KR20210125934A - Adhesive composition and rubber reinforcing material - Google Patents

Abstract

The present invention relates to an adhesive composition comprising (A) latex, (B) poly urethane, (C) an amine-based adhesive enhancing agent, and (G) a water-containing solvent. The composition is environmentally friendly, has less risk of fire, and has excellent adhesiveness.

Description

Adhesive composition and rubber reinforcing material

Cross-Citation with Related Application(s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0043567 dated April 09, 2020, and all contents disclosed in the documents of the Korean patent application are incorporated as a part of this specification.

technical field

The present application relates to an adhesive composition, and a rubber reinforcement. Specifically, the present application relates to an adhesive and a rubber reinforcing material that can be used in a rubber composite such as a tire.

Fiber reinforcement is used to reinforce the strength of the rubber structure. For example, in a rubber tire, polyester fiber, polyamide fiber, aromatic polyamide fiber, polyvinyl alcohol fiber, or the like may be used as a reinforcing material. And, since some fibers have poor adhesion to rubber, the adhesion between rubber and fibers is supplemented after the adhesive is coated on the surface of the fibers. For example, in order to improve the adhesion between the polyester fiber for tire cord (raw cord, raw cord) and the rubber for tire, an adhesive is applied to the polyester fiber.

In the prior art, it was common to use resorcinol-formaldehyde (RF) or a component derived therefrom as an adhesive for the above use. However, RF, which contains phenols resorcinol and formaldehyde, a known carcinogen, is harmful to the human body. do.

Meanwhile, as a method of coating the adhesive composition on the fiber reinforcement, dipping or spraying may be considered. In the process of manufacturing the code to which the above method is applied, each component constituting the adhesive composition should be evenly mixed and dispersed in the solvent included in the composition. In addition, it is important that the composition in which each component is evenly mixed and dispersed can be uniformly coated on the surface of the fiber reinforcement (eg, raw cord) in an appropriate amount even after being immersed or sprayed. This is because, if mixing between the components constituting the adhesive composition is not sufficiently performed or if the flowability of the composition is too high due to excessive use of a solvent, adhesive strength is not secured.

An object of the present application, resorcinol-formaldehyde (Resorcinol- Formaldehyde, hereinafter "RF") to provide an environmentally friendly adhesive composition that does not contain a component.

Another object of the present application is to provide an adhesive composition having excellent adhesion.

Another object of the present application is to provide an adhesive composition having excellent coating processability.

Another object of the present application is to provide a rubber composite and a rubber reinforcing material formed using the adhesive.

The above and other objects of the present application can all be solved by the present application described in detail below.

According to the present application, an adhesive composition comprising (A) latex, (B) polyurethane, (C) an amine-based adhesion promoter and (D) a water-containing solvent, satisfying a predetermined viscosity; a rubber reinforcing material comprising the adhesive composition or a cured product thereof and a fiber cord; and a rubber composite including the rubber reinforcing material.

Hereinafter, an adhesive according to a specific embodiment of the present invention and a rubber reinforcing material manufactured using the same will be described.

In an example related to the present application, the present application relates to an adhesive composition.

_{The composition may include water (H 2} O) as a solvent or dispersion medium for the adhesive composition or individual components included in the composition. For example, in consideration of fire risk, harm to the human body, and ensuring dispersibility of the composition components, in the present application, excess water in the composition (eg, the content of water excluding solids in the total composition is about 40% by weight or more or 50% by weight or more) may be used. Unless otherwise defined in this application, "solid content" in the present application refers to the content of the active ingredient (which may be in solid form) remaining after evaporating the moisture or liquid component (eg, solvent) of the composition or each component included in the composition. can mean Conditions for evaporating moisture or liquid components (eg, solvent) are not particularly limited, but, for example, heating (heating) conditions in the range of 70 to 100° C. for about 0.5 to 3 hours may be applied.

In this regard, the inventors of the present application, the adhesive composition, such as comprising an excess of solvent, for example, water in a content of 40% by weight or more, 50% by weight or more, or 60% by weight or more, and other solids accounting for the content In the case of including this excess water or solvent, it was confirmed that there is a problem in that sufficient adhesive strength cannot be secured while the viscosity of the adhesive composition is lowered, and thus the present invention has been completed.

Accordingly, the composition according to the present application includes (A) latex, (B) polyurethane, (C) an amine-based adhesion promoter and (D) a water-containing solvent, and an Ubbelohde viscometer The relative viscosity (RV) measured at room temperature using

In the present application, "room temperature" is a temperature in a state in which temperature reduction or heating is not particularly performed, and may mean, for example, a temperature in the range of 15 to 30 °C. Specifically, within the above temperature range, the room temperature may be a temperature of 17 °C or higher, 19 °C or higher, 21 °C or higher, or 23 °C or higher, and may be a temperature of 29 °C or lower or 27 °C or lower.

In addition, unless otherwise specified in the present application, the temperature at which the evaluation of the digitized characteristic is performed may be room temperature.

The "relative viscosity" refers to the ratio of the viscosity (characteristic) of the composition to the reference solvent viscosity (property), and the reference solvent used for measuring the relative viscosity may be water (eg, demineralized water or pure water). . Specifically, the relative viscosity (RV) is the time taken until the composition passes through a predetermined scale section of the Ubelode viscometer (T ₁ ) and when water (eg, demineralized water) passes through a scale section of the same size After measuring the time taken to (T ₀ ), it can be calculated by dividing _{T 1} by T _{0 . The relative viscosity calculated by T 1} and T ₀ measured by the same viscometer under the same conditions can be treated as a dimensionless constant. In more detail, it will be described in Experimental Example 1 below with reference to FIG. 1 .

Specifically, the lower limit of the relative viscosity of the composition is, for example, 2.51 or more, 2.52 or more, 2.53 or more, 2.54 or more, 2.55 or more, 2.56 or more, 2.57 or more, 2.58 or more, 2.59 or more, 2.60 or more, 2.61 or more, 2.62 or more, 2.63 or more. or more, 2.64 or more, 2.65 or more, 2.66 or more, 2.67 or more, 2.68 or more, 2.69 or more, or 2.70 or more. And, the upper limit of the relative viscosity of the composition may be, for example, 2.95 or less or 2.90 or less, more specifically 2.89 or less, 2.88 or less, 2.87 or less, 2.86 or less, 2.85 or less, 2.84 or less, 2.83 or less, 2.82 or less, 2.81 or less, 2.80 or less, 2.79 or less, 2.78 or less, 2.77 or less, 2.76 or less, 2.75 or less, 2.74 or less, 2.73 or less, 2.72 or less, or 2.71 or less.

When the relative viscosity is less than the above range, there is a problem in that the low molecular weight polymers formed during the preparation and curing of the composition are transferred to the adherend and the adhesive strength decreases, and accordingly, sufficient physical properties (eg, mechanical strength, etc.) are provided for the purpose. may not be In addition, when the relative viscosity is low, since the flowability is relatively large, it may not be possible to form a sufficient coating layer on the adherend. In addition, for example, when the relative viscosity exceeds the above range, the cohesive force between the high molecular weight polymer formed during the composition preparation and curing process increases, making it difficult for the adhesive to be uniformly distributed (or applied) on the adherend, so the adhesive force is lowered there is a problem with Accordingly, sufficient physical properties (eg, mechanical strength, etc.) for the intended use may not be provided.

As a result, the adhesive composition satisfying the above relative viscosity range, as shown in the following experimental examples, provides excellent adhesion, enables to secure an appropriate level of pick-up rate, and fairness and productivity regarding adhesive preparation and application to improve

All components of the composition described below may be selected and used within a content range that is not inconsistent with the present application such that the viscosity of the entire composition may be satisfied.

