TW201418381A - Rubber laminate and manufacturing method thereof - Google Patents

Abstract

An object of the present invention provides a rubber laminate and a manufacturing method thereof, the rubber laminate has a coating layer that has sufficient adhesion with chloroprene and rubber surface of a natural rubber, and a small static friction coefficient. The present invention provides a rubber laminate and a manufacturing method thereof, the rubber laminate has a coating layer formed by an aqueous coating agent containing an aqueous polyurethane resin dispersion and a rubber substrate, wherein the aqueous polyurethane resin dispersion contains a polyurethane resin having a unit derived from polycarbonate polyol, and has a content ratio of the alicyclic structure of 43 weight% or less based on solid content, and has an isocyanato group bound with a blocking agent.

Description

Rubber laminate and manufacturing method thereof

The present invention relates to a rubber laminate comprising a coating layer formed of an aqueous coating agent containing an aqueous polyurethane resin dispersion and a rubber substrate, and a method for producing the rubber laminate.

Conventionally, as a coating agent for rubber, it is used as a coating agent for a weather strip for a vehicle or a coating agent for a wiper blade, and a solvent containing a polyurethane resin and a siloxane compound is often used. A coating agent (see Patent Document 1 and Patent Document 2). However, with the limitation of the VOC (Volatile Organic Compound) discharge rule, a review of the direction of the substitution of the aqueous coating agent is currently underway.

The aqueous coating agent generally has a poor adhesion to the rubber surface, so the solvent treatment of the rubber surface or the undercoat treatment is performed before the application of the coating agent. However, in this case, it becomes very complicated to need to add one manufacturing step. Therefore, by disposing a decane coupling agent or a reactive additive such as carbodiimide in an aqueous coating agent containing an aqueous polyurethane resin dispersion, it is possible to improve the adhesion to the rubber surface without performing a primer treatment or the like. Technical proposal (see Patent Document 3 and Patent Document 4).

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Patent Laid-Open No. Hei 8-109349

Patent Document 2: Japanese Laid-Open Patent Publication No. 2004-083641

Patent Document 3: Japanese Laid-Open Patent Publication No. 2002-030247

Patent Document 4: Japanese Laid-Open Patent Publication No. 2007-167704

Coating of rubber substrates, such as representative wipers or weather strips, requires a lot of slidability. Applying an aqueous coating agent that forms a coating layer having a high modulus of elasticity to the surface of the rubber, even if a surface having a small coefficient of friction and good slidability is to be obtained, such a coating layer is dense for a rubber substrate of chloroprene rubber or natural rubber. The problem of poor properties is that it is difficult to have good adhesion to a rubber substrate and a low static friction coefficient with respect to a coating layer formed using an aqueous coating agent.

An object of the present invention is to provide a rubber laminate comprising a coating layer formed of an aqueous coating agent containing an aqueous polyurethane resin dispersion, and a coating layer having a rubber surface with chloroprene or natural rubber. It has sufficient adhesion and a small coefficient of static friction.

The present invention has been made to solve the above problems, and specifically has the following configuration.

[1] A rubber laminate comprising a coating layer formed of an aqueous coating agent containing a dispersion of an aqueous polyurethane resin, and a rubber substrate, the aqueous polyurethane resin dispersion containing a plurality of polycarbonate derived from Alcohol unit The polyurethane resin has a content ratio of an alicyclic structure of 43% by weight or less based on a solid content, and has an isocyanate group to which a blocking agent is bonded.

[2] The rubber laminate according to the above [1], wherein the aqueous polyurethane resin dispersion has an isocyanate group having a blocking agent in an amount of 0.1 to 3.0% by weight based on the solid content of the isocyanate group.

[3] The rubber laminate according to [1] or [2] above, wherein the blocking agent is one selected from the group consisting of an anthraquinone compound, a pyrazole compound, and a malonic acid diester compound. the above.

[4] The rubber laminate according to any one of the above [1] to [3] wherein the polyurethane resin has a weight average molecular weight of from 15,000 to 80,000.

[5] The rubber laminate according to any one of the above [1] to [4] wherein the polyurethane resin has a content ratio of an alicyclic structure of 7 to 35% by weight based on the solid content.

[6] The rubber laminate according to any one of the above [1] to [5] wherein the polyurethane resin has a content ratio of the amine ester bond of 7 to 18% by weight and a urea bond on a solid basis. The total value of the ratio.

[7] The rubber laminate according to any one of the above [1] to [6] wherein the polyurethane resin has a content ratio of carbonate bonds of 15 to 40% by weight based on the solid content.

[8] The rubber laminate according to any one of the above [1] to [7] wherein the polyurethane resin has an acid value of 10 to 40 mgKOH/g.

[9] The rubber laminate according to any one of the above [1] to [8] wherein the aqueous polyurethane resin dispersion is such that (a) the polyisocyanate compound and (b) have a number average molecular weight of from 400 to 4,000. Polycarbonate polyol, (c) polyol group containing an acidic group (A) a hydroxylate prepolymer obtained by reacting (d) an isocyanate group blocking agent, any (e) other polyol compound, and further reacting with an isocyanate group of the aforementioned polyurethane prepolymer ( B) The chain extender is reacted, and the obtained polyurethane resin is dispersed in an aqueous medium.

[10] The rubber laminate according to [9] above, wherein the (a) polyisocyanate compound is an alicyclic diisocyanate.

[11] The rubber laminate according to any one of the above [1] to [10] wherein the aqueous coating agent further contains inorganic particles or/and resin beads.

[12] The rubber laminate according to any one of the above [1] to [11] wherein an undercoat layer is present between the coating layer and the rubber substrate.

[13] The rubber laminate according to any one of the above [1], wherein the surface of the rubber substrate or the rubber substrate treated with the primer composition is provided after the application of the aqueous coating agent. The formed coating layer is heated.

[14] The rubber laminate according to any one of the above [1] to [11] wherein the substrate formed of the unsulfurized rubber or the uncoated rubber is treated with the primer composition. The surface of the substrate is provided after the application of the aqueous coating agent, and the formed coating layer and the vulcanized rubber substrate are heated.

[15] A method for producing a rubber laminate, which is applied to a surface of a rubber substrate or a surface of a primer-treated rubber substrate, to apply an aqueous coating agent containing an aqueous polyurethane resin dispersion (the aqueous polyurethane resin dispersion) a polyurethane resin having a unit derived from a polycarbonate polyol, which has a content ratio of an alicyclic structure of 43% by weight or less and an isocyanate group having a blocking agent bonded thereto, based on a solid content, Heating to form a coating layer.

[16] A method for producing a rubber laminate, which is a substrate made of unsulfurized rubber Or a surface of a substrate made of a non-sulfurized rubber treated with a primer composition, and an aqueous coating agent containing a dispersion of an aqueous polyurethane resin (the aqueous polyurethane resin dispersion containing a polycarbonate derived from polycarbonate) is applied The polyurethane resin of the polyol unit is classified into a solid content, has a content ratio of an alicyclic structure of 43% by weight or less, and has an isocyanate group to which a blocking agent is bonded, and then is heated to form a coating layer and a coating layer. Sulfur rubber substrate.

According to the present invention, it is possible to provide a rubber laminate having a coating layer formed of an aqueous coating agent containing a dispersion of an aqueous polyurethane resin, and a coating layer having a coating layer with chloroprene, and a method for producing the rubber laminate The rubber surface of natural rubber has sufficient adhesion and a small coefficient of static friction.

An object of the present invention is to provide a coating layer having sufficient adhesion to a rubber surface from an aqueous coating agent without adding an additive such as a decane coupling agent to the aqueous coating agent, and a rubber laminate having such a layer is provided. It is not excluded to use an additive such as a decane coupling agent.

[coating layer]

The coating layer in the present invention is formed from an aqueous coating agent containing a dispersion of an aqueous polyurethane resin. Here, the aqueous polyurethane resin dispersion contains a polyurethane resin having a unit derived from a polycarbonate polyol, and has a content ratio of an alicyclic structure of 43% by weight or less based on a solid content, and has a bonded bond. The isocyanate group of the terminalizing agent. The content ratio of the alicyclic structure, based on the solid form, from the natural rubber From the viewpoint of adhesion, it is desirably 5 to 43% by weight, preferably 7 to 40% by weight, more preferably 7 to 35% by weight. Further, the content ratio of the isocyanate group to which the blocking agent is bonded is converted into an isocyanate group based on the solid content, and from the viewpoint of adhesion to the natural rubber, it is preferably 0.1 to 3.0% by weight. It is preferably 0.4 to 2.5% by weight, more preferably 0.6 to 2.0% by weight. Further, in the present invention, in the alicyclic structure, it is regarded as a residue corresponding to a cyclohexane (removing two hydrogen atoms from cyclohexane) or a cyclopentane residue (two hydrogens are removed from cyclopentane). Atomic), to calculate the ratio.

The aqueous polyurethane resin dispersion of the present invention may be at least (a) A polyurethane resin obtained by reacting a polyisocyanate compound, (b) a polycarbonate polyol compound having a number average molecular weight of 400 to 4000, (c) an acid group-containing polyol compound, and (d) an isocyanate group blocking agent Dispersed in the water media.

Further, the aqueous polyurethane resin dispersion of the present invention may also be (a) a polycyanate compound, (b) a polycarbonate polyol having a number average molecular weight of 400 to 4000, (c) an acid group-containing polyol compound, (d) an isocyanate group blocking agent, and optionally (e) reacting other polyol compounds to obtain (A) a polyurethane prepolymer, further reacting with (B) a chain extender reactive with the isocyanate group of the (A) polyurethane prepolymer, and obtaining The polyurethane resin is dispersed in an aqueous medium.

In the aqueous polyurethane resin dispersion, isocyanide bonded with a blocking agent The acid ester group can be introduced by blending an isocyanate compound having a blocking agent bonded thereto. For example, in an aqueous dispersion of a polyurethane resin having no isocyanate group to which a blocking agent is bonded, an isocyanate compound to which a blocking agent is bonded may be formulated.

