0.3 inches.

  The materials used to form any part of the golf ball center or core can form a mixture by any mixing technique known to those skilled in the art. Suitable types of mixing techniques include single pass and multipass. Suitable mixers are widely known to those skilled in the art, and such machines may include Banbury mixers, 2-roll mills, twin screw extruders. Conventional mixing speeds for mixing the polymers are typically employed. The mixing temperature depends on the type of polymer component, particularly importantly the type of free radical initiator. Appropriate mixing rates and temperatures are well known to those skilled in the art and can be readily determined without undue experimentation.

  The mixture is subjected to compression or injection to produce a solid sphere for the center or a hemispherical shell for the intermediate layer. The temperature and time of the molding cycle is selected based on the reactivity of the mixture. The molding cycle may have only a single step of molding the mixture for a single time at a single temperature. The production cycle may include a two-step process in which the polymer mixture is held in the mold for an initial time at an initial temperature, after which a second typically is held at a higher temperature for a second time. The In one example, a single step cure cycle is employed. The materials used to form the golf ball center or any portion of the core may be combined by an injection molding process to form a golf ball, which is well known to those skilled in the art. Curing time depends on a variety of selected materials, and those skilled in the art can adjust the curing time up or down based on specific materials and considerations herein.

  The cover thickness is sufficient to achieve sufficient strength, good performance characteristics, and durability. The cover thickness is preferably about 0.1 inches or less, more preferably 0.05 inches or less, and most preferably between about 0.02 inches and 0.04 inches. A preferred structure for a multi-layer golf ball comprises a core, an inner cover layer, and an outer cover layer. Preferably, the thickness of at least one of the inner and outer cover layers is less than about 0.05 inches, more preferably between about 0.02 inches and about 0.04 inches, and most preferably about 0.03 inches. is there.

  The inner cover layer may be formed from a rigid, high flexural modulus, elastic material that is low spin, short distance when hit for a long shot (eg, a driver or long iron) Contributes to properties. The Shore D hardness of the inner cover layer may be 65-80, preferably 69-74, more preferably 70-72. The flexural modulus of the inner cover layer may be at least 65000 psi, preferably 70000 psi to 120,000 psi, more preferably 75000 psi to 100,000 psi. The thickness of the inner cover layer may be 0.020 inches to 0.045 inches, preferably 0.030 inches to 0.040 inches.

  The outer cover layer can be formed from a relatively soft thermoset material to mimic the soft feel and high spin play characteristics of balata balls for “short game” shots. The Shore D hardness of the outer cover layer may be less than 65, preferably 30-60, more preferably 35-50, most preferably 40-45. Further, the material of the outer cover layer may have abrasion resistance suitable for use with a golf ball cover. The outer cover layer disclosed herein may comprise any suitable thermosetting material and can be formed from a moldable reactive liquid material. Materials for the outer cover layer include, but are not limited to, thermosetting urethanes and polyurethanes, thermosetting urethane ionomers, thermosetting urethane epoxies, and polyureas.

