A rubber adhesive, rubber composition and non-tire rubber article

Abstract

The present application relates to the technical field of rubber, in particular to a rubber adhesive, a rubber composition and a non-tire rubber product. The rubber adhesive comprises, by weight fraction, 30-75 parts of base resin, 20-69.9 parts of organic acid salt and 0.1-5 parts of active agent. The rubber composition comprises the rubber adhesive. The non-tire rubber product comprises the rubber composition and steel cord. The rubber adhesive can improve the bonding performance between the peroxide vulcanized rubber system and the steel cord, increase the bonding strength between the rubber and the steel cord under the peroxide vulcanization system, and the rubber system and the steel cord can still maintain good adhesion under the condition of high temperature and long time use.

Description

Technical Field

[0001] The present invention relates to the field of rubber technology, in particular to a rubber adhesive, a rubber composition and a non-tire rubber product. Background Art

[0002] In non-tire rubber products, as product lifecycles and performance improve, a skeleton material is typically used to increase product strength. Skeleton materials typically include steel wire, nylon, and polyester. The bond strength between the rubber and the skeleton plays a crucial role in overall product performance. This is especially true for rubber products used in high temperatures, where excellent heat resistance and strong adhesion between the rubber and the skeleton are crucial, ensuring long-term, high-temperature use improves product performance and service life.

[0003] The sulfur vulcanization system for rubber plays a good role in promoting the bonding strength between rubber and skeleton materials, but the sulfur vulcanization system does not have advantages in heat resistance and aging resistance. The cross-linking bonds in the network structure of the peroxide vulcanization system are CC bonds, which have high bond energy, high thermal stability and chemical stability, excellent heat resistance and resistance to thermal oxidative aging, and no vulcanization reversion phenomenon. The vulcanized rubber has low compression permanent deformation and is widely used in static sealing or high-temperature rubber products. However, compared with traditional sulfur vulcanization, rubber products vulcanized with organic peroxides have low strength, especially low peel strength, and low adhesion between rubber and skeleton materials. The most commonly used adhesive in the industry is zinc monomethacrylate, but the adhesion between rubber and skeleton materials still cannot meet the product performance requirements.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] A first object of the present invention is to provide a rubber adhesive capable of improving the bonding performance of peroxide-cured rubber systems.

[0006] A second object of the present invention is to provide a rubber composition having excellent bonding properties and excellent bonding strength between the rubber composition and other materials, especially steel cords.

[0007] A third object of the present invention is to provide a non-tire rubber product having excellent adhesion between the rubber composition and the steel cord, thereby improving the performance and service life of the non-tire rubber product.

[0008] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are adopted:

[0009] The present invention provides a rubber adhesive, which comprises, by weight, 30 to 75 parts of a base resin, 20 to 69.9 parts of an organic acid salt and 0.1 to 5 parts of an active agent.

[0010] Furthermore, the matrix resin includes one or more of phenolic resin, petroleum resin, coumarone resin and dicyclopentadiene resin.

[0011] Furthermore, the organic acid salt includes organic acid zinc and / or organic acid calcium.

[0012] Preferably, the organic acid salt comprises a C3-C30 unsaturated fatty acid salt.

[0013] Furthermore, the active agent includes a sulfur-containing substance.

[0014] Preferably, the sulfur-containing material includes one or more of HTS, KA9188, TB710 and sulfur.

[0015] The present invention also provides a rubber composition comprising the rubber adhesive described above.

[0016] Preferably, in the rubber composition, the mass percentage of the rubber adhesive is 1% to 20%.

[0017] Furthermore, the rubber composition comprises, by weight, 100 parts of rubber, 40 to 130 parts of reinforcing filler and 1 to 15 parts of the rubber adhesive.

[0018] Furthermore, the rubber composition further includes an additive, and the mass ratio of the additive to the rubber is 13 to 45:100.

[0019] Preferably, the additive comprises the following components in parts by weight: 4 to 20 parts of a vulcanizing activator, 1 to 5 parts of an antioxidant, 2 to 10 parts of a plasticizer, and 6 to 10 parts of a cross-linking agent.