<(a) Polyisocyanate Compound>

In the present invention, as the (a) polyisocyanate compound (hereinafter, also referred to as (a)), The aromatic polyisocyanate, the aliphatic polyisocyanate, the alicyclic polyisocyanate, and the like are not particularly limited.

As an aromatic polyisocyanate, specifically, 1,3- Phenyl diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolyl diisocyanate (TDI), 2,6-tolyl diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanate biphenyl, 3,3'-dimethyl-4,4'-diisocyanate biphenyl, 3,3' -Dimethyl-4,4'-diisocyanate diphenylmethane, 1,5-anaphthyl diisocyanate, 4,4',4"-triphenylmethane triisocyanate, m-isocyanate phenyl sulfonate Isocyanate, p-isocyanate phenylsulfonium isocyanate, and the like.

As an aliphatic polyisocyanate, specifically, it can be exemplified: Ethyl diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethyl Hexamethylene diisocyanate, diazonium diisocyanate, 2,6-diisocyanate methyl hexanoate, bis(2-isocyanateethyl)fumarate, bis(2-isocyanateethyl) Carbonate, 2-isocyanate ethyl-2,6-diisocyanate hexanoate, and the like.

As the alicyclic polyisocyanate, specifically, it can be exemplified: Fluconketone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexyl diisocyanate, methylcyclohexyl diisocyanate (hydrogenated TDI), bis(2-isocyanate) Ethyl ethyl)-4-cyclohexyl-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, and the like.

The above polyisocyanate may be used singly or in combination of plural kinds.

The isocyanate group per one molecule of polyisocyanate is usually two, this In the invention, the polyaminoester resin may be a heteropolycyanate having three or more isocyanate groups such as triphenylmethane triisocyanate in the range of not gelling.

Among the polyisocyanates, from the viewpoint of high adhesion to rubber, It is preferably an alicyclic polyisocyanate having an alicyclic structure, and is selected from the group consisting of isophorone diisocyanate (IPDI) and 4,4'-dicyclohexylmethane diisocyanate from the viewpoint of easy reaction control. One or more of the groups of hydrogenated MDI) are particularly preferable.

<(b) Polycarbonate polyol having a number average molecular weight of 400 to 4000>

In the present invention, as the (b) polycarbonate polyol having a number average molecular weight of 400 to 4,000 (hereinafter, also referred to as (b)), except that the number average molecular weight is from 400 to 4,000, and is a polycarbonate polyol It is not particularly limited, and is preferably one or more selected from the group consisting of polycarbonate diol, polycarbonate triol and polycarbonate tetraol, and polycarbonate diol is preferred.

The number average molecular weight of (b) is preferably from 500 to 3,500, more preferably from 800 to 3,000, particularly preferably from 800 to 2,000.

In the present invention, the number average molecular weight is a value derived by the following method. By using GPC (gel permeation chromatography) method, using a tetrahydrofuran solvent as a solution at room temperature, a calibration curve obtained by using a standard polystyrene sample of a known molecular weight is used, and the same method is used. The retention time of the polycarbonate polyol determined by GPC is applied to the calibration curve to derive the number average molecular weight.

The method for producing the polycarbonate polyol is not particularly limited, and examples thereof include a method of producing a polyol monomer and phosgene, or a known production method using a method of producing a polyol monomer and a carbonate. Among them, a method for producing a polyol monomer and a carbonate is preferred because a chlorine compound or a chlorine ion is not mixed.

As a polyol monomer that is a raw material for polycarbonate polyols, it can be listed. Lift: ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octane Alcohol, 1,9-nonanediol, 1,10-nonanediol, 1,12-dodecanediol, etc.; or 1,3-butanediol, 3-methylpentane-1,5- Aliphatic groups such as diol, 2-ethylhexane-1,6-diol, 2-methyl-1,3-pentanediol, neopentyl glycol, 2-methyl-1,8-octanediol Alkane; 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2,2'-bis(4-hydroxycyclohexyl)propane, 1,4-cyclohexanedimethanol, etc. An aromatic diol such as 1,4-benzenedimethanol; a polyfunctional polyol such as trimethylolpropane or neopentyl alcohol; The polyol monomer may be used as a polycarbonate polyol by using only one type, or a plurality of types may be used in combination to form a polycarbonate polyol.

In the present invention, from the viewpoint of the elastic modulus of the coating layer, as (b) Preferably, a polycarbonate polyol having an alicyclic structure is preferred. In particular, by using a polycarbonate polyol having an alicyclic structure in the main chain, the modulus of elasticity can be increased, and the static friction coefficient can be lowered for a nitrile rubber (NBR) whose static friction coefficient is not easily lowered. In the present invention, the content ratio of the alicyclic structure of (b) is preferably 5 to 40% by weight, preferably 5 to 25% by weight, particularly preferably 5 to 20% by weight. Further, as the (b), a polycarbonate polyol having an alicyclic structure and a polycarbonate polyol having no alicyclic structure may be used in combination. Further, from the viewpoint of adhesion to the rubber substrate, as the (b), a polycarbonate polyol having no alicyclic structure can be used, and in this case, (a) having an alicyclic structure A combination of polyisocyanate compounds is preferred. Further, in the present invention, the content ratio of the alicyclic structure means a cyclohexane residue (two hydrogen atoms removed from cyclohexane) or a cyclopentane residue in the weight average molecular weight of the polycarbonate polyol. (% by weight of two hydrogen atoms removed by cyclopentane).

As the polycarbonate polyol having an alicyclic structure, for example, the polyol monomer is a polycarbonate diol containing an alicyclic diol, and for example, it may be exemplified as having 1,4- A polycarbonate diol of a cyclohexanedimethanol unit, a polycarbonate diol having a 1,4-cyclohexanedimethanol unit and a 1,6-hexanediol unit. Further, as the polycarbonate polyol having no alicyclic structure, for example, a polycarbonate diol in which the polyol monomer is an aliphatic diol, a polycarbonate having a 1,6-hexanediol unit may be mentioned. A diol, a polycarbonate diol having 1,5-pentanediol units and 1,6-hexanediol units.

In the present invention, the weight average molecular weight is a value derived from a standard polystyrene sample having a known molecular weight, similarly to the above-described number average molecular weight.

<(c) Polyol compound containing an acidic group>

In the present invention, the (c) acid group-containing polyol compound (hereinafter also referred to as (c)) may be a compound having two or more hydroxyl groups and one or more acidic groups in one molecule. It is not particularly limited, and a compound having two hydroxyl groups and one acidic group in one molecule is preferred.

Examples of the acidic group include a functional group which exhibits acidity such as a carboxyl group, a sulfonyl group, a phosphoric acid group or a phenolic hydroxyl group, and among them, a carboxyl group is preferred.

As (c), specifically, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N,N-bishydroxyethylglycine, N,N- Dihydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid, and the like. These may be used alone or in combination. Among them, 2,2-dimethylolpropionic acid is preferred from the viewpoint of ease of availability.

<(d) Isocyanate group blocking agent>

The (d) isocyanate group-blocking agent (hereinafter also referred to as (d)) in the present invention is not particularly limited, and those which are cleaved from an isocyanate group at 80 to 180 ° C can be used. Examples of the blocking agent which is dissociated from the isocyanate group at 80 to 180 ° C include a malonic acid diester compound such as dimethyl malonate or diethyl malonate; 1,2- Pyrazole-based compounds such as pyrazole and 3,5-dimethylpyrazole; anthraquinone compounds such as 1,2,4-triazole and methyl ethyl ketone oxime; diisopropylamine and caprolactam. These can be used alone or in combination. In view of the dissociation temperature, one or more selected from the group consisting of an anthraquinone compound, a pyrazole compound, and a malonic acid diester compound is preferred, and is selected from the group consisting of 3,5-dimethylpyrazole and One or more of the ethyl ethyl ketone oxime is preferable, and 3,5-dimethylpyrazole is particularly preferable from the viewpoint of preservation stability.

<(e) Other polyol compounds>

In the present invention, (e) another polyol compound (hereinafter also referred to as (e)) is an optional component and is not an essential component.

In the present invention, (e) is not particularly limited, and examples thereof include a polyester polyol, a polycarbonate polyol having a number average molecular weight of 400 to 4000, an aliphatic diol, an alicyclic diol, and an aromatic group. A diol, a polyfunctional polyol, or the like.

<(A) Polyurethane Prepolymer>

In the present invention, the (A) polyurethane prepolymer (hereinafter also referred to as (A)) is obtained by reacting (a) to (e).

(A) The method for producing the polyurethane prepolymer is not particularly limited, and examples thereof include the following methods.

The first method is to esterify (a) a polyisocyanate compound, (b) a polyol compound, and (c) an acid group-containing polyol compound in the presence or absence of an amine esterification catalyst. The reaction is carried out in the presence or absence of a catalyst and esterified with an amine, followed by reaction with (d) a blocking agent in the presence or absence of a capping catalyst, and a portion of the terminal isocyanate group is blocked. A method of synthesizing (A) a polyurethane prepolymer.

In the second method, (a) a polyisocyanate compound is reacted with (d) a blocking agent in the presence or absence of a capping catalyst to synthesize a portion of the blocked polymer. The isocyanate compound is reacted with (b) a polyol compound, (c) an acidic group-containing polyol compound in the presence or absence of an amine esterification catalyst, and is amine-esterified to synthesize (A) a polyurethane ester prepolymer. The method.

<Amine esterification catalyst>

In the present invention, the amine esterification catalyst is not particularly limited, and examples thereof include a tin-based catalyst (trimethyltin laurate, dibutyltin dilaurate, etc.) or a lead-based catalyst (for example). Salts such as lead octoate, etc., and salts of metals and organic and inorganic acids, and organometallic derivatives, amine-based catalysts (triethylamine, N-ethylmorpholine, tri-ethylenediamine, etc.), diazabicyclo-deca A olefinic catalyst or the like. Among them, from the viewpoint of reactivity, tin dibutyl dilaurate is preferred.

In the present invention, the capping catalyst is not particularly limited, and examples thereof include an alkaline catalyst such as dibutyltin dilaurate or sodium methoxide.