(A) Latex component

(A) Latex is a component used in consideration of the use of a composition. Specifically, the adhesive composition may be used for an adherend, such as a rubber composite or a rubber reinforcing material. When latex is used, it may be advantageous to secure affinity, miscibility, or adhesion with the adherend. In some cases, the latex component included in the adhesive composition may be selected to be the same as the rubber component of the adherend.

As long as it is not contrary to the present application, such as can satisfy the viscosity of the entire composition described above, the type of latex that can be used in the composition is not particularly limited.

In one example, the latex is vinyl-pyridine latex such as natural rubber latex, vinyl-pyridine-styrene-butadiene-based copolymer latex (Vinyl-Pyridine-Styrene-Butadiene-copolymer Latex) (hereinafter, “VP Latex”) , styrene-butadiene-based copolymer latex, acrylic acid ester-based copolymer latex, butyl rubber latex, chloroprene rubber latex, or modified latex thereof may be used. With respect to the modified latex, a specific kind of latex or a method of modifying the latex is not limited. For example, a modified latex obtained by modifying a vinyl-pyridine-styrene-butadiene-based copolymer with a carboxyl group or the like may be used.

Commercially available latex may also be used, as long as it is not contrary to the present application, such as being able to satisfy the viscosity of the overall composition described below. For example, as commercially available VP latex, Denaka's LM-60, APCOTEX's VP-150, Nippon A&L's VB-1099, Closlen's 5218, or Closlen's 0653 may be used.

In one example, a latex component comprising at least one of the latexes described above may be used in the adhesive composition.

In one example, the latex is dispersed in a solvent (water or organic solvent), and may be mixed with other composition components. In this case, within a range that can satisfy the viscosity of the entire composition described above, the content and type of the solvent used in the latex component may be determined.

In one example, the adhesive composition, based on the total content of the composition, the (A) latex may include 1.0% by weight or more, for example, 1.5% by weight or more. The content may mean the content occupied by latex solids in the composition. Specifically, the lower limit of the content of the (A) latex is, for example, 2.0 wt% or more, 3.0 wt% or more, 4.0 wt% or more, 5.0 wt% or more, 6.0 wt% or more, 7.0 wt% or more, 8.0 wt% or more , 9.0 wt% or more, 10.0 wt% or more, 11.0 wt% or more, 12.0 wt% or more, 13.0 wt% or more, 14.0 wt% or more, or 15.0 wt% or more, and the upper limit thereof is, for example, 30 wt% or less , 25 wt% or less, 20 wt% or less, or 15 wt% or less. When the above range is satisfied, it may be advantageous in securing affinity, miscibility, and/or adhesion to a rubber-containing adherend for which the present adhesive is used.

(B) polyurethane dispersion resin (PUD) component

The polyurethane protects or captures the amine-based compound described below, so that the adhesive layer (or coating layer) formed from the adhesive composition can be stably cured. In addition, since polyurethane has excellent affinity with rubber or latex components, it contributes to stably attaching the adhesive composition to an adherend including rubber, and as a result, excellent adhesion to the adherend (especially heat-resistant adhesion). make it possible

In one example, as the polyurethane component, water- _{dispersed polyurethane dispersed in water (H 2} O) may be used. When water-dispersed polyurethane is used, the unique wear resistance and elasticity of polyurethane can also be secured. The content of water included in the water-dispersed polyurethane component is not particularly limited as long as it is not contrary to the present application, such as being able to satisfy the viscosity of the entire composition described above.

For example, the content of water included in the water-dispersed polyurethane component may be in the range of 40 wt% to 80 wt% (when the weight of the water-dispersed polyurethane single component is 100 wt%), and the other content is polyurethane can occupy this In some cases, the water-dispersible polyurethane may contain a known trace amount of additives in a small amount of about 10% by weight or less, about 5% by weight or less, or about 1% by weight or less.

The type of polyurethane is not particularly limited, as long as it is not contrary to the present application, such as being able to satisfy the viscosity of the entire composition described above.

For example, polycarbonate-based urethane, polyester-based urethane, polyacrylic-based urethane, polytetramethylene-based urethane, polycaprolactone-based urethane, polypropylene-based urethane, or polyethylene-based urethane may be used. Also, one or more of those listed above may be used.

In one example, the molecular weight of the polyurethane may be in the range of 250,000 to 350,000. Unless otherwise specified, in the present specification, "molecular weight" may be a weight-average molecular weight (Mw) measured using Gel Permeation Chromatograph (GPC).

Specifically, the lower limit of the polyurethane weight average molecular weight (Mw) is, for example, 255,000 or more, 260,000 or more, 265,000 or more, 270,000 or more, 275,000 or more, 280,000 or more, 285,000 or more, 290,000 or more, 295,000 or more, 300,000 or more, or 305,000 or more. And, the upper limit of the weight average molecular weight (Mw) of the polyurethane is, for example, 345,000 or less, 340,000 or less, 335,000 or less, 330,000 or less, 325,000 or less, 320,000 or less, 315,000 or less, 310,000 or less, 305,000 or less or 300,000 or less. have. When the molecular weight range is satisfied, it is advantageous to secure the viscosity of the entire adhesive composition described above, and as a result, the adhesive strength of the adhesive, fatigue resistance of the rubber reinforcing material, etc., abrasion resistance and elasticity can be secured.

If the above weight average molecular weight range is satisfied, the method for preparing the water-dispersed polyurethane is not particularly limited. For example, as in Preparation Example 1 below, a prepolymer having units derived from polyols, diols and isocyanates is neutralized with a neutralizing agent, and the neutralized prepolymer is stirred with distilled water to proceed with water dispersion, followed by reaction with a chain extender In this way water-dispersible polyurethanes can be prepared.

As described above, if the weight average molecular weight range of the polyurethane is satisfied, the types of polyols, diols, and isocyanates used to form the urethane are not particularly limited.

For example, a diol such as 1,6-HD or 1,4-EG may be used, and as the polyol, a polyester-based polyol or a polyether-based polyol other than the diol may be used. In addition, as the isocyanate, diisocyanate or polyisocyanate may be used, and these may be aliphatic or aromatic isocyanate.

In one example, the polyurethane may have a unit derived from a polyester-based polyol having a weight average molecular weight (Mw) of 5,000 or less. Specifically, the upper limit of the weight average molecular weight of the polyester-based polyol used to form the polyurethane may be, for example, 4,500 or less, 4,000 or less, 3,500 or less, 3,000 or less, 2,500 or less, or 2,000 or less, and the lower limit is, for example, For example, it may be 500 or more, 1,000 or more, or 1,500 or more. When the above range is satisfied, it may be advantageous to control the weight average molecular weight of the polyurethane in the range described above, and to obtain an effect according to the use of the polyurethane.

In one example, in the adhesive composition, the (B) polyurethane may be included in 0.5 wt% or more, based on the total content of the composition. The content may refer to a content occupied by polyurethane solids in the composition. Specifically, the lower limit of the content of the polyurethane may be, for example, 1.0 wt% or more, 1.5 wt% or more, or 2.0 wt% or more, and the upper limit thereof is, for example, 9.0 wt% or less, for example, 9.0 wt% or more. Less than 8.5 wt%, 8.0 wt% or less, 7.5 wt% or less, 7.0 wt% or less, 6.5 wt% or less, 6.0 wt% or less, 5.5 wt% or less, 5.0 wt% or less, 4.5 wt% or less, 4.0 Weight % or less, 3.5 wt% or less, 3.0 wt% or less, 2.5 wt% or less, or 2.0 wt% or less.

In one example, considering the overall viscosity range of the composition, the solid content of the polyurethane satisfying the above-described molecular weight in the composition may be in the range of 1.0 wt% to 5.0 wt%.

When the content range is satisfied, the effect according to the use of the corresponding composition can be sufficiently exhibited. For example, when the content of the polyurethane is less than the above range, the effect of using the polyurethane is insignificant, and the viscosity may be lowered. In addition, when the content of the polyurethane exceeds the above range, while the viscosity of the adhesive is excessively increased, the adhesive force may decrease.