[0020] Furthermore, the rubber composition comprises, by weight, 100 parts of rubber, 40-100 parts of carbon black, 5-30 parts of white carbon black, 3-15 parts of zinc oxide, 1-5 parts of stearic acid, 2-10 parts of plasticizer, 1-5 parts of antioxidant, 1-15 parts of the rubber adhesive, 3-5 parts of trimethylolpropane trimethacrylate and 3-5 parts of dicumyl peroxide.

[0021] Furthermore, the rubber includes one or more of EPDM rubber, nitrile rubber, natural rubber, polyisoprene rubber, polybutadiene rubber and polybutadiene-styrene rubber.

[0022] The present invention also provides a non-tire rubber product comprising the rubber composition and a steel cord.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] The rubber adhesive provided by the present invention can improve the bonding performance of a peroxide-cured rubber system and other materials, and increase the bonding strength between rubber and other materials, especially steel cords, in a peroxide-cured system.

[0025] The peroxide-cured rubber composition of the present invention has excellent bonding properties by adding the above-mentioned rubber adhesive and cooperating with other components. The rubber composition of the present invention has excellent adhesion to the steel cord. Even under high-temperature and long-term use conditions, the rubber composition and the steel cord can still maintain good adhesion, thereby effectively improving the performance and service life of non-tire rubber products made from the peroxide-cured rubber composition and the steel cord. DETAILED DESCRIPTION

[0026] The technical scheme of the present invention will be clearly and completely described below in conjunction with specific embodiments, but it will be understood by those skilled in the art that the following described embodiments are part of embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work premise belong to the scope of protection of the present invention. Those who do not specify specific conditions in the embodiments are carried out according to normal conditions or the conditions recommended by the manufacturer. Those whose reagents or instruments are not specified by the manufacturer are conventional products that can be purchased commercially.

[0027] The following is a detailed description of a rubber adhesive, a rubber composition, and a non-tire rubber product according to embodiments of the present invention.

[0028] In some embodiments of the present invention, a rubber adhesive is provided, which comprises, by weight, 30 to 75 parts of a base resin, 20 to 69.9 parts of an organic acid salt, and 0.1 to 5 parts of an active agent.

[0029] The rubber adhesive of the present invention can improve the bonding performance of a peroxide-cured rubber system and other materials, and increase the bonding strength between rubber and other materials, especially steel cords, in a peroxide-cured system.

[0030] In some embodiments of the present application, typically but not exclusively, the weight fraction of the base resin is 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, or 75 parts, and the like; the weight fraction of the organic acid salt is 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, or 65 parts, and the like; and the weight fraction of the active agent is 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or 5 parts, and the like.

[0031] In some specific embodiments of the present application, the rubber adhesive comprises, by weight fraction, 35-50 parts of the base resin, 40-60 parts of the organic acid salt, and 0.5-1.5 parts of the active agent.

[0032] In some embodiments of the present application, the base resin comprises one or more of phenol-formaldehyde resin, petroleum resin, coumarone resin, and dicyclopentadiene resin; preferably, the base resin comprises dicyclopentadiene resin (DCPD resin).

[0033] In some embodiments of the present application, the organic acid salt comprises zinc and / or calcium organic acid salt; typically but not exclusively, the organic acid salt comprises zinc and / or calcium salt of at least one of propionic acid, butyric acid, hexanoic acid, lauric acid, palmitic acid, stearic acid, ricinoleic acid, lactic acid, tartaric acid, glutaric acid, adipic acid, acrylic acid, monomethyl acrylic acid, dimethyl acrylic acid, oleic acid, benzoic acid, coconut oil acid, corn oil acid, cottonseed oil acid, rapeseed oil acid, rice bran oil acid, olive oil acid, abietic acid, and tall oil acid.

[0034] In some specific embodiments of the present application, the organic acid salt comprises one or more of zinc laurate, calcium stearate, zinc stearate, calcium palmitate, zinc oleate, zinc rice bran oil acid, zinc acrylate, zinc dimethyl acrylate, zinc monomethyl acrylate, and zinc abietate.