<neutralizer>

(A) The acidic group of the polyurethane prepolymer can be neutralized, and the neutralization can be carried out using a neutralizing agent. As the neutralizing agent, there may be mentioned, for example, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, dimethyl group. Organic amines such as ethanolamine, diethylethanolamine, N-methylmorpholine, pyridine; inorganic bases such as sodium hydroxide and potassium hydroxide; ammonia. Among them, organic amines are preferred, and tertiary amines are preferred, and triethylamine is most preferred. These can be used alone or in combination.

<(B) chain extender>

Examples of the chain extender include compounds reactive with isocyanate groups. For example, ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1,4-butanediamine, 1,6-hexa Methyldiamine, 1,4-hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis(aminomethyl)cyclohexane Benzene dimethyl diamine, piperazine , adipic acid dioxime, hydrazine, 2,5-dimethylperazine An amine compound such as diethylenetriamine or triamethylenetetramine, a glycol compound such as ethylene glycol, propylene glycol, 1,4-butanediol or 1,6-hexanediol, represented by polyethylene glycol A polyalkylene glycol, water or the like is preferred, and a first-order diamine compound is preferred. These can be used alone or in combination.

(B) The amount of the chain extender can be appropriately selected. In the case of producing the aqueous polyurethane resin dispersion by the second production method described below, the group reactive with the isocyanate group in the chain extender other than water, and the isocyanate group in the prepolymer, in molar ratio, It can be used in an amount of 2:1 or less. The molar ratio is preferably 1:1 to 0.8:1.

<Water Media>

In the present invention, the polyurethane resin is dispersed in an aqueous medium. Examples of the water-based media include water or a mixed medium of water and a hydrophilic organic solvent.

Examples of the water include, for example, tap water, ion-exchanged water, distilled water, ultrapure water, etc., but in view of the ease of acquisition and the influence of chlorine, the particles become unstable, and it is desirable to cite ions. Exchange water.

Examples of the hydrophilic organic solvent include low-grade monovalent alcohols such as methanol, ethanol, and propanol; polyols such as ethylene glycol and glycerin; N-methylmorpholine, dimethyl hydrazine, and dimethylformamide. An aprotic hydrophilic organic solvent such as N-methylpyrrolidone or N-ethylpyrrolidone.

The amount of the hydrophilic organic solvent in the aqueous medium is preferably from 0 to 20% by weight, preferably from 0 to 15% by weight, particularly preferably from 0 to 10% by weight.

<Aqueous polyurethane resin dispersion>

The method for producing the aqueous polyurethane resin dispersion of the present invention is not particularly limited, and examples thereof include the following production methods.

In the first production method, an aqueous polyurethane resin dispersion can be obtained by mixing all the raw materials and reacting in an aqueous medium, that is, a so-called one-shot process.

In the second production method, (a) a polycyanate compound, (b) a polycarbonate polyol compound, (c) an acid group-containing polyol compound, (d) a blocking agent, and any of (e) reacting with another polyol to produce (A) a polyurethane prepolymer, neutralizing the acidic group of the prepolymer, dispersing in an aqueous medium, and reacting with the (B) chain extender to obtain an aqueous polyurethane resin dispersion, The so-called prepolymer method. The method for producing the aqueous polyurethane resin dispersion of the present invention is preferably a second production method from the viewpoint of dispersibility.

Specifically, the aqueous polyurethane resin dispersion of the present invention can be obtained by a method comprising the following steps.

(1) After reacting (a) a polyisocyanate compound, (b) a polycarbonate polyol compound, (c) an acidic group-containing polyol compound, or any (e) other polyol compound, an isocyanate group and (d) a blocking agent bonding to obtain (A) a polyurethane prepolymer step; (3) a step of neutralizing (A) the acidic group of the polyurethane prepolymer with a neutralizing agent; and (4) neutralizing the acidic group (A) a step of dispersing the polyurethane prepolymer in an aqueous medium; and (5) a step of reacting (A) a polyurethane prepolymer with (B) a chain extender to obtain an aqueous polyurethane resin dispersion.

Steps (4) and (5) can be performed simultaneously. Further, after the prepolymer is dispersed in a solvent other than water, it may be further mixed with water, and then the solvent is distilled off to obtain a desired period. An aqueous polyurethane resin dispersion that is expected. In this case, water also acts as a chain extender.

(A) The reaction of the polyurethane prepolymer with the (B) chain extender can be Performed in machine solvent. In this case, the (A) polyurethane prepolymer which has neutralized the acidic group or the (A) polyurethane prepolymer which does not neutralize the acidic group, and the chain extender are dissolved in an organic solvent and allowed to react. Thereafter, an aqueous medium is added while stirring or the like, and the organic solvent is removed under reduced pressure, whereby an aqueous polyurethane resin dispersion in which the polyurethane resin is dispersed in an aqueous medium can be obtained.

As an organic solvent, as long as it is substantially non-inverse with the isocyanate group The organic solvent which is hydrophilic (water-mixable) is not particularly limited, and examples thereof include ketones such as acetone and ethyl methyl ketone, esters, tetrahydrofuran, and N-methylmorpholine. Ethers, decylamines such as dimethylformamide, N-methylpyrrolidone and N-ethylpyrrolidone, and alcohols. These can be used alone or in combination.

Further, the reaction of (A) the polyurethane prepolymer and the (B) chain extender can be carried out in the presence of a catalyst. The catalyst is not particularly limited, and examples thereof include a tin-based catalyst (such as trimethyl laurate or tin dibutyl laurate) or a lead-based catalyst (such as lead octoate), and a metal or an organic or inorganic acid. A salt, an organometallic derivative, an amine-based catalyst (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), a diazabicycloundecene-based catalyst, or the like. Among them, from the viewpoint of reactivity, tin dibutyl dilaurate is preferred.

As described above, a polyurethane resin containing a unit derived from a polycarbonate polyol is prepared, and has a content ratio of an alicyclic structure of 43% by weight or less on a solid content basis, and has a terminal blocking agent bonded thereto. An aqueous isocyanate-based polyurethane resin dispersion which can be used in an aqueous coating agent. From the viewpoint of film forming properties, the solid content concentration of the aqueous polyurethane resin dispersion in the aqueous coating agent, It is preferably 15 to 40% by weight, more preferably 20 to 35% by weight.

The content ratio of the alicyclic structure in the aqueous polyurethane resin dispersion, It is 43% by weight or less based on the solid content. The adhesion to the natural rubber can be exhibited as long as it is 43% by weight or less. In the aqueous polyurethane resin dispersion, the content ratio of the alicyclic structure of the polyurethane resin is desirably 5 to 43% by weight, preferably 7 to 40% by weight, more preferably 7 to 35% by weight, particularly preferably It is 20 to 35% by weight.

Blocking with a blocking agent in an aqueous polyurethane resin dispersion The content ratio of the isocyanate group is preferably from 0.1 to 3.0% by weight, preferably from 0.4 to 2.5% by weight, particularly preferably from 0.6 to 2.0% by weight, based on the solid content. In particular, when the content ratio of the blocked isocyanate group is from 0.4 to 2.5% by weight, the adhesion to the natural rubber is good.

Aqueous polyurethane resin dispersion, which is mixed with a plurality of kinds to seal The aqueous dispersion of the isocyanate-based polyurethane resin blocked by the terminalizing agent can adjust the content ratio of the alicyclic structure, the content ratio of the isocyanate group blocked by the blocking agent, and the like.

Further, in the aqueous polyurethane resin dispersion, a blocking agent is bonded The isocyanate group can be introduced by blending an isocyanate compound having a blocking agent bonded thereto. For example, an isocyanate compound to which a blocking agent is bonded may be formulated in an aqueous dispersion of a polyurethane resin having no isocyanate group to which a blocking agent is bonded. Examples of the isocyanate compound to which the blocking agent is bonded include a water-dispersible polyisocyanate, and a polyisocyanate which imparts hydrophilicity by a polyethylene oxide chain is anionic dispersing agent or nonionic dispersion. The agent is dispersed in water, etc.

Examples of the polyisocyanate include diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate; trimethylolpropane adducts of such diisocyanates; biuret and tris A derivative (modified substance) of a polyisocyanate such as a polyisocyanate or the like is not limited to the related examples. These polyisocyanates may be used alone or in combination of two or more. The water-dispersible blocked polyisocyanate is one in which the isocyanate group of the water-dispersible polyisocyanate is blocked with a blocking agent. As the blocking agent, for example, diethyl malonate, ethyl acetate, ε-caprolactam, butanone oxime, cyclohexanone oxime, 1,2,4-triazole, Dimethyl-1,2,4-triazole, 3,5-dimethylpyrazole, imidazole, etc., and the present invention is not limited to the related examples. These blocking agents may be used alone or in combination of two or more. Among these blocking agents, it is desirable to have a temperature of 160 ° C or less, and preferably a temperature of 150 ° C or less. Examples of suitable blocking agents include butanone oxime, cyclohexanone oxime, and 3,5-dimethylpyrazole. Among these, 3,5-dimethylpyrazole is more preferred. Water-dispersed blocked polyisocyanate, for example, manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: TAKENATE WB-720, TAKENATE WB-730, TAKENATE WB-920, etc.; Bayeramine ester (manufactured by Bayer), trade name: Bayhydur BL116, Bayhydur BL5140, Bayhydur BL5235, Bayhydur TPLS 2186, Desmodur VPLS 2310, etc. can be easily obtained as commercial products. In the case of formulating an isocyanate compound having a blocking agent bonded thereto, from the viewpoint of adhesion to natural rubber, it is preferably 0.1 to 30% by weight, and 1 to 10% by weight, based on the solid content. Better.

To use a polyisocyanate group having a blocking agent with a bonding agent The aqueous polyurethane resin dispersion of the amine ester resin is preferred, and the content ratio of the isocyanate group of the blocking agent to the polyurethane resin is bonded to the isocyanate in terms of solid content. The ester group is preferably from 0.1 to 3.0% by weight, preferably from 0.3 to 2.5% by weight, particularly preferably from 0.5 to 2.0% by weight.