If the golf ball comprises an inner cover layer, this layer may comprise any material known to those skilled in the art, which may be partially or sufficient with thermoplastic and thermoset materials such as ethylene. One or more golf balls that are neutralized with zinc, sodium, lithium, magnesium, potassium, calcium, manganese, neckel and other cations with ionic copolymers or terpolymers with methacrylate or acrylate Homopolymer or copolymer inner cover material, which may include:
(1) Vinyl resins, such as those produced by polymerization of vinyl chloride, or those produced by copolymerization of vinyl chloride with vinyl acetate, acrylic esters or vinylidene chloride;
(2) using polyolefins such as polyethylene, polypropylene, polybutylene and copolymers such as ethylene methyl acrylate, ethylene ethyl acrylate, ethylene vinyl acetate, ethylene methacrylic acid or ethylene acrylic acid or propylene acrylic acid and single site or metallocene catalysts Copolymers and homopolymers produced;
(3) polyurethanes, such as those made from polyols and diisocyanates or polyisocyanates and those disclosed in US Pat. No. 5,334,673;
(4) polyureas such as those described in US Pat. No. 5,484,870;
(5) Polyamides such as those made from poly (hexamethylene adipamide) and other diamines and dibasic acids, and those made from amino acids such as poly (caprolactam), and polyamides and SURLYN, polyethylene, ethylene copolymers, Blends with ethyl-propylene-nonconjugated diene terpolymers and the like;
(6) acrylic resins and blends of these resins with polyvinyl chloride, elastomers, and the like;
(7) thermoplastics such as urethane; olefinic thermoplastic rubbers such as blends of polyolefins with ethylene-propylene-nonconjugated diene terpolymers; block copolymers of styrene and butadiene, isoprene or ethylene-butylene rubber; or copoly (ether- Amide), for example, PEBAX ™ commercially available from ELF Atchem of Philadelphia, PA;
(8) A polyphenylene oxide resin or a blend of polyphenylene oxide and high impact polystyrene, marketed under the trademark NORYL ™ by General Electric Company of Pittsfield, MA;
(9) Thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / glycol modified and elastomers under the trade name HYTREL ™ by EI DuPont de Neumours & Co. of Wilmington, DE And marketed under the name LOMOD (TM) by the General Electric Company of Pittsfield, MA;
(10) Blends comprising acrylonitrile butadiene styrene, polybutylene terephthalate, polyethylene terephthalate, styrene maleic anhydride, polyethylene, elastomers, and similar polycarbonates, and polyvinyl chloride having acrylonitrile butadiene styrene or ethylene vinyl acetate or other elastomers. And (11) blends of thermoplastic rubber with polyethylene, propylene, polyacetal, nylon, polyester, cellulose ester, and the like.

Preferably the inner cover comprises a polymer, for example:
Homopolymers or copolymers based on ethylene, propylene, butene-1 or hexane-1, which contain functional monomers such as acrylic acid and methacrylic acid and fully or partially neutralized ionomer resins and their Blends, methyl acrylate, methyl methacrylate homopolymers and copolymers, imidized, polymers containing amino groups, polycarbonate, reinforced polyamide, polyphenylene oxide, high impact polystyrene, polyether ketone, polysulfone, poly (phenylene sulfide), acrylonitrile Butadiene, acrylic-styrene-acrylonitrile, poly (ethylene terephthalate), poly (butylene terephthalate), poly (ethylene vinyl alcohol), poly (tetra Ruoroechiren) and those containing functional comonomers a copolymers thereof, and blends thereof. Suitable inner cover compositions are further disclosed in thermoplastic or thermosetting pyriurethanes and thermoplastic or thermosetting polyureas, such as US patent application Ser. No. 10 / 895,537, ie US Patent Application Publication No. 2005/0004325, to the present applicant. Including The contents of this patent application are incorporated herein by reference.

An intermediate water vapor barrier layer may be disposed around the core to prevent or minimize moisture, typically water vapor, from penetrating the golf ball core. The water vapor transmission rate of the water vapor barrier layer is preferably less than the water vapor transmission rate of the cover, more preferably less than the water vapor transmission rate of an ionomer resin such as Surlyn ™, which is from about 0.45. The range is about 0.95 (g · mm) / (m ² · day). The water vapor transmission rate is defined as the amount of water vapor that diffuses through a material having a predetermined thickness under a unit area and unit time. Preferred standards for measuring water vapor transmission rate include ASTM F1249-90 entitled “Standard Test Method for Water Vapor Transmission Rate of Plastic Films and Sheets Using Modulated Infrared Sensor”, “Flexible Barrier Using Infrared Detection Technology” ASTM F372-99 etc. entitled “Standard Test Method for Water Vapor Permeability of Materials”. The water vapor barrier layer can be formed from any materials and formulations disclosed herein and that achieve the desired vapor transmission rate. Other formulations suitable for the water vapor barrier layer include those disclosed in commonly assigned US patent application 10/611833, ie, US patent application publication 2004/0048688, the contents of which are hereby incorporated by reference. Include here