(C) amine-based adhesion promoter component

The amine-based adhesion promoter (C) participates in the curing of the composition to form a stable coating layer on the adherend, and can improve the problem of lowering adhesion caused by excessive water content in the composition.

Specifically, in the present application, (B) water-dispersible polyurethane and (G) an amine-based adhesion promoter having a long chain structure in consideration of a decrease in viscosity due to the use of an excessive amount of solvent. Since the amine-based adhesion promoter having a long chain structure can form a large molecular weight (compared to the case where the amine-based adhesion promoter is not used) during the preparation and curing of a composition containing an excess of a solvent (eg, water), the molecular weight to ensure the cohesive force at an appropriate level. As a result, a stable adhesive coating layer can be formed on the adherend. As a result, excellent adhesion and sufficient physical properties (eg, mechanical strength, etc.) suitable for the use may be provided.

In one example, fatty acid amide is used as the amine-based adhesion promoter (C). Although not particularly limited, the fatty acid amide may be a reactant formed by a reaction (eg, dehydration condensation) _{between a fatty acid (C 1} ) and an amine compound (C _{2 ).}

In relation to the amine-based adhesion promoter (C), “fatty acid” may mean a carboxylic acid having a long saturated or unsaturated aliphatic chain. In this case, the number of carbon atoms in the aliphatic chain of the fatty acid may be in the range of 6 to 30. Specifically, the carbon number of the aliphatic chain may be, for example, 8 or more, 10 or more, 12 or more, or 14 or more, and may be 28 or less, 26 or less, 24 or less, 22 or less, or 20 or less. The long chain of the fatty acid contributes to providing a long chain structure to the amine-based adhesion promoter, thereby providing excellent adhesion and physical properties.

In one example, the fatty acid (C ₁ ) may be a saturated fatty acid that does not have a double bond in the aliphatic chain. As described above, if the number of carbon atoms in the chain is in the range of 6 to 30, it is not particularly limited, but usable saturated fatty acids include caprylic acid (CH ₃ (CH ₂ ) ₆ COOH), capric acid (CH ₃ (CH _{2 ) 8} COOH). ), lauric acid (CH ₃ (CH ₂ ) ₁₀ COOH), myristic acid (CH ₃ (CH ₂ ) ₁₂ COOH), palmitic acid (CH ₃ (CH ₂ ) ₁₄ COOH), stearic acid (CH ₃ ( CH ₂ ) ₁₆ COOH), arichidic acid (CH ₃ (CH ₂ ) 18 COOH), _{behenic acid (CH 3 (CH 2 ) 20 COOH), lignoceric acid (CH 3} (CH ₂ ) ₂₂ COOH) or cerotic acid (CH ₃ (CH ₂ ) ₂₄ COOH) and the like. Also, one or more of the fatty acids listed above may be used together to form an amine-based adhesion promoter.

In one example, considering the long-chain structure of fatty acids, myristic acid (CH ₃ (CH ₂ ) ₁₂ COOH), palmitic acid (CH ₃ (CH ₂ ) ₁₄ COOH), stearic acid (CH ₃ (CH ₂ ) ₁₆ COOH) or arichidic acid (CH ₃ (CH ₂ ) ₁₈ COOH) can be used. Also, one or more of the fatty acids listed above may be used together to form an amine-based adhesion promoter.

In the present application, in relation to the amine-based adhesion promoter (C), the term “amine compound” may refer to a compound in which a hydrogen atom of ammonia is substituted with an organic group as well as ammonia. The type of organic group is not particularly limited.

In one example, with respect to the amine-based adhesion promoter (C), the “amine compound” may be a diamine. When diamine is used, the amine-based adhesion promoter (C) may be a fatty acid bis amide.

In one example, the diamine may be an alkylene diamine having 1 to 12 carbon atoms. Although not particularly limited, as the alkylene diamine, for example, ethylene diamine may be used.

In one example, the amine-based adhesion promoter may be represented by Formula 1 below.

[Formula 1]

In Formula 1, R ₁ and R ₂ may each independently be a substituted or unsubstituted aliphatic chain group having 6 to 30 carbon atoms, and A may be a divalent group having 1 to 12 carbon atoms. In this case, R ₁ and R ₂ may be a unit derived from the fatty acid (C ₁ ) described above, and A may be a unit derived from the _{amine compound (C 2 ) described above.}

In one example, R ₁ and R ₂ of Formula 1 may be the same. In another example, R ₁ and R ₂ in Formula 1 may be different.

In one example, A in Formula 1 may be an alkylene group having 1 to 8, 2 to 6, or 2 to 4 carbon atoms.

In one example, the amine-based adhesion promoter may exist in a solid state or a liquid state. When the amine-based adhesion promoter is in a solid state, it is dispersed in a solvent (water or organic solvent) and may be mixed with other composition components. In this case, the content and type of the solvent used in the amine-based adhesion promoter component may be determined within a range that can satisfy the viscosity of the entire composition described above.

In one example, the adhesive composition may include a predetermined amount of the (C) amine-based adhesion promoter and (D) an amine-based chain extender to be described later. _{For example, the weight (W 1} ) of the (C) amine-based adhesion promoter included in the adhesive composition may be greater than _{the weight (W 2} ) of the (D) amine-based chain extender. The content (W ₁ , W ₂ ) may mean a solid content occupied by (C) an amine-based adhesion promoter and (D) an amine-based chain extender, respectively.

Further, in one example, in the adhesive composition, the (C) by weight of the extended amine by weight of the adhesion promoter (W ₁₎ and the (C) an amine-based chain, the (W ₂₎ the ratio (W ₁ / W ₂₎ may range from 1.5 to 10.0. Specifically, the ratio (W ₁ /W ₂ ) may be 2.0 or more, 2.5 or more, 3.0 or more, 3.5 or more, 4.0 or more, 4.5 or more, 5.0 or more, 5.5 or more, 6.0 or more, and 9.5 or less, 9.0 or less, 8.5 or more. or less, 8.0 or less, 7.5 or less, 7.0 or less, and 6.5 or less. If the ratio (W ₁ /W ₂ ) does not satisfy the range, since it does not satisfy the viscosity range of the composition described above, there is a problem in that the adhesive strength is reduced.

In one example, the ratio (W ₁ /W ₂ ) may be in the range of 3.0 to 5.0. Specifically, within the above range, the ratio (W ₁ /W ₂ ) may be 3.5 or more, 4.0 or more, or 4.5 or more. As confirmed in the experiment below, when the corresponding range is satisfied, better adhesion can be provided to the tire cord.

In one example, the adhesive composition may include 1.0 wt% or more of the (C) amine-based adhesion promoter, based on the total content of the composition. The content may mean the solid content occupied by the (C) amine-based adhesion promoter. Specifically, (C) the lower limit of the content of the amine-based adhesion promoter may be, for example, more than 1.0 wt%, more specifically, 1.5 wt% or more, or 2.0 wt% or more, and the upper limit thereof is, for example, 5.0 wt% % or less, 4.5 wt% or less, 4.0 wt% or less, 3.5 wt% or less, 3.0 wt% or less, 2.5 wt% or less, or 2.0 wt% or less. When the content range is satisfied, the effect according to the use of the corresponding composition can be sufficiently exhibited.

(D) amine-based chain extender component

The amine-based chain extender (D) may refer to an amine-based compound that does not correspond to the above-described (C) amine-based adhesion promoter. That is, (D) the amine-based chain extender and (C) the amine-based adhesion promoter have different structures. For example, the amine-based chain extender may be used in the sense of encompassing primary, secondary or tertiary amines that do not have a chain structure derived from the fatty acids described above.