[0035] In some embodiments of the present application, the organic acid salt comprises C3-C30 unsaturated fatty acid salt.

[0036] In some embodiments of the present application, the C3-C30 unsaturated fatty acid salt comprises zinc and / or calcium salt of at least one of ricinoleic acid, acrylic acid, monomethyl acrylic acid, oleic acid, olive oil acid, and tall oil acid.

[0037] In some embodiments of the present application, the active agent comprises sulfur-containing substance; preferably, the sulfur-containing substance comprises one or more of HTS, KA9188, TB710, and sulfur.

[0038] In some specific embodiments of the present application, the active agent comprises TB710.

[0039] The matrix resin in the rubber adhesive of the present invention improves the compatibility between the adhesive resin and the rubber, and makes the rubber adhesive uniformly dispersed in the rubber. When the rubber composition is vulcanized under certain temperature and pressure conditions, the matrix resin in a molten state diffuses toward the surface of the adherend (rubber and metal) by means of Brownian motion, so that the polar groups of the two are close to each other and generate adsorption force. Finally, the molecular contact and secondary force are generated to play a bonding role. The double bonds in the matrix resin form a strong cross-linked network with the rubber during the vulcanization process; under the action of the organic acid salt, rubber-metal ion bonds are formed between the rubber and the metal, thereby improving the interface bonding force. At the same time, the double bonds in the unsaturated fatty acid salt can also form a cross-linked network with the rubber during the vulcanization process, and the network formed with the matrix resin is mutually entangled and interpenetrated, thereby improving the bonding force between the rubber and the metal. The activator further promotes the generation of more rubber-metal ion bonds, thereby greatly improving the interface bonding force.

[0040] In some embodiments of the present invention, a method for preparing the rubber adhesive is also provided, comprising the following steps:

[0041] After the base resin and the organic acid salt are mixed evenly, the activator is added and mixed evenly to obtain the rubber adhesive.

[0042] In some embodiments of the present invention, a rubber composition is further provided, comprising the rubber adhesive.

[0043] In some embodiments of the present invention, the mass percentage of the rubber adhesive in the rubber composition is 1% to 20%; typically but not limitatively, for example, the mass percentage of the rubber adhesive is 1%, 5%, 10%, 15% or 20%, etc.; preferably, the mass percentage of the rubber adhesive in the rubber composition is 1.5% to 10%.

[0044] In some embodiments of the present invention, the rubber composition comprises, by weight, 100 parts of rubber, 40 to 130 parts of reinforcing filler, and 1 to 15 parts of rubber adhesive; preferably, the rubber composition comprises, by weight, 100 parts of rubber, 40 to 100 parts of reinforcing filler, and 1 to 10 parts of rubber adhesive.

[0045] Reinforcing filler can be organic filler, inorganic filler and mixture thereof.In rubber composition, as the organic filler of reinforcing filler, the most commonly used is carbon black, and all carbon blacks that are usually used in tire are all applicable in rubber composition of the present invention, as ASTM grade is the reinforcing carbon black (such as N115, N234, N330, N375 etc.) of 100,200,300 series, or the carbon black (such as N660, N772 etc.) of ASTM grade higher series.In rubber composition, as the inorganic filler of reinforcing filler, commonly used is siliceous filler, aluminum filler and mixture thereof.The filler of siliceous type (particularly silicon dioxide (SiO 2 )) or aluminum type (particularly aluminum oxide (Al 3 O 2 )) is very suitable as inorganic filler.For silicon dioxide, any one of wet process silicon dioxide and dry process silicon dioxide classified according to its preparation method can be used.

[0046] In some embodiments of the present invention, the rubber composition further comprises an additive; preferably, the additive comprises at least one of a vulcanization activator, an antioxidant, a plasticizer, and a cross-linking agent.

[0047] In some embodiments of the present invention, the additive includes the following components in parts by weight: 4 to 20 parts of a vulcanizing activator, 1 to 5 parts of an antioxidant, 2 to 10 parts of a plasticizer, and 6 to 10 parts of a cross-linking agent.