  Either the inner cover layer or the outer cover layer can be made from a polymer containing α, β-unsaturated carboxylic acid groups or ionic derivatives thereof blended with an organic fatty acid or salt thereof and a suitable cation source. The acid portion of a highly neutralized polymer ("HNP"), typically an ionomer based on ethylene, is preferably greater than about 70%, more preferably greater than about 90%, most preferably at least about 100% neutralized. HNP can also be blended with the second polymer component, and if this component contains acid groups, it can be neutralized according to conventional methods, with the organic fatty acids of the present invention, or both. The second polymer component may be partially or fully neutralized, preferably ionomer copolymers and ionomer terpolymers, ionomer precursors, thermoplastics, polyamides, polycarbonates, polyesters, polyurethanes, polyureas, heat Includes plastic elastomers, polybutadiene rubber, balata, metallocene catalyzed polymers (grafted and ungrafted), single site polymers, highly crystalline acid polymers, cationic ionomers, and the like.

The acid copolymer can be described as an E / X / Y copolymer, where E is ethylene, X is an α, β-ethylenically unsaturated carboxylic acid, and Y is a softening comonomer. For example, X is acrylic acid or methacrylic acid, and Y is a C _1-8 alkyl acrylate or methacrylate ester. X is present in an amount of 0-50%, preferably 1-35%, more preferably 5-30%, most preferably 10-20%, alternatively 5-15% by weight of the polymer. To do. Y is preferably from about 0 to about 50%, more preferably from 5 to 45%, more preferably from 8 to 35%, even more preferably from 5 to 25%, most preferably from 10 to 20% by weight of the polymer. Alternatively, it is present in an amount of 17-40% by weight, for example 24% -35% by weight.

  The organic acid is an aliphatic, mono-functional (saturated, unsaturated or polyunsaturated) organic acid. These organic acid salts can also be used. The organic acid salt of the present invention is composed of barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver, aluminum, tin, or calcium. Salts, salts of fatty acids, in particular salts of stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid or dimerized derivatives thereof. The organic acids and salts of the present invention must be relatively non-migratory (no blooming on the surface of the polymer under normal pressure) and non-volatile (do not evaporate at the temperature required for melt blending) preferable.

  HNP is added to thermoplastic polymer components such as copolyetheresters, copolyesteresters, copolyetheramides, elastomeric polyolefins, styrene diene block copolymers and their hydrogenated derivatives, copolyesteramides, thermoplastic polyurethanes such as copolyether urethane, Polyester urethanes, copolyureaurethanes, epoxy-based polyurethanes, polycaprolactone-based polyurethanes, polyureas, and polycarbonate-based polyurethane fillers, and other components can be blended. Examples of these materials are disclosed in US Patent Application Publications 2001/0018375 and 2001/0019971, the contents of which are incorporated herein by reference.

  Preferably, the base ionomer resin has a melt index (MI) of at least 20 dg / min or at least 40 dg / min, more preferably at least 75 dg / min, and most preferably at least 150 dg / min. Examples of specific soft elastic ionomers include MI and neutralization levels of partially neutralized ethylene / (meth) acrylic acid / butyl (resulting in melt processable polymers of beneficial physical properties). It is a (meth) acrylate copolymer. These copolymers are at least partially neutralized. Preferably, the acid copolymer is neutralized with one or more alkali metal, transition metal or alkaline earth metal cations. Useful cations for preparing the ionomers of this invention are lithium, sodium, potassium, magnesium, calcium, barium, or zinc or combinations of these cations. Preferably, a cation source is used in excess of that required to 100% neutralize all acid moieties in the ionomer blend.

  An organic fatty acid or salt thereof is added only enough to increase the flexibility of the copolymer. Preferably, the organic fatty acid or salt thereof is added by at least about 5% (by weight) based on the total amount of copolymer and organic acid. More preferably, the organic fatty acid or salt thereof is added at least about 15%, even more preferably at least about 20%. Preferably, the organic fatty acid is added up to about 50% (weight basis) relative to the total amount of copolymer and organic fatty acid. More preferably, the organic acid or salt thereof is added up to about 40%, even more preferably up to about 35%. Non-volatile, non-imigrated organic fatty acids preferably contain one or more aliphatic, monofunctional, saturated or unsaturated, less than 36 carbon atoms. It has an organic fatty acid or a salt thereof.