The amine-based chain extender participates in the curing of the composition to form a stable coating layer on the adherend. In consideration of its function, the (D) amine-based chain extender may be referred to as an amine-based curing agent. Alternatively, (C) the amine-based adhesion promoter may be referred to as a first amine compound, and (D) the amine-based chain extender may be referred to as a second amine compound.

If it is different from the (C) amine-based adhesion promoter, the type of the (D) amine-based chain extender is not particularly limited. For example, an aliphatic amine, an alicyclic amine or an aromatic amine may be used.

In one example, a commercially available product may be used as the (D) amine-based chain extender. Specifically, DAEJUNG's Piperazine, Kukdo Chemical's G640, Huntsman's HK511, etc. may be used.

In one example, the adhesive composition comprises (D) an amine-based chain extender, as described above, such that the weight of the (D) amine-based chain extender is less than the weight of the (C) amine-based adhesion promoter. can do.

In one example, as described above, the adhesive composition may include (C) the amine-based adhesion promoter and (D) the amine-based chain extender in a predetermined weight ratio (W ₁ /W ₂ ).

In one example, the adhesive composition may include 3.0 wt% or less of the (D) amine-based chain extender, based on the total content of the composition. The content may refer to the solid content occupied by the (D) amine-based chain extender. Specifically, (D) the upper limit of the content of the amine-based chain extender may be, for example, 2.5 wt% or less, or 2.0 wt% or less, or 1.0 wt% or less. And, the lower limit of the content may be, for example, 0.05 wt% or more, 0.1 wt% or more, 0.2 wt% or more, 0.3 wt% or more, 0.4 wt% or more, or 0.5 wt% or more. When the content range of the amine-based chain extender described above is satisfied, the effect according to the use of the composition may be sufficiently exhibited. For example, (D) when the content of the amine-based chain extender is less than the above range, curing of the composition is not sufficient, and when it exceeds the above range, the adhesive strength may be reduced due to excessive curing.

In one example, based on the content of the entire composition, the _{sum of the weight (W 1} ) of the (C) amine-based adhesion promoter and (D) the weight of the amine-based chain extender (W ₂ ) is 1.0 weight % or more, specifically more than 1.0 wt%, 1.5 wt% or more, 2.0 wt% or more, 2.5 wt% or more, 3.0 wt% or more, 3.5 wt% or more, 4.0 wt% or more, 4.5 wt% or more, or 5.0 wt% or more can And, the upper limit is, for example, 8% by weight or less, 7.0% by weight or less, 6.0% by weight or less, 5.0% by weight or less, more specifically 4.5% by weight or less, 4.0% by weight or less, 3.5% by weight or less, 3.0% by weight or less % or less, 2.5 wt% or less, 2.0 wt% or less, or 1.5 wt% or less. When the above-described content range is satisfied, the effect according to the combination of the (C) amine-based adhesion promoter and (D) the amine-based chain extender can be sufficiently exhibited.

(E) Epoxy component

In one example, the adhesive composition may further include (E) an epoxy compound. The epoxy compound functions as a kind of curing agent, forms a three-dimensional network structure during heat treatment of the adhesive, and imparts adhesion and layer stability to the coating layer formed from the adhesive composition.

On the premise that the viscosity range of the entire composition described above is satisfied, the type of the epoxy compound included in the adhesive composition is not particularly limited. For example, diethylene glycol-diglycidyl ether, polyethylene glycol-diglycidyl ether, polypropylene glycol-diglycidyl ether, neopentyl glycol-diglycidyl ether, 1,6-hexanediol- Diglycidyl ether, glycerol-polyglycidyl ether, trimethylolpropane-polyglycidyl ether, polyglycerol-polyglycidyl ether, pentaerythol-polyglycidyl ether, diglycerol-polyglycidyl ether glycidyl ether-based compounds such as dil ether and sorbitol-polyglycidyl ether; novolac-type epoxy resins such as phenol novolac-type epoxy resins and cresol novolak-type epoxy resins; and a bisphenol type epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin may be used as the epoxy compound.

In addition, a known or commercially available epoxy resin may be used for the adhesive composition on the premise that the viscosity range of the entire composition described above is satisfied. For example, NAGASE's EX614B, Kolon's KETL6000, Ipox chemical's CL16, or Raschig's GE500 may be used as the epoxy resin.

In one example, the equivalent weight of the epoxy resin (Epoxy Equivalent Weight, g / eq) may be in the range of 120 to 300 g / eq. When the equivalent weight of the epoxy resin is less than 120, it may be difficult to form a network structure because the polymerization unit of the epoxy resin is small. In addition, when the equivalent weight of the epoxy resin is more than 300, the number of epoxy per unit molecule is relatively insufficient, so that the adhesive force may decrease.

In one example, the adhesive composition may include 0.5% by weight or more of the (E) epoxy compound, based on the total content of the composition. The content may mean a solid content occupied by the (E) epoxy compound in the composition. Specifically, (E) the lower limit of the content of the epoxy compound may be, for example, 1.0% by weight or more, 2.0% by weight or more, 3.0% by weight or more, 4.0% by weight or more, or 5.0% by weight or more. In addition, the upper limit of the content may be, for example, 10% by weight or less, specifically 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, or 1.5% by weight or less.

When the content range of the epoxy compound described above is satisfied, the effect according to the use of the composition can be sufficiently exhibited. For example, if an epoxy compound exceeding the above range is used, adhesive strength may be reduced due to excessive curing of the composition. In addition, when an epoxy compound less than the above range is used, it is difficult to obtain an effect according to the use of the epoxy compound.

(F) isocyanate component

In one example, the adhesive composition may further include (F) isocyanate. The isocyanate functions as a kind of crosslinking agent, forming a three-dimensional network structure during heat treatment for the adhesive, thereby imparting adhesive strength and layer stability to the coating layer formed from the adhesive composition.

The type of isocyanate included in the adhesive composition is not particularly limited, but may be selected in consideration of the viscosity range of the entire composition described above.

For example, as the isocyanate, a compound containing an aromatic group, that is, an aromatic isocyanate may be used. In the case of the aromatic polyisocyanate, it may be advantageous to increase the low viscosity of the aqueous composition since a high reaction rate can be secured as compared with the non-aromatic polyisocyanate.

In one example, the aromatic group included in the isocyanate compound may be a phenyl group, and the isocyanate containing such an aromatic group includes, for example, methylenediphenyldiisocyanate, methylenediphenylpolyisocyanate, or polymethylenepolyphenylpolyisocyanate. can be used

In one example, the isocyanate compound may have a blocked terminal (Blocked isocyanate). The blocked isocyanate compound can be prepared, for example, by a reaction of adding a known blocking agent to the polyisocyanate compound. Blocking agents that can be used include, for example, phenol, thiophenol, chlorophenol, cresol, resorcinol, p-sec-butylphenol, ptert-butylphenol, p-sec-amylphenol, p-octylphenol, p- phenols such as nonylphenol; secondary or tertiary alcohols such as isopropyl alcohol and tert-butyl alcohol; aromatic secondary amines such as diphenylamine and xylidine; phthalic acid imides; lactams such as ?-valerolactam; caprolactams such as ε-caprolactam; active methylene compounds such as malonic acid dialkyl ester, acetylacetone, and acetacetic acid alkyl ester; oximes such as acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime; A basic nitrogen compound, such as 3-hydroxypyridine, acidic sodium sulfite, etc. can be used.

In one example, a commercially available water-dispersed blocked isocyanate may be used provided that the viscosity range of the entire composition described above is satisfied. For example, EMS's IL-6 or MEISEI Chemical's DM-6500 may be used as the isocyanate according to an embodiment of the present invention.