Amine ester bonding of polyurethane resin in aqueous polyurethane resin dispersion The total content ratio of the urea bond is preferably 7 to 18% by weight based on the solid content. When the total content ratio of the amine ester bond to the urea bond is within this range, the coating film has no tack and good adhesion to rubber. The total ratio of the content of the amine ester bond to the urea bond is desirably 7 to 15% by weight, preferably 8 to 14% by weight.

Carbonate bond of polyurethane resin in aqueous polyurethane resin dispersion The content ratio of the knot is preferably 15 to 40% by weight based on the solid content. When the content ratio of the carbonate bond is within this range, the adhesion to the natural rubber is good. The content ratio of the carbonate bond is desirably 15 to 35% by weight, preferably 18 to 30% by weight.

The acid value of the aqueous polyurethane resin dispersion is divided into solid forms. It is preferably 10 to 40 mgKOH/g. When the acid value is within this range, the dispersibility of the resin to water is good. The acid value is desirably 14 to 30 mgKOH/g, preferably 15 to 26 mgKOH/g.

In the aqueous polyurethane resin dispersion, the weight average molecular weight of the polyurethane resin is preferably from 15,000 to 80,000. When the weight average molecular weight is within this range, the coating film has no tackiness and good adhesion to rubber. The weight average molecular weight is desirably from 20,000 to 70,000, preferably from 25,000 to 60,000.

<Other additives>

In the aqueous coating agent of the present invention, in addition to the aqueous polyurethane resin dispersion In addition, various additives can also be added. As the additive, there may be mentioned a crosslinking agent, a plasticizer, an antifoaming agent, a leveling agent, an antifungal agent, a rust inhibitor, a matting agent, a flame retardant, a rocking agent, a lubricant (for example, eucalyptus oil), and an antistatic agent. Agents (such as carbon black), conductive additives, viscosity reducers, tackifiers, thinners, pigments, dyes, perfumes, UV absorbers, light stabilizers (such as hindered amine light stabilizers (HALS)), antioxidants , organic fillers (such as resin beads), inorganic fillers (such as inorganic particles), pH adjusters, fusion aids, rheology modifiers, surfactants, freeze-thaw additives, wetting agents, wet edges (wet edge) additives.

From the point of view of friction, it is to add inorganic particles and resin beads. One or more of them are preferred. Thus, in the case where the resin is regarded as 100% by weight, it may be formulated in an amount of 90% by weight or less, preferably 0.1% to 50% by weight. Examples of the inorganic particles include cerium oxide fine particles or pigments. The cerium oxide fine particles are not particularly limited, and known cerium oxide fine particles such as powdered cerium oxide or colloidal cerium oxide can be used. As a commercially available powdered cerium oxide fine particle, for example, ACEMATT TS 100 manufactured by Evonik Degussa, OK 607, AEROSIL 50, 200 manufactured by Japan AEROSIL Co., Ltd., and Sildex H31, H32, H51 manufactured by Asahi Glass Co., Ltd. H52, H121, H122, E220 A and E220 manufactured by Japan's cerium oxide industry, SYLYSIA 470 manufactured by Fuji Sylysia Co., Ltd., and SG (Flake) manufactured by Nippon Sheet Glass Co., Ltd.

Examples of the pigments include organic pigments and inorganic pigments, and these may be used alone or in combination of two or more. Examples of the organic pigment include azo pigments such as benzidine and Hansa yellow, azomethine pigments, methine pigments, anthraquinone pigments, phthalocyanine pigments such as phthalocyanine blue, and violet. Perinone pigment, anthraquinone pigment, diketopyrrolopyrrole pigment, thioindigo pigment, sub a quinophthalone pigment such as an aminoisoindoline pigment, an imidoisoinone pigment, a quinophthalone red or a quinophthalone violet, a flavanthrone pigment, an indanthrone pigment, Pyrimidine pigment, carbazole pigment, monoarylide yellow, diarylate yellow, benzimidazolone yellow, tolyl orange, naphthol orange, quinophthalone pigment, etc., but not limited These are the same. These organic pigments may be used alone or in combination of two or more.

As the inorganic pigment, for example, titanium dioxide, antimony trioxide, zinc oxide, zinc antimony white, lead white, red iron oxide, black iron oxide, iron oxide, chromium oxide green, carbon black, yellow lead, molybdenum red may be mentioned. , iron ferrocyanide (Prussian blue), ultramarine (ultramarine), lead chromate, etc., mica, clay, aluminum powder, talc, aluminum silicate and other flat-shaped pigments, calcium carbonate, magnesium hydroxide, hydroxide Excipient pigments such as aluminum, barium sulfate, and magnesium carbonate are not limited to these. These inorganic pigments may be used alone or in combination of two or more.

As a resin bead, it is made of polystyrene, polyamine, and poly An organic polymer of one or a mixture of two or more kinds of vinyl chloride, polyolefins, polyurethanes, polyesters, polyacryls, polyacrylates, polyacrylonitriles, and epoxy resins. Examples of the polystyrene include polystyrene homopolymer, polystyrene rubber or styrene butadiene rubber mixed with polystyrene or grafted polystyrene having improved punching strength. As the ABS copolymer, examples of the polyamines include nylon 6 and nylon 66 polymers, and examples of the polyolefins include low density polyethylene, high density polyethylene, and linear low density poly. Examples of the polyesters and the like include polyethylene terephthalate, and examples of the polyacrylic acid include polyacrylic acid, polymethacrylic acid, and the like. Such copolymers with polyacrylates, etc. Examples of the polyacrylates include polymethyl methacrylate and polyethyl methacrylate. Examples of the polyacrylonitrile include polyacrylonitrile, acrylonitrile, methacrylonitrile, and acrylic acid. A copolymer such as a methyl ester or the like. From the standpoint of low cost, it is especially preferred to use polyurethane, polyacrylate or polyamine, and more preferably polyurethane. The shape of the resin beads may be a spherical shape, a disk shape, a fractured cross section or a shape of a protrusion, or any other shape, and it is preferably a spherical shape from the viewpoint of ease of manufacture in a certain shape.

From the viewpoint of wettability, it is preferred to add a surfactant. this Or, in the case where the resin is regarded as 100% by weight, it may be formulated in an amount of 5% by weight or less, preferably 0.05 to 3% by weight. The surfactant is preferably a fluorene-based surfactant, and a polyoxyalkylene-based compound or the like is used, and examples thereof include a polyether-modified organic siloxane. It is desirable to use BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348, etc., which are manufactured by BYK Chemical Co., Ltd., Japan.

As a crosslinking agent, carbodiimide, melamine, epoxy compound, Oxazoline and the like. The amount of the crosslinking agent to be added is preferably from 0.3 to 15% by weight, more preferably from 1 to 10% by weight, based on the solid content. By such an ideal addition amount, the viscosity of the surface of the coating layer can be suppressed, and the adhesion to the substrate can be improved.

Further, an emulsion or dispersion of another resin may be added. As As other resin, for example, a polyester resin, a polyether resin, a polycarbonate resin, an acid alcohol (alkyd) resin, a polyolefin resin, a decyl alkane resin, a (meth)acrylic resin, an epoxy resin, and a fiber may be mentioned. A resin, a carboxyl modified styrene-butadiene latex, an ethylene-vinyl acetate resin or a partial saponified product thereof or a fully saponified product.

Further, other resins are preferably one or more hydrophilic groups. Examples of the hydrophilic group include a hydroxyl group, a carboxyl group, a sulfonic acid group, and a polyethylene glycol group.

Other resins are selected from the group consisting of polyester resins, acrylic resins, and poly At least one of the groups of the olefin resins is preferred.

Polyester resin, usually by esterification of acid and alcohol It is produced by transesterification. As the acid component, when a polyester resin is produced, a compound which is usually used as an acid component can be used. As the acid component, for example, an aliphatic polybasic acid, an alicyclic polybasic acid, an aromatic polybasic acid or the like can be used.

The hydroxyl value of the polyester resin is preferably from about 10 to 300 mgKOH/g, more preferably from about 50 to 250 mgKOH/g, still more preferably from about 80 to 180 mgKOH/g. The acid value of the polyester resin is preferably from about 1 to 200 mgKOH/g, more preferably from about 15 to 100 mgKOH/g, still more preferably from about 25 to 60 mgKOH/g.

The weight average molecular weight of the polyester resin is preferably from 500 to 500,000, more preferably from 1,000 to 300,000, still more preferably from 1,500 to 200,000.

As the acrylic resin, an acrylic resin containing a hydroxyl group is preferred. The hydroxyl group-containing acrylic resin is a hydroxyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, for example, in an organic solvent. It is produced by copolymerization of a solution polymerization method or an emulsion polymerization method in water by a known method.

The polymerizable unsaturated monomer having a hydroxyl group is a compound having one or more hydroxyl groups and a polymerizable unsaturated bond in one molecule. For example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 3- a monoester of a (meth)acrylic acid such as hydroxypropyl ester or 4-hydroxybutyl (meth)acrylate and a dihydric alcohol having 2 to 8 carbon atoms; an ε-caprolactone modified body of such a monoester; N-hydroxymethyl (meth) acrylamide; allyl alcohol; (meth) acrylate having a polyoxyethylene chain at the molecular end of the hydroxyl group and having a polyoxyethylene chain.

a hydroxyl group-containing acrylic resin having an anionic functional group good. With respect to the hydroxyl group-containing acrylic resin having an anionic functional group, for example, a polymerizable unsaturated monomer having an anionic functional group such as a carboxylic acid group, a sulfonic acid group or a phosphoric acid group can be used as the polymerizable unsaturated monomer. It is made in one type.

The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably from 1 to 200 mgKOH/g, and from 2 to 100 mgKOH/g, from the viewpoint of storage stability of the aqueous polyurethane resin dispersion or water resistance of the obtained coating layer. The right and left are preferred, and it is preferably about 3 to 60 mgKOH/g.