Fatty acid / fatty acid salt modification processes are known in the art. For example, a modified highly neutralized soft elastic acid copolymer ionomer can be produced by the following (a) and (b).
(A) (1) To an ethylene, β-ethylenically unsaturated C _3-8 carboxylic acid copolymer or melt processable ionomer thereof, which has been crystallized by adding a softening monomer or other means, (2 ) Non-volatile, non-migratory organic acids that substantially enhance elasticity and destroy (preferably remove) residual ethylene crystallinity are melt blended simultaneously or sequentially, and simultaneously and sequentially,
(B) the neutralization level of all acid moieties (including the acid moiety in the acid copolymer and the acid moiety in the organic acid if the non-volatile, non-migratory organic acid is an organic acid) is 70% or more, A sufficient amount of cation source is added to achieve a level of preferably 80% or more, more preferably 90% or more, and most preferably 100% or more.

  The weight ratio of X to Y in the composition is at least about 1:20. Preferably, the weight ratio of X to Y is at least about 1:15, more preferably about 1:10. Further, the weight ratio of X to Y in the composition is up to about 1: 1.67, more preferably up to about 1: 2. Most preferably, the weight ratio of X to Y in the composition is up to about 1: 2.2. Specific acid copolymers are ethylene / (meth) acrylic acid / n-butyl (meth) acrylate, ethylene / (meth) acrylic acid / iso-butyl (meth) acrylate, ethylene / (meth) acrylic acid / methyl (meth). Acrylate and ethylene / (meth) acrylic acid / methyl (meth) acrylate terpolymers.

The optional filler may be an inorganic material having a density greater than about 4 g / cm ³ , preferably greater than 5 g / cm ³ , in an amount between 0 and about 60% by weight, based on the total weight of the composition. Exists. Examples of useful fillers are zinc oxide, barium sulfide, lead silicate, tungsten carbide, and other well-known fillers used in golf balls. The filler material is preferably non-reactive or almost non-reactive and does not harden or increase compression and does not significantly reduce the coefficient of restitution. An additional optional additive is an acid copolymer wax (eg, Allied wax AC143, which is an ethylene / 16-18% acrylic acid copolymer, which is considered to have an average molecular weight of 2040), which is a filler material. Helps to prevent reaction between (eg ZnO) and the acid portion of the ethylene copolymer. Other optional additives include a TiO _2, which bleaches, brighteners, surfactants, used as a processing aid.

  Although the outer cover layer can be made using any of the materials listed above, the outer cover preferably comprises a polyurethane, polyurea, or epoxy formulation, which generally includes at least one polyisocyanate. , At least one telechelic polyal, and at least one curing agent reaction product. Suitable outer cover formulations include thermoplastic or thermosetting polyurethanes and thermoplastic or thermosetting polyureas, such as, for example, US patent application Ser. No. 0004325, the contents of which are incorporated herein by reference.

  The CoR of the manufactured golf ball is typically greater than about 0.7, preferably greater than about 0.75, more preferably greater than about 0.78, and most preferably greater than about 0.8. The Atti compression of a golf ball is typically at least about 40, preferably from about 50 to about 120, more preferably from about 60 to about 100. The dimple area of a golf ball is typically greater than about 60 percent, preferably greater than about 65 percent, and more preferably greater than about 75 percent. The material hardness of the outer cover is measured by ASTM-D2240 and is less than about 45 Shore D, preferably less than about 40 Shore D, more preferably between about 25 and about 40 Shore D, and most preferably about 30 to about 40 Shore. May be between D. Alternatively, the material hardness of the outer cover material may be less than about 60 Shore D, preferably less than about 55 Shore D, and more preferably between about 40 to about 55 Shore D. The material hardness of the intermediate layer or inner cover layer is preferably less than about 70 Shore D, more preferably between about 30 and about 70 Shore D, and most preferably between about 50 and about 65 Shore D.