[0048] In some embodiments of the present invention, the vulcanization active agent includes zinc oxide and / or stearic acid.

[0049] In some embodiments of the present invention, the antioxidant includes a p-phenylenediamine rubber antioxidant and / or a ketamine rubber antioxidant.

[0050] In some embodiments of the present invention, the plasticizer includes one or more of a paraffin-based rubber plasticizer, an aromatic-based rubber plasticizer, and a cycloalkyl-based rubber plasticizer.

[0051] In some embodiments of the present invention, the crosslinking agent comprises trimethylolpropane trimethacrylate and / or dicumyl peroxide.

[0052] In some embodiments of the present invention, the rubber composition comprises, by weight, 100 parts of rubber, 40-100 parts of carbon black, 5-30 parts of white carbon black, 3-15 parts of zinc oxide, 1-5 parts of stearic acid, 2-10 parts of plasticizer, 1-5 parts of antioxidant, 1-15 parts of rubber adhesive, 3-5 parts of trimethylolpropane trimethacrylate and 3-5 parts of dicumyl peroxide.

[0053] In some specific embodiments of the present invention, the rubber composition includes, by weight, 100 parts of rubber, 40-50 parts of carbon black, 5-15 parts of white carbon black, 5-15 parts of zinc oxide, 1-5 parts of stearic acid, 2-5 parts of plasticizer, 2-5 parts of antioxidant, 4-8 parts of rubber adhesive, 3-4 parts of trimethylolpropane trimethacrylate and 3-4 parts of dicumyl peroxide.

[0054] The rubber composition of the present invention, by adding the above-mentioned rubber adhesive and cooperating with other components, makes the obtained peroxide-cured rubber composition have excellent bonding performance; the rubber composition has excellent adhesion to the steel cord, and even under high temperature and long-term use conditions, the rubber composition and the steel cord can still maintain good adhesion.

[0055] In some embodiments of the present invention, the rubber includes one or more of EPDM rubber, nitrile rubber, natural rubber, polyisoprene rubber, polybutadiene rubber and polybutadiene-styrene rubber; preferably, the rubber includes EPDM rubber.

[0056] In some embodiments of the present invention, a method for preparing a rubber composition comprises the following steps:

[0057] A 1.6-liter Banbury internal mixer was used to mix the remaining components except trimethylolpropane trimethacrylate and diisopropylbenzene peroxide to obtain a masterbatch. After the masterbatch was allowed to stand for 20 to 30 hours, it was mixed with trimethylolpropane trimethacrylate and diisopropylbenzene peroxide in the 1.6-liter Banbury internal mixer, and then sheeted using an open rubber mixer for standby use.

[0058] In some embodiments of the present invention, the rubber composition is vulcanized at a temperature of 150-200° C. to obtain a vulcanized rubber.

[0059] In some embodiments of the present invention, a non-tire rubber product is also provided, comprising the rubber composition and a steel cord.

[0060] In the non-tire rubber product of the present invention, the rubber composition and the steel cord have excellent bonding performance, thereby effectively improving the performance and service life of the non-tire rubber product.

[0061] Examples 1 to 6

[0062] The raw materials of the vulcanized rubber provided in this embodiment include, by weight:

[0063] 100 parts of ethylene propylene diene monomer rubber (EPDM), 40 parts of carbon black (N330), 10 parts of white carbon black, 10 parts of zinc oxide, 1 part of stearic acid, 2 parts of plasticizer (TP759), 2 parts of p-phenylenediamine antioxidant, 3 parts of rubber adhesive, 3.7 parts of trimethylolpropane trimethacrylate (TMPTMA, 60% active ingredient) and 3.7 parts of diisopropyl peroxide (DCP, 40% active ingredient).

[0064] The method for preparing the vulcanized rubber of this embodiment comprises the following steps:

[0065] The remaining components except trimethylolpropane trimethacrylate and diisopropylbenzene peroxide were mixed for 6 minutes in a 1.6-liter Banbury internal mixer to obtain a masterbatch. After the masterbatch was allowed to stand for 24 hours, it was mixed with trimethylolpropane trimethacrylate and diisopropylbenzene peroxide in a 1.6-liter Banbury internal mixer for 3.5 minutes, and then sheeted using an open rubber mixer for standby use, thereby obtaining a rubber composition. The rubber composition was vulcanized at a temperature of 170° C. for 30 minutes to obtain a vulcanized rubber.