In one example, the adhesive composition may include 1 wt% or more of (F) isocyanate, based on the total content of the composition. The content may mean a solid content occupied by (F) isocyanate in the composition. Specifically, (F) the lower limit of the content of isocyanate may be, for example, 2.0 wt% or more, 3.0 wt% or more, 4.0 wt% or more, or 5.0 wt% or more. In addition, the upper limit of the content may be, for example, 10 wt% or less, 9.0 wt% or less, 8.0 wt% or less, 7.0 wt% or less, 6.0 wt% or less, or 5.0 wt% or less.

When the content range of the isocyanate described above is satisfied, the effect according to the use of the composition can be sufficiently exhibited. For example, when an isocyanate exceeding the above range is used, the fatigue degree of the reinforcing material having an adhesive coating layer may increase due to excessive crosslinking, and physical properties may be deteriorated. In addition, when an isocyanate less than the above range is used, the physical properties of the adhesive layer may decrease because crosslinking does not occur sufficiently.

In one example, when the (E) epoxy compound is used together, (F) the isocyanate compound may be used so that the epoxy compound and the isocyanate compound have a weight ratio of 4:1 to 1:4. In another example, on the premise that the content range is satisfied, the weight of (F) isocyanate in the entire composition may be greater than the weight of (E) epoxy compound. When the above content is satisfied, sufficient crosslinking and curing at an appropriate level can be achieved.

(G) solvent

In the present application, the solvent component may mean a component excluding a component whose content can be measured as a solid content, such as components (A) to (F) and (H) to be described later. For example, the solvent component may be referred to as a non-solid component.

The adhesive composition of the present application includes water (H ₂ O) as the solvent component (G). For example, in the present application, an organic solvent (eg, toluene or ethanol, etc.) may not be used in consideration of the risk of harm to the human body and flammability, or an excess of water may be used as a solvent together with a small amount of the organic solvent.

In one example, the adhesive composition, based on the total weight of the composition for which the viscosity is measured, 40% by weight or more, 45% by weight or more, 50% by weight or more, 55% by weight or more, 60% by weight or more, 65% by weight or more It may include a solvent component in an amount of 70% by weight or more, 70% by weight or more, 75% by weight or more, or 80% by weight or more, and 90% by weight or less, and the solvent may be water.

In another example, an excess or most of the solvent content may be occupied by water. For example, an excess (eg, about 40% by weight or more) of the solvent component included in the composition may be water, and the remaining content excluding water in the solvent (eg, 30% by weight or less, 25% by weight or less, 20% by weight or less) or less, 15 wt% or less, 10 wt% or less, or 5 wt% or less) may be occupied by an organic solvent or the like.

That is, according to an embodiment of the present application, the adhesive composition may be viewed as an aqueous composition or an aqueous composition.

In one example, water used as a solvent in the adhesive composition may be demineralized water (or pure water, demineralized water).

In one example, based on the total weight of the composition for which the viscosity is measured, the content of water is 40 wt% or more, 45 wt% or more, 50 wt% or more, 55 wt% or more, 60 wt% or more, 65 wt% or more , 70 wt% or more, 75 wt% or more, or 80 wt% or more. The upper limit of the water content may be, for example, 85% by weight or less, 80% by weight or less, 75% by weight or less, 70% by weight or less, 65% by weight or less, or 60% by weight or less.

In one example, the content of water in the entire composition may mean the content of water mixed as a solvent.

In another example, the content of water in the overall composition is determined not only the content of water to be mixed as a solvent, but also the solvent ( For example, water or other small amounts of organic solvents) may be included.

When the content of the solvent is less than the above range, the degree of dispersibility and miscibility of each component forming the composition deteriorates, the coating workability deteriorates, and the adhesive force of the adhesive layer formed on the adherend may be reduced. In addition, when the content of the solvent exceeds the above range, it is not easy to form an adhesive layer on the adherend, so that the physical properties required for a rubber reinforcing material or a rubber composite cannot be sufficiently exhibited, and fairness is poor, such as taking a long time to dry. and increase the production cost.

As described above, in the present application, components other than the solvent (eg, (A) to (F) component and/or (H) component) are mixed in the solvent (G) of the above content to constitute a composition. The content of components other than the solvent may be the solid content of each component. For example, the composition may include 60 to 85% by weight of solvent and 15 to 40% by weight of solids.

(H) other ingredients

The adhesive composition of the present application does not contain resorcinol-formaldehyde or a component derived therefrom. That is, the composition of the present application may be, that is, an RF-free composition. Accordingly, an environmentally friendly adhesive composition that is not harmful to the human body compared to the prior art using RF components can be provided. In addition, the use of such adhesive compositions provides the advantage of reducing after-care and post-treatment costs.

Other than that, on the premise that it is not contrary to the present application described above, known additives and the like may be included in a small range.

As described above, the composition of the present application may be a mixture of components (A) to (D) and (G), or a mixture in which (E) and/or (F) are further mixed thereto. The composition in which the above components are mixed may include each component in the above-described solid content. The use of these compositions may be for coating or bonding applications.

In another example related to the present application, the present application relates to a rubber reinforcement material. The rubber reinforcement may be, for example, a tire cord coated with the adhesive described above on a base substrate. The base substrate may be a raw cord including a fiber component.

Specifically, the tire cord may include: a raw cord; and a coating layer formed on the raw cord. The coating layer may be or include a coating layer formed from the above-described adhesive composition, and may be coated in a shape surrounding the raw code.

The fibers included in the raw cord are not particularly limited, but may be, for example, polyester fibers, nylon fibers, aramid fibers, cellulose fibers or glass fibers.

In one example, the raw cord may be a two-ply or three-ply cord formed by twisting 2 to 3 strands of fibers.

In one example, the raw code may be a hybrid code. For example, the raw cord may be a hybrid cord formed by twisting lower-twisted yarns having different types of fibers, such as including an aramid lower-twisted yarn and a nylon lower-twisted yarn.

In the case of a hybrid cord formed by twisting different types of lower twisted yarns, fatigue resistance may be low due to a difference in physical properties (eg, modulus, etc.) between the lower twisted yarns, which may result in poor tire stability. However, since the adhesive composition described above not only forms an appropriate coating layer on the hybrid raw cord as the adherend but also provides excellent adhesion between the hybrid raw cord as the adherend and the tire composition adjacent thereto, the inner skin of the tire according to the use of the hybrid cord This is expected to improve the property degradation problem to some extent.

In one example, the number of twists of the fiber strands used to form the raw cord is, for example, 200 TPM (twist per meter) or more, 250 TPM or more, 300 TPM or more, 350 TPM or more, 400 TPM or more, 450 TPM or more. or more, 500 TPM or more, or 550 TPM or more. In addition, the upper limit of the number of twists may be, for example, 800 TPM or less, 750 TPM or less, 700 TPM or less, 650 TPM or less, 600 TPM or less, 550 TPM or less, 500 TPM or less, 450 TPM or less, or 400 TPM or less.

In one example, the coating layer may be or include a coating layer formed from the adhesive composition described above. Specifically, the tire cord may be formed by coating the adhesive composition on the raw cord. A method of coating the adhesive composition is not particularly limited. For example, the coating may be made by a known dipping or spraying method.

In one example, the coating layer included in the tire cord may include a first coating layer; and a second coating layer formed on the first coating layer. Specifically, the tire cord may sequentially include a raw cord, a first coating layer, and a second coating layer (see FIG. 2 ).

Although not particularly limited, the first coating layer and the second coating layer may have a visible boundary.

In one example, the first coating layer may include the same component as the second coating layer.

In one example, the first coating layer may include a component different from that of the second coating layer. Specifically, the first coating layer may be formed by dipping the raw code into the composition (first coating solution) for forming a first coating layer including a reactive active group-imparting component. That is, the first coating layer is formed to surround the raw cord or its surface. The type of the reactive active group-imparting component used in the first coating layer is not particularly limited, but, for example, the first coating solution may include one or more compounds selected from epoxy and isocyanate. The solvent component included in the first coating layer forming composition (first coating solution) is not particularly limited, but water (eg, demineralized water) may be used in consideration of miscibility with the second coating layer. The second coating layer is formed by dipping the tire cord (or tire cord precursor) on which the first coating layer is formed on the surface of the second coating layer-forming composition (second coating solution), and the second coating layer-forming composition (second coating solution) is It may be the same as the adhesive composition satisfying the above-described viscosity.