  The core or center Atti compression may be less than 100, preferably less than 90, more preferably between 40-8, most preferably between 50-70. In an alternative, low compression embodiment, the core or center compression may be less than 25. The overall outer diameter of the core is 1.650 inches or less, preferably 1.620 inches or less, more preferably between 1.500 inches and 1.620 inches, and most preferably between 1.540 inches and 1.590 inches. It may be. The outer diameter of the golf ball intermediate layer or inner cover layer is preferably between 1.580 inches and 1.640 inches, more preferably between 1.590 and 1.630 inches, and most preferably between 1.600 inches and 1. Between 630 inches. The diameter of the golf ball is preferably 1.680 inches to 1.800 inches, more preferably 1.680 inches to 1.760 inches, and most preferably 1.680 inches to 1.740 inches.

  The various additives disclosed herein and formulations having such additives may be employed in golf equipment, for example, golf club inserts such as putters, irons and wood, and golf shoes and parts thereof. .

  While it will be appreciated that the exemplary embodiments of the invention described herein will satisfy preferred embodiments of the invention, it should be understood that various modifications and other embodiments can occur to those skilled in the art. Examples of such changes include slight changes in the numerical values described above. Accordingly, the numerical values recited above and in the claims include such numerical values and include values that are close to or very close to the values described above and recited in the claims. Accordingly, the claims are intended to cover all such modifications and other embodiments, and are to be understood as falling within the spirit and scope of this invention.

Claims (18)