[0066] The preparation method of the rubber adhesive provided in this embodiment comprises the following steps:

[0067] The base resin is crushed by a high-speed mixer, and an organic acid salt is added and mixed evenly, and then an activator is added and further crushed and mixed to obtain a rubber adhesive.

[0068] The preparation methods of the vulcanized rubbers provided in Examples 1 to 6 are the same, except that the components and amounts of the rubber adhesive are different. The components and amounts of the rubber adhesives in Examples 1 to 6 are shown in Table 1. The general technical indicators of the rubber adhesive, including appearance and weight loss upon heating (100°C), are recorded in Table 1.

[0069] Table 1

[0070]

[0071] Example 7

[0072] The vulcanized rubber and preparation method thereof provided in this embodiment refer to Example 3, except that the weight portion of the rubber adhesive is 1 part.

[0073] Example 8

[0074] The vulcanized rubber and preparation method thereof provided in this embodiment refer to Example 3, except that the weight portion of the rubber adhesive is 5 parts.

[0075] Comparative Example 1

[0076] The vulcanized rubber provided in this comparative example is composed of the following raw materials in parts by weight:

[0077] 100 parts of ethylene propylene diene monomer rubber (EPDM), 40 parts of carbon black (N330), 10 parts of white carbon black, 10 parts of zinc oxide, 1 part of stearic acid, 2 parts of plasticizer (TP759), 2 parts of p-phenylenediamine antioxidant, 3 parts of zinc monomethacrylate (rubber adhesive), 3.7 parts of trimethylolpropane trimethacrylate (TMPTMA, 60% active ingredient) and 3.7 parts of diisopropyl benzene peroxide (40% active ingredient).

[0078] The preparation method of the vulcanized rubber in this comparative example is similar to that in Example 1.

[0079] Comparative Example 2

[0080] The vulcanized rubber provided in this comparative example is composed of the following raw materials in parts by weight:

[0081] 100 parts of ethylene propylene diene monomer rubber (EPDM), 40 parts of carbon black (N330), 10 parts of white carbon black, 10 parts of zinc oxide, 1 part of stearic acid, 2 parts of plasticizer (TP759), 2 parts of p-phenylenediamine antioxidant, 1 part of resorcinol, 0.5 parts of cobalt salt, 1.5 parts of hexahydroxymethyl melamine hexmethyl ether (HMMM, RA65), 1.4 parts of sulfur and 1 part of accelerator (NS).

[0082] The preparation method of the vulcanized rubber of this comparative example comprises the following steps:

[0083] The remaining components except sulfur and accelerator (NS) were mixed for 6 minutes in a 1.6-liter Banbury internal mixer to obtain a masterbatch. After the masterbatch was allowed to stand for 24 hours, it was mixed with sulfur and accelerator (NS) in a 1.6-liter Banbury internal mixer for 3.5 minutes, and then sheeted using an open rubber mixer for standby use, thereby obtaining a rubber composition. The rubber composition was vulcanized at a temperature of 150° C. for 30 minutes to obtain a vulcanized rubber.

[0084] Comparative Example 3

[0085] The vulcanized rubber provided in this comparative example is composed of the following raw materials in parts by weight:

[0086] 100 parts of ethylene propylene diene monomer rubber (EPDM), 40 parts of carbon black (N330), 10 parts of white carbon black, 10 parts of zinc oxide, 1 part of stearic acid, 2 parts of plasticizer (TP759), 2 parts of p-phenylenediamine antioxidant, 3 parts of DCPD resin (rubber adhesive), 3.7 parts of trimethylolpropane trimethacrylate (TMPTMA, 60% active ingredient) and 3.7 parts of diisopropyl benzene peroxide (40% active ingredient).

[0087] The preparation method of the vulcanized rubber in this comparative example is similar to that in Example 1.