When the hydroxyl group-containing acrylic resin has an acid group such as a carboxyl group, the acid value of the hydroxyl group-containing acrylic resin is preferably from about 1 to 200 mgKOH/g, and from 2 to 2, from the viewpoint of water resistance of the obtained coating layer. It is preferably about 150 mgKOH/g, more preferably about 5 to 100 mgKOH/g.

The weight average molecular weight of the hydroxyl group-containing acrylic resin is preferably from 1,000 to 200,000, more preferably from 2,000 to 100,000, still more preferably from 3,000 to 50,000.

As the polyether resin, a polymer having an ether bond or The copolymer is, for example, a polysiloxane derived from an aromatic polyhydroxy compound such as a polyoxyethylene polyether, a polyoxypropylene polyether, a polyoxybutylene polyether, a bisphenol A or a bisphenol F. Ether, etc.

As the polycarbonate resin, it can be exemplified by a bisphenol compound. Examples of the produced polymer include bisphenol A/polycarbonate and the like.

As the polyurethane resin, it can be exemplified by acrylic acid, poly An amine ester-bonded resin obtained by reacting various polyol components such as an ester, a polyether or a polycarbonate with a polyisocyanate.

As the epoxy resin, a bisphenol compound and a ring can be cited. A resin obtained by the reaction of oxychloropropane or the like. Examples of the bisphenol include bisphenol A and bisphenol F.

As the acid alcohol resin, phthalic acid, p-phenylene a polybasic acid such as formic acid or succinic acid, and a polyhydric alcohol, which is further reacted with a modifier such as a fat/fat fatty acid (soybean oil, linseed oil, coconut oil, stearic acid, etc.) or a natural resin (rosin, amber, etc.). Acid alcohol resin.

As a polyolefin resin, an olefin type monomer is suitable A preferred polyolefin monomer is a polyolefin resin obtained by polymerization or copolymerization by a usual polymerization method, using an emulsifier for water dispersion, or by emulsion polymerization of an olefin monomer together with a suitable other monomer. The resin obtained. Further, depending on the case, a so-called chlorinated polyolefin modified resin obtained by chlorinating the above polyolefin resin may also be used.

Examples of the olefin monomer include ethylene, propylene, and the like. 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-decene, An α-olefin such as 1-dodecene; a conjugated diene such as butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene or styrene; or a non-conjugated diene These monomers may be used singly or in combination of plural kinds.

As another monomer copolymerizable with an olefin type monomer, for example, Can be listed: vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, horse The anhydride may be used alone or in combination of plural acids.

Carboxyl modified styrene-butadiene latex refers to styrene and dibutyl The olefin monomer is used as a main component, and among them, a synthetic latex obtained by copolymerizing a monomer composition containing a vinyl monomer having a carboxyl group such as a few % (meth)acrylic acid or fumaric acid .

An aqueous coating agent which can be used in an aqueous polyurethane resin dispersion, It is prepared by blending any additives.

The rubber laminate of the present invention is provided with the above aqueous coating agent The formed coating layer and the rubber substrate. The coating layer may be formed by laminating at least a part of the rubber substrate. For example, one or both of the layers of the rubber substrate may cover the entire area of the faces or cover a portion of the faces.

As the rubber constituting the rubber substrate, it can be exemplified that it is selected from ethylene - Propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), nitrile rubber (NBR), butyl rubber (BR), chloroprene rubber (CR), natural rubber (NR), etc. It is preferably one or more selected from the group consisting of ethylene-propylene-diene rubber (EPDM), nitrile rubber (NBR), chloroprene rubber (CR), and natural rubber (NR), and more preferably selected from the group consisting of chloroprene One or more kinds of olefin rubber (CR) and natural rubber (NR).

a rubber substrate provided with a coating layer, which may be of any shape, A sheet-like base material, a rod-shaped base material, etc. are mentioned. Specific examples include rubber rollers, automobile tires, weatherproof linings, wipers, shoes, sandals, rubber long shoes, rubber handbags, mechanical or vibration-proof members of buildings. The rubber base material may contain various additives such as an anti-aging agent, a vulcanization accelerator, an ultraviolet absorber, and a lubricant.

Rubber substrate, which can be unsulphurized rubber, sulfurized once in the middle Rubber, any type of vulcanized rubber that is vulcanized to achieve the desired crosslink density. When a non-sulfurized rubber or a primary vulcanized rubber is used as the rubber substrate, after the aqueous coating agent is applied, it is possible to carry out vulcanization or secondary vulcanization while forming the coating layer by heating.

The method for forming the rubber substrate is not particularly limited, and may be used. Various methods such as press forming, injection molding, or extrusion molding are used for forming.

The rubber laminate of the present invention can be formed on the surface of the rubber substrate, After the above aqueous coating agent is applied, it is heated and formed into a coating layer to be produced.

On the surface of the rubber substrate, it can be modified with a naphthene (methyl) An undercoat composition such as an acrylic emulsion or a chlorinated polyolefin is treated, and by applying an aqueous coating agent to the surface thus treated to form a coating layer, a primer layer can be produced between the rubber substrate and the coating layer. Rubber laminate.

When a non-sulfurized rubber is used as a substrate, on the surface thereof, After the application of the above aqueous coating agent, it is also possible to add sulfur while heating and forming a coating layer. The surface can be treated with a primer composition.

As the surface to which the aqueous coating agent is applied, there is no particular limitation, and It is preferred to use a degreased surface. The method of degreasing is not particularly limited, and a known method can be used.

As a method of applying the aqueous coating agent, it is possible to use: spray coating A known method such as cloth, spin coating, dipping, roller coating, reverse roll coating, or gravure coating.

After the aqueous coating agent is appropriately applied, it is heated to form a coating layer. The heating step can also serve as a drying step. Or, you can set the dry before heating For the drying step, a normal temperature drying method or a vacuum drying method may be employed.

Heating can be carried out at 40 to 250 ° C, desirably 80 to 200 ° C. The heating time can be appropriately selected, and for example, it can be from 1 to 60 minutes. By heating, the isocyanate-bonded blocking agent in the aqueous coating agent is removed, and a crosslinking reaction is carried out to obtain a coating layer having excellent hardness. The heating step can also serve as a drying step. Alternatively, a drying step may be additionally provided before heating, and a normal temperature drying method or a vacuum drying method may be employed.

Further, a coating agent is applied onto the unvulcanized rubber molded body, and the rubber molded body is vulcanized after drying the coating agent or simultaneously with drying to obtain a rubber laminate.

Further, a coating agent is applied to the rubber molded body which has been subjected to the vulcanization once, and the rubber molded body is secondarily vulcanized after drying the coating agent or simultaneously with drying, and a rubber laminated body can also be obtained.

Usually, the primary sulfurization is carried out at a lower temperature or less than the secondary sulfur addition. The temperature of the primary sulfurization is not particularly limited, and it is preferably carried out at a relatively low temperature such as 150 ° C or lower. Moreover, the time of one-time vulcanization is also not particularly limited, and is preferably 1 to 30 minutes.

As a method of primary vulcanization, a method of heating vulcanization in a mold after being formed by injection molding, or a method of heating vulcanization in a heating furnace after being formed by extrusion molding, or It is a method of heating and adding sulfur in a mold after being formed by a hot press method.

The thickness of the coating layer is not particularly limited and may be 1 to 300 μm, preferably 2 to 100 μm, preferably 3 to 40 μm.

[Examples]

Next, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited thereto.

Further, the measurement of the physical properties was carried out as follows.

(1) Hydroxy valence: Measured according to the B method of JIS K 1557.

(2) Content ratio of free isocyanate group: 0.5 g of the reaction mixture after completion of the esterification reaction of the amine was used as a sample, and 0.1 mL of a solution of 0.1 mmol/L (liter) of dibutylamine-tetrahydrofuran (THF) and tetrahydrofuran were added. In a mixed solution of (THF) 20 mL, the undigested dibutylamine was titrated with 0.1 mol/L hydrochloric acid. From this difference between the titration value and the blank test, the molar concentration of the isocyanate group remaining in the reaction mixture was calculated. The molar ratio of the molar concentration to the isocyanate group is determined as the content ratio of the free isocyanate group. Further, the indicator drug used in the titration is bromophenol blue.

(3) The content ratio of the solid fraction of the amine ester bond, indicating the content ratio based on the solid content of the urea bond: the ratio of each raw material of the aqueous polyurethane resin dispersion to calculate the amine ester bond and the urea bond of the molar Concentration (mole/g), converted to weight fraction. The weight fraction is based on the solid content of the aqueous polyurethane resin dispersion. 0.3 g of the aqueous polyurethane resin dispersion was applied onto a glass substrate at a thickness of 0.2 mm, and dried by heating at 140 ° C for 4 hours, and then the residual weight was measured, and this was divided by the weight before drying as a solid content concentration. The weight fraction was calculated by taking the product of the total weight of the aqueous polyurethane resin dispersion and the solid content concentration as the solid component weight.

(4) Content ratio of the solid content of the carbonate bond: The molar concentration (mol/g) of the carbonate bond is calculated from the ratio of the raw materials of the aqueous polyurethane resin dispersion and converted into a weight fraction. By. Weight fraction is the aqueous polyurethane tree The solid content of the lipid dispersion was calculated based on the same ratio as the content ratio of the solid fraction-bonded solid fraction.

(5) Content ratio of solid fraction of the alicyclic structure: The weight fraction of the alicyclic structure calculated from the ratio of the contents of the respective raw materials of the aqueous polyurethane resin dispersion. The weight fraction is calculated by the same method as the solid content of the aqueous polyurethane resin dispersion as a reference, and the content ratio of the solid fraction based on the amine ester bond.

(6) Acid value: The molar concentration (mol/g) of the carboxyl group was calculated from the ratio of the respective raw materials of the aqueous polyurethane resin dispersion, and the weight of potassium hydroxide necessary for neutralizing the sample of 1 g (mgKOH/ g). The sample weight was calculated by taking the solid content of the aqueous polyurethane resin dispersion as a standard and the same ratio as the solid content standard of the amine ester-bonded bond.

(7) Weight average molecular weight of the polyurethane resin in the aqueous polyurethane resin dispersion: a conversion value obtained by a calibration curve of a standard polystyrene prepared in advance by gel permeation chromatography (GPC).