  A golf ball having a core and at least one layer disposed around the core, wherein the core or the layer is formed from a base polymer, a crosslinking initiator, and at least one additive. And said additive is borane, borate, boronate, borinate, heterocyclic compound having at least one boron atom as a ring member, boron-containing organic sulfide, sulfur-containing silico compound, salt of such additive and boron A golf ball characterized by being selected from the group consisting of a metal salt, an organic metal salt, and a non-metal salt of a complex. The additive comprises a BR _3, or BR _3, monoorganosiloxane, diorgano or triorgano compounds, boric acid, sulfur-substituted borate, amine borate esters, boron acids, diboronate, borinic acid, dioxaborolane, dioxaborinane, B (OR ) ₃ , B (OR ″) ₃ , R′B (OR) ₂ , YR ″ B (OR) ₂ , Y ′ [R ″ B (OR) ₂ ] ₂ , R ′ ₂ B (OR) ₂ , S _y [ (R ″) _z G] ₂ is selected from the group consisting of compounds having the structure, metal or non-metal salts of such additives, tetraorgano-borane anion R ₄ B ^— , wherein R and R ′ are H And the same or different monovalent radicals having up to 40 carbon atoms, optionally containing one or more heteroatoms and optionally one or more electric Substituted with an withdrawing group, R ″ is the same or different divalent radical having up to 20 carbon atoms, optionally containing one or more heteroatoms, optionally substituted with one or more electron withdrawing groups Y is selected from thiocyano (-SCN), epoxy, glycidyl, epithio, vinyl, allyl, amine, and AZ groups, A is an oxygen or sulfur atom, Z is H, a metal cation, an organometallic cation, and Y ′ is a divalent radical selected from polysulfide S _y or polyselenium Se _y ; G is a monovalent radical containing the same or different Si; x The golf ball according to claim 1, wherein y is an integer of 0, 1, 2, or 3; y is an integer of 1 to 8; and z is 0 or 1. Fuball.   The golf ball of claim 1, wherein the blend further comprises at least one component selected from the group consisting of metal salts of unsaturated acids having 3 to 8 carbon atoms, fillers, fatty acids and salts thereof.   The core has a first coefficient of restitution, the golf ball has a second coefficient of restitution, and at least one of the first and second coefficient of restitution is 0.8 or more. Golf ball.   The golf ball of claim 1, wherein the additive is present in an amount of 0.1 phr to 5 phr based on the weight of the base polymer.   The golf ball according to claim 1, wherein the additive has at least one C—O—B bond, and the carbon in the bond is the second or third carbon.   The golf ball of claim 1, wherein the formulation further comprises at least one amino-based compound.   The golf ball according to claim 1, wherein the core has a diameter of 1.5 inches or more, and the core has a compression of 45-80.   The golf ball according to claim 1, wherein the core has a diameter of 1.5 inches or more, the core has a compression of 50 to 90, and the core has a center and an outer core layer.   The golf ball of claim 1, wherein the at least one layer is an outer cover layer having a thickness of 0.05 inches or less and a flexural modulus of 2000 psi to 30000 psi.   The golf ball further includes an outer cover layer, and the at least one layer is an intermediate layer that is disposed between the core and the outer cover layer and each layer has a thickness of 0.05 inch or less. 1. The golf ball according to 1.   A golf ball having a core and an outer cover layer disposed about the core, wherein the core has a diameter of 1.53 inches or greater, the core comprising a base polymer, a crosslinking initiator, and at least one A compound formed from an additive, wherein the additive is borane, borate, boronate, borinate, a heterocyclic compound having at least one boron atom as a ring member, a boron-containing organic sulfide, a sulfur-containing silico compound, A golf ball characterized in that it is selected from the group consisting of salts of such additives and metal salts, organometallic salts, and non-metallic salts of boron complexes. The additive comprises a BR _3, or BR _3, monoorganosiloxane, diorgano or triorgano compounds, boric acid, sulfur-substituted borate, amine borate esters, boron acids, diboronate, borinic acid, dioxaborolane, dioxaborinane, B (OR ) ₃ , B (OR ″) ₃ , R′B (OR) ₂ , YR ″ B (OR) ₂ , Y ′ [R ″ B (OR) ₂ ] ₂ , R ′ ₂ B (OR) ₂ , S _y [ (R ″) _z G] ₂ is selected from the group consisting of compounds having the structure, metal or non-metal salts of such additives, tetraorgano-borane anion R ₄ B ^— , wherein R and R ′ are H And the same or different monovalent radicals having up to 40 carbon atoms, optionally containing one or more heteroatoms and optionally one or more electric Substituted with an withdrawing group, R ″ is the same or different divalent radical having up to 20 carbon atoms, optionally containing one or more heteroatoms, optionally substituted with one or more electron withdrawing groups Y is selected from thiocyano (-SCN), epoxy, glycidyl, epithio, vinyl, allyl, amine, and AZ groups, A is an oxygen or sulfur atom, Z is H, a metal cation, an organometallic cation, and Y ′ is a divalent radical selected from polysulfide S _y or polyselenium Se _y ; G is a monovalent radical containing the same or different Si; x 13 is an integer from 0, 1, 2 or 3; y is an integer from 1 to 8; and z is 0 or 1. Luffball.   The golf ball of claim 12, wherein the core has a compression of 45-70, and the golf ball has a coefficient of restitution of 0.8 or more.   The golf ball according to claim 12, further comprising an intermediate layer disposed between the core and the outer cover layer and having a thickness of 0.05 inch or less.   A golf ball having a core and an outer core layer disposed around the core, the core having a diameter of 1.53 inches or more, a first coefficient of restitution, and a first compression, the outer cover layer Is formed from polyurethane or polyurea, the thickness of the outer cover layer is 0.05 inches or less, the core layer increases the base polymer, the crosslinking initiator, and the first coefficient of restitution, and And / or having at least one additive that reduces the second compression, wherein the additive is borane, borate, boronate, borinate, a heterocyclic compound having at least one boron atom as a ring member, boron-containing From the group consisting of organic sulfides, sulfur-containing silico compounds, salts of such additives and metal salts of boron complexes, organometallic salts, and non-metallic salts Golf ball, characterized in that it has been-option.   The golf ball of claim 16, wherein the core has a compression of 45-70 and the golf ball has a coefficient of restitution of 0.8 or more.   17. The at least one layer is an outer cover layer, and the golf ball further comprises an intermediate layer disposed between the core and the outer cover layer and having a layer thickness of 0.05 inches or less. The golf ball described.