In one example, the first coating solution may include an isocyanate compound and an epoxy compound. In this case, the epoxy compound and the isocyanate compound may be used in a weight ratio of 4:1 to 1:4, 3:1 to 1:3, or 2:1 to 1:2 to achieve sufficient crosslinking and curing at an appropriate level.

In another example, on the premise that the content range is satisfied, the weight of the isocyanate compound in the entire composition may be greater than the weight of the epoxy compound.

In another example related to the present application, the present application relates to a method of manufacturing a rubber reinforcement. The manufacturing method of the rubber reinforcing material includes applying a coating solution on a base substrate for a rubber reinforcing material and drying the coating solution to form a coating layer.

A method of applying the coating solution on the base substrate is not particularly limited, but may be, for example, spraying or immersion, preferably immersion.

In one example, the rubber reinforcement may be a tire cord.

In one example, the base substrate may be a fiber substrate, specifically, raw cord. The description regarding the material for forming the raw code and the like is the same as described above.

In one example, the coating solution may be the adhesive composition described above.

In one example, the method comprises the steps of: forming a first coating layer on the base substrate by applying a first coating solution on the base substrate for rubber reinforcement and drying; and forming a second coating layer on the first coating layer by drying the second coating solution on the first coating layer.

A method of applying the first coating solution on the base substrate or applying the second coating solution on the first coating layer is not particularly limited, but may be, for example, spraying or immersion, preferably immersion.

In one example, the components of the first coating solution and the second coating solution may be the same or different.

For example, the first coating solution may include an epoxy compound and an isocyanate compound in order to impart a reactive group to the fiber substrate or the like. In this case, the epoxy compound and the isocyanate compound may be used in a weight ratio of 4:1 to 1:4, 3:1 to 1:3, or 2:1 to 1:2 to achieve sufficient crosslinking and curing at an appropriate level.

In one example, the first coating solution may include a solvent. That is, the first coating solution may include an epoxy compound, an isocyanate compound, and a solvent.

When the solvent is insufficient, the primary coating by immersion is not performed smoothly, and when the content of the solvent is excessively large, the reactive group is not sufficiently provided to the base substrate for reinforcing rubber. Considering these points, the solvent has a content of 94 to 99% by weight, and the mixture of the epoxy compound and the isocyanate compound has a content of 1 to 6% by weight based on the total weight of the first coating solution. That is, the first coating solution includes 1 to 6% by weight of a mixture consisting of an epoxy compound and an isocyanate compound and 94 to 99% by weight of a solvent based on the total weight. Although not particularly limited, the solvent that may be included or used in the first coating solution may be water.

In one example, the base substrate for the rubber reinforcement may be dried after being immersed in the first coating solution. Specifically, the first coating solution is applied on the base substrate for rubber reinforcement by immersion. Thereafter, the first coating solution is dried and cured to form a first coating layer.

In an embodiment according to the present application, drying of the first coating solution applied on the base substrate may be performed at a temperature of 100 to 160° C. for 30 to 150 seconds. In addition, in an embodiment of the present application, after the drying, curing the dried first coating solution at a temperature of 200 to 260° C. for 30 to 150 seconds may be performed. A first coating layer is formed on the base substrate for rubber reinforcement according to the drying and curing. Through drying and curing under the above conditions, the first coating layer may be stably formed on the base substrate for rubber reinforcement.

Although not particularly limited, a tension in the range of 0.05 to 3.00 g/d may be applied to the raw cord during the dipping, drying, and/or curing process. However, another embodiment of the present invention is not limited thereto, and tension may not be applied to the raw code.

In one example, the second coating solution different from the first coating solution including the epoxy compound and the isocyanate compound may be an adhesive composition satisfying the above-described viscosity. Specifically, the second coating solution may include at least (A) latex, (B) water-dispersible polyurethane, (C) amine-based adhesion promoter, and (G) water-containing solvent.

In an embodiment according to the present application, the method may further include forming a second coating layer on a base substrate for a rubber reinforcing material to which a reactive active group is imparted, that is, on the first coating layer. A process (eg, method and conditions) of forming the second coating layer may be the same or similar to that of forming the first coating layer.

For example, a second coating solution is applied on the base substrate and the first coating layer, and then drying and curing of the second coating solution may be performed. Application of the second coating solution may be made by immersion or spraying.

In embodiments related to the present application, drying of the second coating solution may be performed at a temperature of 100 to 160° C. for 30 to 150 seconds. In addition, in the embodiment related to the present application, the curing of the second coating solution after the drying may be made at a temperature of 200 to 260° C. for 30 to 150 seconds. By drying and curing under the above conditions, the second coating layer may be stably formed on the first coating layer. As a result, a rubber reinforcement having a coating layer is provided.

Although not particularly limited, a tension in the range of 0.05 to 3.00 g/d may be applied to the raw cord during the dipping, drying, and/or curing process. However, another embodiment of the present invention is not limited thereto, and tension may not be applied to the raw code.

A method of manufacturing a rubber reinforcement according to an embodiment of the present application will be described with reference to FIGS. 2 and 3 as follows.

The raw cord 10 may be manufactured and/or distributed while being wound around the first winder 100 . Then, the raw code 10 may be immersed in the first coating solution 21 ′ contained in the first coating tank 200 and applied on the raw code 10 . During the immersion process, tension, immersion time and temperature may be appropriately adjusted, which may be appropriately adjusted by those skilled in the art.

Subsequently, the first coating solution 21 ′ applied to the raw cord 10 may be dried and cured. Drying may be performed in the drying apparatus 300 . Conditions such as temperature and time for drying and curing are as described above.

Next, a step of forming the second coating layer 22 on the first coating layer 21 is performed. The second coating layer forming step is a step of applying the rubber-based adhesive composition to the raw cord 10 to which the active group is provided by the first coating layer 21 . A second coating solution having a composition different from that of the first coating solution may be used to form the second coating layer, and a dipping process may be applied similarly to the formation of the first coating layer.

To form the second coating layer 22 , the raw cord 10 coated with the first coating layer 21 is immersed in the second coating solution 22 ′. The second coating solution 22 ′ is contained in the second coating tank 400 . The second coating solution 22 ′ is applied on the first coating layer 21 by the immersion. During the immersion process, tension, immersion time and temperature may be appropriately adjusted, which may be appropriately adjusted by those skilled in the art.

Subsequently, drying and curing of the second coating solution 22 ′ is performed. The drying and curing may be performed in the drying apparatus 500 . Conditions such as temperature and time for drying and curing are as described above.

Through the fixing as described above, the second coating layer 22 is formed on the first coating layer 21 . The tire cord 30 manufactured in this way is wound around the second winder 600 .

As described above, the tire cord 30 having the coating layer formed by dipping may be referred to as a dip cord.

In another example related to the present application, the present application relates to a rubber composite. The rubber composite may be, for example, a tire. The tire includes the aforementioned tire cord.

In addition to the tire cord, the tire may have a generally known configuration, as shown in FIG. 4 .

According to an embodiment of the present application, an adhesive composition that is environmentally friendly, has a low risk of fire, has excellent adhesion, and is advantageous in improving workability (fairness) and reducing costs is provided. In addition, the present application has the effect of the invention of providing a rubber reinforcing material or rubber composite with improved physical properties (eg, mechanical strength or fatigue resistance, etc.) prepared using the adhesive composition.