[0088] Test Example 1

[0089] The properties of the vulcanized rubbers prepared in Examples 1 to 3, 7 and 8 were tested, and the results are shown in Table 2; the properties of the vulcanized rubbers prepared in Comparative Examples 1 to 3 were tested, and the results are shown in Table 3.

[0090] Among them, the tensile properties test: the tensile strength and elongation at break of vulcanized rubber are tested according to the standard GB / T 528-2009; the tensile strength is the tensile stress recorded at the moment of fracture of the tensile specimen, in MPa; the elongation at break is the elongation of the specimen at the time of fracture, in %.

[0091] Shore Hardness Test: Evaluates the Shore hardness of vulcanized rubber according to standard GB / T 531.1-2008. A higher hardness value indicates a higher rigidity of the vulcanized rubber.

[0092] Table 2

[0093]

[0094]

[0095] Table 3

[0096] Comparative Example 1 Comparative Example 2 Comparative Example 3 50% modulus of elongation (Mpa) 2.6 2.5 2.4 100% modulus of tensile stress (Mpa) 4.9 4.0 3.8 Tensile strength (Mpa) 19.2 15.8 16.9 Elongation at break (%) 226 283 311 Shore A hardness (degrees) 76 76 75

[0097] The adhesion between the vulcanized rubbers obtained in Examples 1 to 3, 7 and 8 and Comparative Examples 1 to 3 and the steel wire was tested, and the results are shown in Table 4.

[0098] The bond strength between vulcanized rubber and steel cord is tested according to GB / T 16586-2014. The test speed is 100 mm / min, and the steel cord is embedded in the rubber to a thickness of 25 mm. The steel cord is then pulled out of the vulcanized rubber, and the maximum force required to pull it out is measured. A higher force indicates better adhesion.

[0099] Table 4

[0100]

[0101]

[0102] Tables 2, 3, and 4 show that, compared with the comparative examples, the rubber adhesives in the examples increased the tensile strength of the rubber and extended its elongation at break, with a certain impact on the tensile stress of the vulcanized rubber. In terms of steel wire adhesion, Example 3 exhibited significant advantages over Comparative Examples 1, 2, and 3, both before and after aging. This is primarily due to the double bonds in the matrix resin and the double bonds in the fatty acid metal salt in the rubber adhesive in Example 3, which formed a strong crosslinked network with the rubber. These two networks intertwined and interpenetrated synergistically. Simultaneously, under the action of the organic acid salt, rubber-metal ionic bonds formed between the rubber and the metal. The synergistic interaction between the various components of the rubber adhesive enhanced the adhesion between the rubber and the steel wire. The adhesion between the rubber and the steel wire increased with increasing adhesive resin dosage. However, after reaching a certain dosage, the adhesion decreased.

[0103] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A rubber composition, characterized in that The composition comprises, by weight, 100 parts of rubber, 40-100 parts of carbon black, 5-30 parts of white carbon black, 3-15 parts of zinc oxide, 1-5 parts of stearic acid, 2-10 parts of plasticizer, 1-5 parts of antioxidant, 1-15 parts of rubber adhesive, 3-5 parts of trimethylolpropane trimethacrylate and 3-5 parts of dicumyl peroxide; The rubber adhesive comprises: 30-75 parts of base resin, 20-69.9 parts of organic acid salt and 0.1-5 parts of active agent; The base resin includes one or more of petroleum resin, coumarone resin and dicyclopentadiene resin; The organic acid salt includes C3~C30 unsaturated fatty acid salt.

2. The rubber composition according to claim 1, characterized in that The active agent includes a sulfur-containing substance.

3. The rubber composition according to claim 2, characterized in that The sulfur-containing material includes one or more of HTS, KA9188, TB710 and sulfur.

4. The rubber composition according to claim 1, characterized in that The rubber includes one or more of EPDM rubber, nitrile rubber, natural rubber, polyisoprene rubber, polybutadiene rubber and polybutadiene-styrene rubber.

5. A non-tire rubber product, characterized in that: The invention comprises the rubber composition according to any one of claims 1 to 4 and a steel cord.

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