(8) The solid content of the aqueous polyurethane resin dispersion is bonded to the content ratio of the isocyanate group of the blocking agent (in terms of isocyanate group): it means that the amount of the capping agent is converted into isocyanate group. The weight is divided by the ratio of the solids weight of the aqueous polyurethane resin dispersion. The solid content of the aqueous polyurethane resin dispersion was calculated by the same method as the content ratio of the solid fraction bonded to the above amine ester.

(9) The adhesion of the coating layer was evaluated as follows. In 100 g of the aqueous polyurethane resin dispersion of the examples and the comparative examples, 1.5 g of ACEMATT TS100 (dry cerium oxide, medium diameter 10 μm, manufactured by Evonik), and 0.1 g of BYK-345 (surfactant (polyether) were added. Modified oxime), BYK Chemical Company As a water-based coating agent. The surface of each rubber sheet was wiped and degreased with a cotton-impregnated cotton wool, and the prepared aqueous coating agent was applied as a bar coater, and the vulcanized rubber and the unsulfurized rubber (before vulcanization) were dried by heating at 150 ° C. After 20 minutes, the rubber before the second sulfur addition after sulfurization (in the middle of sulfur addition) was added with sulfur at 150 ° C for 5 minutes, and then the aqueous coating agent was applied and dried by heating at 150 ° C for 20 minutes to obtain a coating layer (dry coating layer). The thickness of the film was 6 μm) and the checkerboard peel test was performed. In the coating layer of 20 mm × 20 mm, the incisions were made at intervals of 2 mm in the longitudinal and lateral directions. After the tape was adhered, the number of cells remaining on the surface of the rubber sheet at the time of peeling was visually counted and evaluated. A case where 15 of 100 are left is represented by 15/100.

(10) The surface of each rubber sheet was wiped and degreased with a cotton-impregnated cotton wool, and then the aqueous coating agent was applied by a bar coater, and dried by heating at 150 ° C for 20 minutes, and left for 48 hours, and then "HEIDON TRIBOGEAR" was used. 3D Muse type: 37" (manufactured by Shinto Scientific Co., Ltd.) The static friction coefficient at room temperature was measured.

[Example 1] [Manufacture of Aqueous Polyurethane Resin Dispersion (1)]

In a reaction vessel into which a stirrer, a reflux cooling tube, and a thermometer are inserted, ETERNACOLL (registered trademark) UH-200 (manufactured by Ube Industries, polycarbonate diol; number average molecular weight 2000; hydroxyl value 56.1 mgKOH/g; 1,6- 232 g of polycarbonate diol obtained by reacting hexanediol with dimethyl carbonate), 18.5 g of 2,2-dimethylolpropionic acid (DMPA) and 176 g of N-methylpyrrolidone (NMP) under nitrogen Placed under the stream. 125 g of 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), 0.33 g of dibutyltin dilaurate (catalyst) were added and heated to 90 ° C, and an amine esterification reaction was carried out for 5 hours. Then, 10.4 g of 3,5-dimethylpyrazole (DMPZ) was injected, and stirring was continued for 1.5 hours at the same temperature. A polyurethane prepolymer is obtained. The content of the free isocyanate group at the end of the amine esterification reaction was 1.78 wt%. From the addition/mixing of 13.9 g of triethylamine to the reaction mixture, 564 g was taken out, and 870 g of water was added under vigorous stirring. Next, 36.5 g of a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine was added to carry out a chain extension reaction to obtain an aqueous polyurethane resin dispersion (1). The content ratio of the amine ester bond of the aqueous polyurethane resin dispersion (1), the content ratio of the urea bond, the content ratio of the carbonate bond, the content ratio of the blocked isocyanate group (in terms of isocyanate group), and the acid value The weight average molecular weight and the content ratio of the alicyclic structure are shown in Table 1.

[Embodiment 2] [Manufacture of Aqueous Polyurethane Resin Dispersion (3)]

In the same reaction vessel as in Example 1, ETERNACOLL UM90 (1/3) (registered trademark; Polyethylene diol produced by Ube Industries; number average molecular weight 894; hydroxyl value 125.5 mg KOH/g; Cyclohexane dimethanol and 1,6-hexanediol (a molar ratio of 1:3) to a polycarbonate diol obtained by reacting dimethyl carbonate) 210 g, 2,2-dimethylolpropionic acid ( DMPA) 31.6 g and N-methylpyrrolidone (NMP) 149 g were placed under a nitrogen stream. 208 g of 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI) and 0.34 g of dibutyltin dilaurate (catalyst) were added, and the mixture was heated to 90 ° C, and an amine esterification reaction was carried out for 5 hours. Thereafter, 15.9 g of methyl ethyl ketone oxime (MEKO) was injected, and stirring was continued for 1.5 hours at the same temperature to obtain a polyurethane prepolymer. The content of the free isocyanate group at the end of the amine esterification reaction was 3.01% by weight. From the addition/mixing of 24.0 g of triethylamine in the reaction mixture, 603 g was taken out and added to 835 g of water with vigorous stirring. Next, 65.1 g of a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine was added to carry out a chain extension reaction to obtain an aqueous polyurethane resin dispersion (2). The obtained aqueous polyurethane resin dispersion (2) had a solid content-based amine ester bond content ratio of 11.7% by weight, and the solid content-based urea bond content ratio was 5.1% by weight, and the solid fraction was based on carbonate-bonded The content ratio was 15.2% by weight, the content ratio of the blocked isocyanate group on the basis of the solid content (in terms of isocyanate group) was 1.6% by weight, the acid value was 27.9 mgKOH/g, and the weight average molecular weight was 28 × 10 ³ , and the solid content standard was The content ratio of the alicyclic structure was 33.7 wt%.

80 g of the aqueous polyurethane resin dispersion (1) obtained in Example 1 and 20 g of the aqueous polyurethane resin dispersion (2) were mixed with a disperser to obtain an aqueous polyurethane resin dispersion (3). The amine ester bond content ratio, the content ratio of the urea bond, the content ratio of the carbonate bond, the content ratio of the blocked isocyanate group (in terms of isocyanate group), and the acidity of the obtained aqueous polyurethane resin dispersion (3) The content, the weight average molecular weight, and the content ratio of the alicyclic structure are shown in Table 1.

[Example 3] [Manufacture of Aqueous Polyurethane Resin Dispersion (5)]

In the same reaction vessel as in Example 1, ETERNACOLL (registered trademark) UC-100 (manufactured by Ube Industries, polycarbonate diol; number average molecular weight: 1000; hydroxyl value: 112.2 mgKOH/g; 1,4-cyclohexane) 153 g of polycarbonate diol obtained by reacting dimethanol with dimethyl carbonate, 27 g of polytetramethylene glycol ether, 22.4 g of 2,2-dimethylolpropionic acid (DMPA), and N-ethylpyrrole 116 g of ketone (NEP) was placed under a stream of nitrogen. 144 g of 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI) and 0.3 g of dibutyltin dilaurate (catalyst) were added, and the mixture was heated to 90 ° C, and an amine esterification reaction was carried out for 5 hours. The free isocyanate group content at the end of the amine esterification reaction was 3.93% by weight. From the addition/mixing of 13.8 g of triethylamine in the reaction mixture, 436 g was taken out and added to 750 g of water with vigorous stirring. Next, 34.5 g of a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine was added to carry out a chain extension reaction to obtain an aqueous polyurethane resin dispersion (4). The content ratio of the solid ester-based amine ester bond of the obtained aqueous coating agent was 10.6% by weight, the content ratio of the solid bond-based urea bond was 6.5% by weight, and the solid content-based carbonate bond content ratio was 14.9. % by weight, the content ratio of the blocked isocyanate group on the solid content basis (in terms of isocyanate group) is 0.0% by weight, the acid value is 25 mgKOH/g, and the weight average molecular weight is 200 × 10 ³ , and the solid content is based on the alicyclic structure. The content ratio was 44.8 wt%.

80 g of the aqueous polyurethane resin dispersion (1) obtained in Example 1 and 20 g of the aqueous polyurethane resin dispersion (4) were mixed with a disperser to obtain an aqueous polyurethane resin dispersion (5). The content ratio of the amine ester bond of the obtained aqueous polyurethane resin dispersion (5), the content ratio of the urea bond, the content ratio of the carbonate bond, and the content ratio of the blocked isocyanate group (in terms of isocyanate group), The acid value, the weight average molecular weight, and the content ratio of the alicyclic structure are shown in Table 1.

[Comparative Example 1] [Manufacture of Aqueous Polyurethane Resin Dispersion (6)]

In the same reaction vessel as in Example 1, ETERNACOLL (registered trademark) UH-200 (manufactured by Ube Industries, polycarbonate diol; number average molecular weight 2011; hydroxyl value: 55.8 mgKOH/g; 1,6-hexane 301 g of polycarbonate diol obtained by reacting alcohol with dimethyl carbonate, 16.5 g of 2,2-dimethylolpropionic acid (DMPA) and 135 g of N-ethylpyrrolidone (NEP), placed under a nitrogen stream In. 92.0 g of isophorone diisocyanate (IPDI) and 0.31 g of dibutyltin dilaurate (catalyst) were added, and the mixture was heated to 80 ° C, and an amine esterification reaction was carried out for 5 hours. The free NCO group content at the end of the amine esterification reaction was 1.67 wt%. Of the 12.4 g of triethylamine added/mixed to the reaction mixture, 495 g was taken out and added to 745 g of water under vigorous stirring. Next, 29.4 g of a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine was added to carry out a chain extension reaction. To the aqueous polyurethane resin dispersion (6). The content ratio of the amine ester bond of the obtained aqueous polyurethane resin dispersion (6), the content ratio of the urea bond, the content ratio of the carbonate bond, and the content ratio of the blocked isocyanate group (in terms of isocyanate group), The acid value, the weight average molecular weight, and the content ratio of the alicyclic structure are shown in Table 1.