1 schematically shows a Ubelode viscometer in order to explain a method of measuring the relative viscosity of the adhesive composition of the present application.
2 schematically illustrates a cross-section of a tire cord that may be manufactured using an adhesive composition according to an example of the present application.
3 schematically shows a manufacturing process of a tire cord.
4 schematically illustrates a cross-section of a tire that may be manufactured using an adhesive composition according to an example of the present application.

Hereinafter, the action and effect of the invention will be described in more detail through specific examples of the invention. However, this is presented as an example of the invention and the scope of the invention is not limited in any sense by this.

manufacturing example

Preparation Example 1: Preparation of water-dispersed polyurethane

A polyester-based polyol (weight average molecular weight: about 2,000), a diol (1,6-Hexane diol), and an ionomer (DMBA: Dimethylol butanoic acid) were added to a reactor and stirred at 75±5° C. for 4 hours. Then, an aliphatic isocyanate (H ₁₂ MDI: Dicyclohexymethane-4,4'-diisocyanate) was reacted for 2 hours to prepare a prepolymer, and after lowering the reaction temperature of the prepared prepolymer to 60° C., a neutralizing agent (TEA: Triethanolamine) was added to neutralize. At this time, a stirrer was used for dispersion, and the RPM of the stirrer was maintained at 1,000 to 1,500 to disperse. After dispersing, the solvent (Acetone) was removed from the prepolymer under reduced pressure. Thereafter, distilled water was added to the neutralized prepolymer to have a solid content of 60% by weight, followed by stirring to proceed with water dispersion. Finally, an aqueous dispersion polyurethane having a weight average molecular weight of about 308,000 was prepared by adding a chain extender (EDA: Ethylene diamine).

Preparation Example 2: Preparation of compositions of Examples and Comparative Examples

The compositions of Examples and Comparative Examples were prepared by performing mixing and stirring under the same conditions at the same content (% by weight) as in Table 1 below. Specifically, each component was mixed and stirred at about 20 °C for 24 hours.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 (A) Latex 14.7 13.7 12.7 11.7 14.7 14.7 14.7 14.7 14.7 (B) Water-dispersible polyurethane 1.8 1.8 1.8 1.8 0.8 2.8 3.8 1.8 1.8 (C) Amine-based adhesion promoter 1.8 1.8 1.8 1.8 1.8 1.8 1.8 2.8 3.8 (D) amine-based chain extender 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.6 0.85 (E) Epoxy compound 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 (F) isocyanate 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7 (G) solvent total content 76.4 77.4 78.4 79.4 77.4 75.4 74.4 75.2 73.95 water (pure) 46.8 49.2 51.7 54.2 48.4 45.1 43.4 43.7 40.7 Units (content): (A) to (F) each weight percent of solids, and weight percent of (G) solvent, which are non-solids.
(A) Latex: Closlen's 0653 VP Latex
(B) Water-dispersed polyurethane: The water-dispersed polyurethane prepared in Preparation Example 1 is used
(C) Amine-based adhesion promoter (primary amine compound): N,N'-Ethylenebis(stearamide), a reaction product of ethylenediamine and stearic acid
(D) amine-based chain extender (second amine compound): Piperazine
(E) Epoxy compound: NAGASE's EX614B whose equivalent weight is adjusted in the range of 120 to 300 g/eq
(F) Isocyanate: IL-6 from EMS
(G) solvent: non-solid component including demineralized water

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 (A) Latex 0 32 14.7 14.7 14.7 14.7 (B) Water-dispersible polyurethane 1.8 1.8 0.2 10 1.8 4.5 (C) amine-based adhesion promoter 1.8 1.8 1.8 1.8 0.5 6 (D) amine-based chain extender 0.4 0.4 0.4 0.4 0.4 0.4 (E) Epoxy compound 1.2 1.2 1.2 1.2 1.2 1.7 (F) isocyanate 3.7 3.7 3.7 3.7 3.7 3.4 (G) solvent total content 91.1 59.1 78 68.2 77.7 69.3 water (pure) 83.1 4.1 49.5 33.1 50.7 29.6 Units (content): (A) to (F) each weight percent of solids, and weight percent of (G) solvent, which are non-solids.
(A) Latex: Closlen's 0653 VP Latex
(B) Water-dispersed polyurethane: The water-dispersed polyurethane prepared in Preparation Example 1 is used
(C) Amine-based adhesion promoter (primary amine compound): N,N'-Ethylenebis(stearamide), a reaction product of ethylenediamine and stearic acid
(D) amine-based chain extender (second amine compound): Piperazine
(E) Epoxy compound: NAGASE's EX614B whose equivalent weight is adjusted in the range of 120 to 300 g/eq
(F) Isocyanate: IL-6 from EMS
(G) solvent: non-solid component including demineralized water

Preparation Example 3: Preparation of raw cord and tire cord

After preparing 2 strands (11, 12) of lower twisted yarn (Z-direction) having a twist number of 360 TPM using aramid yarn (1,500 de) and nylon yarn (1,260 de), the lower twisted yarn of the two strands was twisted at 360 TPM A ply-twisted yarn (1,500 de A / 1,260 de N) was prepared by twisting together (S-direction) with a twist number of . The ply-twisted yarn thus prepared was used as a raw cord (10).

A tire cord 30 was manufactured by forming a coating layer 20 on the raw cord 10 . Specifically, the raw cord made of aramid and nylon is immersed in the first coating solution, and then treated at a drying temperature of 150 ° C. and a curing temperature of 240 ° C. for about 1 minute, respectively, to form the first coating layer 21, thereby reacting the raw cord with the active group was given. In this case, the first coating solution is prepared by mixing an epoxy compound and an isocyanate compound, which are some of the components used in Preparation Example 2, in a weight ratio of about 1: 2, and 97% by weight of demineralized water.

Then, the adhesive compositions of Examples and Comparative Examples prepared according to Preparation Example 2 (hereinafter, second coating solution) were applied to the raw code on which the first coating layer was formed. Specifically, the raw cord on which the first coating layer was formed was immersed in the second coating solution, dried and cured to form the second coating layer 22 . At this time, drying and curing were performed by treatment for about 1 minute each at a drying temperature of 150 °C and a curing temperature of 235 °C. The first coating liquid immersion process and the second coating liquid immersion process were performed continuously, and the tension condition at this time was 0.5 g/d. Through the above process, a tire cord 30 was manufactured in the form of a dipped cord.

Experimental example

Experimental Example 1: Measurement of the relative viscosity of the compositions of Examples and Comparative Examples

The viscosity of each composition prepared in Preparation Example 2 was measured after standing for 30 minutes in a constant temperature water bath (about 25° C.) using an Ubbelohde viscometer. Specifically, after adding a certain amount of demineralized water to the Ubelode viscometer through the following process, the viscosity characteristics of the demineralized water are measured, and after measuring the viscosity characteristics of the composition in the same way, the relative viscosity is calculated based on the already measured viscosity characteristics of the demineralized water. Calculated. The results are shown in Table 2.

A viscosity measurement process will be described with reference to FIG. 1 as follows.

(1) Inject the sample (composition or demineralized water) into tube A of the Ubelode viscometer.

(2) After setting the constant temperature water bath to 25 ℃, fix the part C so that it is submerged in the water bath and leave it for 30 minutes.

(3) Using a pipette filler, let the sample come to the middle of part C.

(4) After that, let the sample flow down and measure the time it takes for the liquid level of the sample to pass through the upper scale of B and pass the lower scale of B.

(5) Calculate the relative viscosity by applying the measured time to the formula for calculating the relative viscosity below.

<Relative viscosity calculation formula>

Relative viscosity = T ₁ / T ₀

(T ₁ : Time taken for the adhesive composition to pass through the upper scale of B and pass through the lower scale of B, T ₀ : When demineralized water passes through the upper scale of B and passes through the lower scale of B time taken)

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Viscosity (RV) 2.71 2.68 2.64 2.58 2.67 2.73 2.77 2.72 2.73

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Viscosity (RV) 1.84 4.68 2.43 3.21 2.24 3.14

Experimental Example 2: Check the degree of resin pick up

In the adhesive (composition) of Examples and Comparative Examples prepared in Preparation Example 2, the raw cord prepared in Preparation Example 3 was immersed for 20 seconds, then rolled up and dried. Specifically, using a tensile tester, the raw cord was immersed in the adhesive solution at a constant speed (about 250 mm/min) and wound up therefrom. Then, the rolled up raw cord was dried in an oven at 240° C. for 1 minute and 30 seconds.

Resin Pick Up degree (RPU, %) was calculated as in [Equation 1] below, and the results are described in Table 3.

[Equation 1]

(W _b - W _a )/W _a x 100

In Equation 1, W _b is the weight (g) of the raw cord after immersion, and W _a is the weight (g) of the raw cord before immersion.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 RPU (%) 4.9 4.7 4.5 4.2 4.8 5.2 5.5 5.2 5.4

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 RPU (%) 2.2 8.7 3.8 6.5 3.2 6.8

As can be seen in Tables 3 and 4, it can be seen that the adhesive compositions of Comparative Examples 1, 3, and 5 have lower viscosity and higher flowability than those of Examples. If the flowability is too high, the pick-up rate is low as shown in Table 6. Accordingly, the coating layer may not be evenly formed on the adherend or the object to be coated, and sufficient adhesion may not be provided. The results of comparison of adhesive strength using the compositions of Examples and Comparative Examples can be confirmed in Tables 8 and 9 below.

In addition, as shown in Tables 3 and 4, it can be seen that the adhesive compositions of Comparative Examples 2, 4, and 6 have higher viscosity and lower flowability than in Examples. When the flowability is too low, the adhesive strength may decrease because sufficient mixing between the constituent components of the composition is not achieved. The results of comparison of adhesive strength using the compositions of Examples and Comparative Examples can be confirmed in Tables 8 and 9 below.

Experimental Example 3: Adhesion evaluation

Adhesion per unit area to the tire cord prepared in Preparation Example 3 was evaluated using the compositions of Examples and Comparative Examples, respectively. The adhesive strength evaluation was performed by measuring the adhesive peel strength of the tire cord using the method of ASTM D4393.

Specifically, a 0.6 mm thick rubber sheet, cord paper (tire cord of Preparation Example 3), a 0.6 mm thick rubber sheet, cord paper (tire cord of Preparation Example 3), and a 0.6 mm thick rubber sheet are sequentially laminated, , 60 kg/cm ² The sample was prepared by vulcanization at 170 ° C. for 15 minutes at a pressure of. Then, the sample was cut to prepare a specimen having a width of 1 inch. For reference, the rubber sheet has the composition shown in Table 7 below, and is a sheet used for carcass constituting a tire. By using a laminate using such a rubber sheet, the adhesion of the tire cord to the carcass layer can be confirmed.

For the prepared specimen, a peel test was performed at 25° C. at a rate of 125 mm/min using a universal testing machine (Instron) to measure the adhesion of the tire cord to the carcass layer, and the relative size of the measured adhesion is shown. 8 and 9. At this time, the average value of three times of the load generated during peeling was calculated as the adhesive force.

rubber sheet component Content (weight ratio based on 100 parts by weight of natural rubber) natural rubber 100 zinc oxide 3 carbon black 29.8 stearic acid 2.0 pine tar 7.0 Mercaptobenzothiazole 1.25 sulfur 3.0 diphenylguanidine 0.15 Phenylbetataphthalamine 1.0

Example
10 Example
11 Example
12 Example
13 Example
14 Example
15 Example
16 Example
17 Example
19 Adhesive composition used Example 1 Example
2 Example
3 Example
4 Example
5 Example
6 Example 7 Example
8 Example
9 Adhesion (%) 100 97 96 96 95 98 100 99 100 * Adhesive composition used: means the adhesive composition used when forming the second coating layer
* Adhesion: Comparative comparison proceeds based on 100% of the result of Example 10

Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Adhesive composition used Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Adhesion (%) 54 72 81 82 85 79 * Adhesive composition used: means the adhesive composition used when forming the second coating layer
* Adhesion: Comparative comparison proceeds based on 100% of the result of Example 10

10: Raw code
11: Ha Yeonsa
12: Ha Yeonsa
20: coating layer
21: first coating layer
21': first coating solution
22: second coating layer
22': second coating solution
30: tire cord
100: first winder
200: first coating tank
300: first drying device
400: second coating tank
500: second drying device
600: second winder
1000: tread
2000: shoulder
3000: sidewall
4000: cap ply
5000: belt
6000: body fly or carcass
7000: inner liner
8000: Apex
9000: bead

Claims (20)

(A) latex, (B) polyurethane, (C) an amine-based adhesion promoter, and (G) a water-containing solvent;
The adhesive composition, wherein the relative viscosity measured at room temperature using a Ubelode viscometer satisfies the range of 2.50 to 3.00.
The method of claim 1,
The (C) amine-based adhesion promoter, a fatty acid (C ₁ ) and an amine compound (C ₂ ), an adhesive composition.
3. The method of claim 2,
The fatty acid (C ₁ ) is a saturated fatty acid having an aliphatic chain having 6 to 30 carbon atoms, the adhesive composition.
3. The method of claim 2,
The amine compound (C ₂ ) is an alkylene diamine having 1 to 12 carbon atoms, the adhesive composition.
The method of claim 1,
The (C) amine-based adhesion promoter is represented by Formula 1, the adhesive composition:
[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently a substituted or unsubstituted aliphatic chain group having 6 to 30 carbon atoms, and A is a divalent group having 1 to 12 carbon atoms.
The method of claim 1,
(D) the adhesive composition further comprising an amine-based chain extender.
7. The method of claim 6,
_{The weight (W 1} ) of the (C) amine-based adhesion promoter _{is greater than the weight (W 2} ) of the (D) amine-based chain extender, the adhesive composition.
8. The method of claim 7,
The (C) amine by weight of the adhesion promoter (W ₁₎ and the (D) the weight of the extended amine-based chain, the (W ₂₎ between the weight ratio (W ₁ / W ₂₎ is 1.5 to 10 range of the adhesive composition.
7. The method of claim 6,
An adhesive composition comprising, based on the total weight of the composition, 1.0% by weight or more of the (C) amine-based adhesion promoter.
The method of claim 1,
An adhesive composition comprising water in an amount of 40% by weight or more based on the total weight of the composition.
The method of claim 1,
Based on the total weight of the composition, the adhesive composition comprising the (A) latex in the range of 1.0 to 30% by weight.
The method of claim 1,
The (B) polyurethane adhesive composition comprising a polyurethane having a weight average molecular weight (Mw) in the range of 250,000 to 350,000.
13. The method of claim 12,
Based on the total weight of the composition, an adhesive composition comprising the polyurethane in the range of 0.5 to 9.0% by weight.
The method of claim 1,
(E) The adhesive composition further comprising an epoxy compound.
The method of claim 1,
(F) The adhesive composition further comprising an isocyanate compound.
raw cord comprising fibers; and a coating layer formed on the raw code,
The coating layer is formed from the adhesive composition according to claim 1, a rubber reinforcement.
17. The method of claim 16,
The raw cord is a hybrid cord formed by upper-twisting two different types of lower-twist yarns.
18. The method of claim 17,
The hybrid cord is a rubber reinforcing material comprising a lower-twisted aramid yarn and a lower-twisted nylon yarn.
17. The method of claim 16,
as code; a first coating layer formed on the raw code; and a second coating layer formed on the first coating layer and formed from the adhesive composition according to claim 1 sequentially,
The first coating layer is a rubber reinforcing material comprising at least one compound selected from epoxy and isocyanate as a reactive active group imparting component.
A rubber composite comprising the rubber reinforcing material according to claim 16 .

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