[Comparative Example 2] [Manufacture of Aqueous Polyurethane Resin Dispersion (7)]

In the same reaction vessel as in Example 1, ETERNACOLL (registered trademark) PH-200 (manufactured by Ube Industries, polycarbonate diol; number average molecular weight 2000; hydroxyl value 56.1 mgKOH/g; 1,5-pentanediol) And 1,6-hexanediol (molar ratio is 1:1) and polycarbonate diol obtained by reaction with dimethyl carbonate) 301 g, 2,2-dimethylolpropionic acid (DMPA) 16.3 g and N - Ethylpyrrolidone (NEP) 132 g was placed under a nitrogen stream. 90.0 g of isophorone diisocyanate (IPDI) and 0.30 g of dibutyltin dilaurate (catalyst) were added, and the mixture was heated to 80 ° C, and an amine esterification reaction was carried out for 5 hours. The free NCO group content at the end of the amine esterification reaction was 1.74% by weight. From the addition/mixing of 12.0 g of triethylamine in the reaction mixture, 506 g was taken out and added to 758 g of water with vigorous stirring. Next, 31.3 g of a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine was added to carry out a chain extension reaction to obtain an aqueous polyurethane resin dispersion (7). The content ratio of the amine ester bond of the obtained aqueous coating agent (aqueous polyurethane resin dispersion (7)), the content ratio of urea bond, the content ratio of carbonate bond, and the content ratio of blocked isocyanate group (conversion) The isocyanate group), the acid value, the weight average molecular weight, and the content ratio of the alicyclic structure are shown in Table 1.

[Example 4] [Manufacture of Aqueous Polyurethane Resin Dispersion (8)]

100 g of aqueous polyurethane resin dispersion (6) and Bayhydur BL 5140 (end capping) The content ratio of the amine ester bond of the aqueous polyurethane resin dispersion (8) formed by the aqueous polyurethane resin dispersion (6) and the aqueous blocked polyisocyanate (2) was mixed with 2 g of polyisocyanate, manufactured by Bayer Amine Co., Ltd. The content ratio of the urea bond, the content ratio of the carbonate bond, the content ratio of the blocked isocyanate group (in terms of isocyanate group), the acid value, the weight average molecular weight, and the content ratio of the alicyclic structure are shown in Table 1. Recorded.

[Comparative Example 3] [Manufacture of Aqueous Polyurethane Resin Dispersion (9)]

In the same reaction vessel as in Example 1, ETERNACOLL (registered trademark) UM-90 (3/1) (manufactured by Ube Industries, polycarbonate diol; number average molecular weight 916; hydroxyl group 122.5 mgKOH/g; a polycarbonate diol obtained by reacting 4-cyclohexanedimethanol and 1,6-hexanediol (mole ratio of 3:1) with dimethyl carbonate) 1500 g, 2,2-dimethylolpropane 220 g of acid (DMPA) and 1350 g of N-methylpyrrolidone (NMP) were placed under a nitrogen stream. 1450 g of 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI) and 2.6 g of dibutyltin dilaurate (catalyst) were added and heated to 90 ° C, and an amine esterification reaction was carried out for 5 hours. The free NCO group content at the end of the amine esterification reaction was 3.97 wt%. Of the 149 g of triethylamine added/mixed to the reaction mixture, 4340 g was taken out and added to a mixed solution of 6900 g of water and 15 g of triethylamine under vigorous stirring. Next, 626 g of a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine was added to carry out a chain extension reaction to obtain an aqueous polyurethane resin dispersion (9). The content ratio of the amine ester bond of the obtained aqueous polyurethane resin dispersion (9), the content ratio of the urea bond, the content ratio of the carbonate bond, and the content ratio of the blocked isocyanate group (in terms of isocyanate group), The acid value, the weight average molecular weight, and the content ratio of the alicyclic structure are shown in Table 1.

[Comparative Example 4] [Manufacture of Aqueous Polyurethane Resin Dispersion (10)]

In the same reaction vessel as in Example 1, ETERNACOLL (registered trademark) UM-90 (1/3) (manufactured by Ube Industries, polycarbonate diol; number average molecular weight 894; hydroxyl group 125.5 mgKOH/g; a polycarbonate diol obtained by reacting 4-cyclohexanedimethanol and 1,6-hexanediol (mole ratio 1:3) with dimethyl carbonate) 180 g, 2,2-dihydroxymethylpropane Acid (DMPA) 27.1 g and N-methylpyrrolidone (NMP) 163 g were placed under a nitrogen stream. 177 g of 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI) and 0.3 g of dibutyltin dilaurate (catalyst) were added and heated to 90 ° C, and an amine esterification reaction was carried out for 5 hours. The free NCO group content at the end of the amine esterification reaction was 3.73% by weight. 523 g of the 20.7 g of triethylamine added/mixed in the reaction mixture was taken out and added to 915 g of water with vigorous stirring. Next, 73.2 g of a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine was added to carry out a chain extension reaction to obtain an aqueous polyurethane resin dispersion (10). The content ratio of the amine ester bond of the obtained aqueous polyurethane resin dispersion (10), the content ratio of the urea bond, the content ratio of the carbonate bond, and the content ratio of the blocked isocyanate group (in terms of isocyanate group), The acid value, the weight average molecular weight, and the content ratio of the alicyclic structure are shown in Table 1.

[Example 5] [Manufacture of Aqueous Polyurethane Resin Dispersion (11)]

In the same reaction vessel as in Example 1, ETERNACOLL (registered trademark) UH-200 (polycarbonate diol manufactured by Ube Industries; number average molecular weight 2007; hydroxyl value 55.9 mgKOH/g; 1,6-hexanediol) 128 g of polycarbonate diol obtained by reaction with dimethyl carbonate, 8.88 g of 2,2-dimethylolpropionic acid (DMPA) and 63.4 g of N-methylpyrrolidone (NMP), placed under a nitrogen stream In. Add 4,4'-dicyclohexylmethane diisocyanate 58.6 g of an acid ester (hydrogenated MDI) and 0.18 g of dibutyltin dilaurate (catalyst) were heated to 90 ° C, and an amine esterification reaction was carried out for 5 hours. Thereafter, 2.06 g of 3,5-dimethylpyrazole (DMPZ) was injected, and stirring was continued for 1.5 hours at the same temperature to obtain a polyurethane prepolymer. The free isocyanate group content at the end of the amine esterification reaction was 2.38 wt%. 232 g of 6.5 g of triethylamine was added/mixed to the reaction mixture, and it was added to 305 g of water with vigorous stirring. Next, 20.0 g of a 35% by weight aqueous solution of 2-methyl-1,5-pentanediamine was added to carry out a chain extension reaction to obtain an aqueous polyurethane resin dispersion (11). The content ratio of the amine ester bond of the obtained aqueous polyurethane resin dispersion (11), the content ratio of the urea bond, the content ratio of the carbonate bond, and the content ratio of the blocked isocyanate group (in terms of isocyanate group), The acid value, the weight average molecular weight, and the content ratio of the alicyclic structure are shown in Table 1.

[Comparative Example 5] [Manufacture of Aqueous Polyurethane Resin Dispersion (12)]

In the same reaction vessel as in Example 1, ETERNACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries, polycarbonate diol; number average molecular weight 897; hydroxyl value: 125.1 mgKOH/g; 1,4- 211 g, 2,2-dimethylolpropionic acid (carbonate diol) obtained by reacting cyclohexanedimethanol and 1,6-hexanediol (3:1 molar ratio with dimethyl carbonate) DMPA) 31.8 g and N-methylpyrrolidone (NMP) 149 g were placed under a nitrogen stream. 207 g of 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI) and 0.36 g of dibutyltin dilaurate (catalyst) were added and heated to 90 ° C, and an amine esterification reaction was carried out for 5 hours. Thereafter, 16.2 g of methyl ethyl ketone oxime (MEKO) was injected, and stirring was continued for 1.5 hours at the same temperature to obtain a polyurethane prepolymer. The content of the free isocyanate group at the end of the amine esterification reaction was 2.79% by weight. Of the 24.3 g of triethylamine added/mixed to the reaction mixture, 570 g was taken out and added to 807 g of water with vigorous stirring. its 59.5 g of a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine was added thereto in a chain extension reaction to obtain an aqueous polyurethane resin dispersion (12). The content ratio of the amine ester bond of the obtained aqueous polyurethane resin dispersion (12), the content ratio of the urea bond, the content ratio of the carbonate bond, the content ratio of the blocked isocyanate group (in terms of isocyanate group), The acid value, the weight average molecular weight, and the content ratio of the alicyclic structure are shown in Table 1.

[Embodiment 6] [Manufacture of Aqueous Polyurethane Resin Dispersion (13)]

As the aqueous polyurethane resin dispersion (13), the aqueous polyurethane resin dispersion (2) obtained in Example 2 was used. The content ratio of the amine ester bond of the aqueous polyurethane resin dispersion (2), the content ratio of the urea bond, the content ratio of the carbonate bond, the content ratio of the blocked isocyanate group (in terms of isocyanate group), and the acid value The weight average molecular weight and the content ratio of the alicyclic structure are shown in Table 1.

[Embodiment 7] [Manufacture of Aqueous Polyurethane Resin Dispersion (14)]

In the same reaction vessel as in Example 1, ETERNACOLL UH-300 (registered trademark; Polypropylene diol produced by Ube Industries; number average molecular weight 2906; hydroxyl value 38.6 mgKOH/g; 1,6-hexanediol and 330 g of polycarbonate diol obtained by the reaction of dimethyl carbonate, 21.6 g of 2,2-dimethylolpropionic acid (DMPA), and 159 g of N-methylpyrrolidone (NMP) were placed under a nitrogen stream. 125 g of 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI) and 0.35 g of dibutyltin dilaurate (catalyst) were added, and the mixture was heated to 90 ° C, and an amine esterification reaction was carried out for 5 hours. Thereafter, 10.9 g of 3,5-dimethylpyrazole (DMPZ) was injected, and stirring was continued for 1.5 hours at the same temperature to obtain a polyurethane prepolymer. The free isocyanate group content at the end of the amine esterification reaction was 1.85% by weight. by 600 g of 600 g of triethylamine was added/mixed to the reaction mixture, and it was added to 850 g of water with vigorous stirring. Next, 41.7 g of a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine was added to carry out a chain extension reaction to obtain an aqueous polyurethane resin dispersion (14). The content ratio of the amine ester bond of the obtained aqueous polyurethane resin dispersion (14), the content ratio of the urea bond, the content ratio of the carbonate bond, and the content ratio of the blocked isocyanate group (in terms of isocyanate group), The acid value, the weight average molecular weight, and the content ratio of the alicyclic structure are shown in Table 1.

[Embodiment 8] [Manufacture of Aqueous Polyurethane Resin Dispersion (15)]

In the same reaction vessel as in Example 1, ETERNACOLL UH-300 (registered trademark; Polypropylene diol produced by Ube Industries; number average molecular weight 2906; hydroxyl value 38.6 mgKOH/g; 1,6-hexanediol and 330 g of polycarbonate diol obtained by the reaction of dimethyl carbonate, 20.3 g of 2,2-dimethylolpropionic acid (DMPA), and 151 g of N-methylpyrrolidone (NMP) were placed under a nitrogen stream. 102 g of isophorone diisocyanate (IPDI) and 0.35 g of dibutyltin dilaurate (catalyst) were added and heated to 90 ° C, and an amine esterification reaction was carried out for 5 hours. Thereafter, 6.76 g of 3,5-dimethylpyrazole (DMPZ) was injected, and stirring was continued for 1.5 hours at the same temperature to obtain a polyurethane prepolymer. The content of the free isocyanate group at the end of the amine esterification reaction was 1.21% by weight. 585 g of the triethylamine added/mixed in the reaction mixture was taken out and added to 830 g of water with vigorous stirring. Next, 26.7 g of a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine was added to carry out a chain extension reaction to obtain an aqueous polyurethane resin dispersion (15). The content ratio of the amine ester bond of the obtained aqueous polyurethane resin dispersion (15), the content ratio of the urea bond, the content ratio of the carbonate bond, and the content ratio of the blocked isocyanate group (in terms of isocyanate group), Acid value, weight average molecular weight, and alicyclic structure The ratio is shown in Table 1.

[Embodiment 9] [Manufacture of Aqueous Polyurethane Resin Dispersion (16)]

In the same reaction vessel as in Example 1, ETERNACOLL UH-100 (registered trademark; Polyethylene diol produced by Ube Industries; number average molecular weight 1000; hydroxyl value 112.2 mgKOH/g; 1,6-hexanediol and 250 g of polycarbonate diol obtained by the reaction of dimethyl carbonate, 21.0 g of 2,2-dimethylolpropionic acid (DMPA) and 149 g of N-methylpyrrolidone (NMP) were placed under a nitrogen stream. 176 g of 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI) and 0.35 g of dibutyltin dilaurate (catalyst) were added and heated to 90 ° C, and an amine esterification reaction was carried out for 5 hours. Thereafter, 9.34 g of 3,5-dimethylpyrazole (DMPZ) was injected, and stirring was continued for 1.5 hours at the same temperature to obtain a polyurethane prepolymer. The content of the free isocyanate group at the end of the amine esterification reaction was 2.92% by weight. 590 g of which was added/mixed with 15.8 g of triethylamine in the reaction mixture was added to 840 g of water with vigorous stirring. Next, 64.6 g of a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine was added to carry out a chain extension reaction to obtain an aqueous polyurethane resin dispersion (16). The content ratio of the amine ester bond of the obtained aqueous polyurethane resin dispersion (16), the content ratio of the urea bond, the content ratio of the carbonate bond, and the content ratio of the blocked isocyanate group (in terms of isocyanate group), The acid value, the weight average molecular weight, and the content ratio of the alicyclic structure are shown in Table 1.

In Table 1, each abbreviated noun means the following.

H12-MDI: 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI)

IPDI: isophorone diisocyanate

UH-100: Ube Industries Co., Ltd. ETERNACOLL UH-100

UC100: Ube Industries Co., Ltd. ETERNACOLL UC100

UH-200: Ube Industries Co., Ltd. ETERNACOLL UH-200

PH-200: Ube Industries Co., Ltd. ETERNACOLL PH-200

UH-300: Ube Industries Co., Ltd. ETERNACOLL UH-300

UM90 (3/1): Ube Industries Co., Ltd. ETERNACOLL UM90 (3/1)

UM90 (1/3): Ube Industries Co., Ltd. ETERNACOLL UM90 (1/3)

BI: Bayydur BL 5140, manufactured by Bayer Amine Co., Ltd.

The aqueous polyurethane resin dispersion obtained in each of the examples and the comparative examples was used in the manner described in the evaluation of the adhesion of the coating layer (9) to prepare each aqueous coating agent, which was prepared by EPDM, NBR, CR, and NR. The surface of the rubber sheet is wiped and degreased with a cotton-impregnated cotton wool so that the dried coating layer is about 6 In the manner of μm, each aqueous coating agent was applied by a bar coater and dried at 150 ° C for 20 minutes to obtain a rubber laminate.

The coating layer of the aqueous coating agent in the rubber laminate obtained was evaluated for adhesion to the rubber sheet. Further, the static friction coefficient of the surface of the coating layer was measured. The results are combined and represented in Table 2.

In Table 2, each abbreviated word indicates the following.

NBR: nitrile rubber (static coefficient of friction without coating layer: 0.787)

CR: chloroprene rubber (static coefficient of friction without coating layer: 0.462)

NR: natural rubber (static coefficient of friction without coating layer: 0.439)

EPDM: ethylene-propylene-diene rubber (static friction coefficient without coating layer: 1.190 or more)

In Examples 1, 4, and 6, the period in which the coating layer was provided was changed, and the adhesion of the ethylene-propylene-diene rubber (EPDM) to the natural rubber (NR) was evaluated. The results are shown in Table 3. The conditions are as described in the above evaluation method of adhesion.

(industrial use possibility)

The rubber laminate of the present invention can be used in a rubber roller, a tire, a wiper, a weatherproof lining, a shoe (sole, etc.), a sandal, a rubber long shoe, a rubber handbag, a vibration-proof member of a machine or a building, or the like.

Claims (16)

A rubber laminate comprising a coating layer formed of an aqueous coating agent containing a dispersion of an aqueous polyurethane resin, and a rubber substrate containing a polyurethane having a unit derived from a polycarbonate polyol The resin has a content ratio of an alicyclic structure of 43% by weight or less based on the solid content, and has an isocyanate group to which a blocking agent is bonded. The rubber laminate according to claim 1, wherein the aqueous polyurethane resin dispersion has an isocyanate group in an amount of 0.1 to 3.0% by weight based on the solid content, and has an isocyanate group bonded to the blocking agent. . The rubber laminate according to claim 1 or 2, wherein the blocking agent is one or more selected from the group consisting of an anthraquinone compound, a pyrazole compound, and a malonic acid diester compound. . The rubber laminate according to any one of claims 1 to 3, wherein the polyurethane resin has a weight average molecular weight of from 15,000 to 80,000. The rubber laminate according to any one of claims 1 to 4, wherein the polyurethane resin has a content ratio of an alicyclic structure of 7 to 35% by weight based on the solid content. The rubber laminate according to any one of claims 1 to 5, wherein the polyurethane resin has a content ratio of an amine ester bond of 7 to 18% by weight and a bond of urea in a solid form. Contains the total value of the ratio. The rubber laminate according to any one of claims 1 to 6, wherein the polyurethane resin has a content ratio of carbonate bonds of 15 to 40% by weight based on the solid content. The rubber laminate according to any one of claims 1 to 7, wherein Among them, the polyurethane resin has an acid value of 10 to 40 mgKOH/g. The rubber laminate according to any one of claims 1 to 8, wherein the aqueous polyurethane resin dispersion is a polymer having (a) a polyisocyanate compound and (b) a number average molecular weight of 400 to 4,000. (A) Polyurethane prepolymer obtained by reacting a carbonate polyol, (c) an acid group-containing polyol compound, (d) an isocyanate group blocking agent, or any (e) other polyol compound, further The (B) chain extender reactive with the isocyanate group of the aforementioned polyurethane prepolymer is reacted, and the obtained polyurethane resin is dispersed in an aqueous medium. The rubber laminate according to claim 9, wherein the (a) polyisocyanate compound is an alicyclic diisocyanate. The rubber laminate according to any one of claims 1 to 10, wherein the aqueous coating agent further contains inorganic particles or/and resin beads. The rubber laminate according to any one of claims 1 to 11, wherein an undercoat layer is present between the coating layer and the rubber substrate. The rubber laminate according to any one of claims 1 to 11, wherein the surface of the rubber substrate or the rubber substrate treated with the primer composition is provided after the application of the aqueous coating agent. The coating layer formed. The rubber laminate according to any one of claims 1 to 11, wherein the substrate formed of the unsulfurized rubber or the uncoated rubber is treated with the primer composition. The surface of the substrate is provided after the application of the aqueous coating agent, and the formed coating layer and the vulcanized rubber substrate are heated. A method for producing a rubber laminate, which is applied to a surface of a rubber substrate or a surface of a primer-treated rubber substrate, to apply an aqueous coating agent containing an aqueous polyurethane resin dispersion (the aqueous polyurethane resin dispersion contains From polycarbonate The polyurethane resin of the unit of the ester polyol has a content ratio of an alicyclic structure of 43% by weight or less and an isocyanate group having a blocking agent bonded thereto in a solid form, and is heated to form a coating layer. A method for producing a rubber laminate, which comprises applying a water-containing polyurethane resin dispersion to a substrate made of an unsulfurized rubber or a surface of a substrate made of a non-sulfurized rubber treated with a primer composition. An aqueous coating agent (the aqueous polyurethane resin dispersion containing a polyurethane resin having a unit derived from a polycarbonate polyol, having a content ratio of an alicyclic structure of 43% by weight or less on a solid content basis, and having a bond After the isocyanate group having a blocking agent, it is heated to simultaneously form a coating layer and a vulcanized rubber substrate.