JP2003261724A - Aqueous emulsion of polyolefin derivative, method for producing the same and laminate using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous emulsion having excellent preservation stability at high temperature. <P>SOLUTION: The aqueous emulsion of a polyolefin derivative contains an emulsifier, and 0.2-5 wt.% water-insoluble organic solvent. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous emulsion of a polyolefin derivative having excellent storage stability at high temperatures, a method for producing the same, and a laminate using the same.

[0002]

2. Description of the Related Art Polyolefin resins are relatively inexpensive and have excellent properties such as moldability, mechanical properties, electrical properties, water vapor barrier properties, chemical resistance, water resistance, heat resistance, etc. It is widely used as parts, home appliances parts, building materials, etc. However, despite having such characteristics, the polyolefin resin is crystalline and does not have a highly reactive functional group on the surface, and therefore it is difficult to adhere or coat the polyolefin resin substrate.

In order to improve this, it is widely known that these olefin polymers are subjected to surface treatment from the viewpoints of adhesion with other materials, coating properties, printability and the like. Especially for non-polar olefin polymers, it can be said that the surface of the olefin polymer molding is treated with chemical, electrical treatment such as solvent treatment, flame treatment, corona discharge treatment and plasma treatment. And a method of forming a primer layer by subjecting the surface of the molded body to a primer treatment.

Among them, the primer treatment method is advantageous in that it does not require complicated steps and facilities, has little variation in treatment effect, and can be applied to a molded article having a complicated shape. It is used as a primer. Currently, modified polyolefins such as chlorinated are widely used, but in recent years, hydrogenated derivatives of conjugated diene polymers such as hydroxyl group-containing polybutadiene and polyisoprene have been attracting attention in the process of dechlorination.

However, in the primer treatment method, it is general that a solution of a polyolefin derivative in an organic solvent such as toluene, xylene and / or esters is applied as a primer to the surface of a molded article. Therefore, a large amount of organic solvent is released into the atmosphere when the primer is applied, which causes a problem of environmental pollution and a problem of health of workers.

In order to solve this problem, various methods of using a primer as an aqueous emulsion have been studied.
All had problems in storage stability as an emulsion. In particular, aqueous emulsions made by conventional methods
Although there are some that are stable at room temperature, a storage test at 40 ° C, taking into consideration the storage stability in the summer, causes a phenomenon such as peeling on the top of the emulsion within a month, a so-called creaming phenomenon. It had a drawback. The emulsion that caused the creaming phenomenon was a major cause of loss of smoothness and transparency of the coating film when used as a primer.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to improve the high temperature storage stability of an aqueous emulsion of a polyolefin derivative, particularly a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer, and to reduce environmental pollution problems. An object of the present invention is to provide an aqueous emulsion having excellent storage stability and suitable for use as a primer.

[0008]

Therefore, the researcher of the present invention has diligently studied to solve the above-mentioned problems, and as a result, by adding a predetermined amount of a water-insoluble organic solvent to an aqueous emulsion of a polyolefin derivative, The present inventors have found that the high temperature storage stability of an aqueous emulsion is greatly improved and have reached the present invention.

That is, the gist of the present invention lies in an emulsion of a polyolefin derivative, which comprises an emulsifier and a water-insoluble organic solvent in an amount of 0.2% by weight or more and 5% by weight or less. Another gist of the present invention is that the water-insoluble organic solvent has a solubility in water of 20 ° C.
In the above aqueous emulsion which is an organic solvent of 1% by weight or less. Another subject matter of the present invention resides in the above-mentioned aqueous emulsion, wherein the polyolefin derivative is a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer.

Another aspect of the present invention is that a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer is represented by the following formula (I) or / and
The above-mentioned aqueous emulsion contains a constitutional repeating unit represented by (II).

[0011]

[Chemical 2]

[In the formulas (I) and (II), R represents a hydrogen atom or a methyl group. Another gist of the present invention is that the hydroxyl group-containing conjugated diene-based polymer has a constitutional repeating unit of 1,2-addition product of 1,3-butadiene and 1,4-addition product of the former 0-40 mol%. In the latter aqueous emulsion, the latter is contained in a proportion of 100 to 60 mol%.

Another subject matter of the present invention resides in the aqueous emulsion used as a primer. Another gist of the present invention is to emulsify a solution containing a polyolefin derivative, a water-insoluble organic solvent of 0.2 wt% or more and 5 wt% or less, an emulsifier, and water by shear mixing at 60 ° C. or more. It lies in a characteristic method for producing an aqueous emulsion.

Another subject matter of the present invention lies in a laminate characterized in that a coating layer of the aqueous emulsion is formed on the surface of an olefin polymer.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is an aqueous emulsion of a polyolefin derivative, which is characterized by containing an emulsifier and a water-insoluble organic solvent in an amount of 0.2% by weight or more and 5% by weight or less. [Olefin derivative] The polyolefin derivative of the present invention means a polyolefin resin, for example, polypropylene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer or other ethylene or / and propylene and other monomer (eg, butene, Block copolymers and / or random copolymers with (pentene, hexene, heptene, octene, etc.), or copolymers of these components and two or more components consisting of monomers other than ethylene and propylene, alone or in admixture of two or more. Mixtures of diene copolymers, chlorinated products thereof, hydrogenated products, introduced hydroxyl groups, and those prepared by copolymerizing α, β-unsaturated carboxylic acids such as maleic acid. .

When used as a primer for a polyolefin, a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer is preferable, and among them, a hydrogenated derivative of a conjugated diene polymer mainly having a hydroxyl group at the terminal, such as butadiene. , Isoprene, chloroprene,
Radical polymerization of a conjugated diene such as 1,3-pentadiene using a hydroxyl group-containing radical polymerization initiator such as hydrogen peroxide to directly give a conjugated diene polymer having a hydroxyl group at the terminal, or A living polymer having an alkali metal bonded to the terminal was produced using an anionic polymerization catalyst such as an alkali metal, and then a conjugated diene polymer having a hydroxyl group at the terminal was obtained by reacting with an epoxy compound or formaldehyde. Those produced by hydrogenating a hydroxyl group-containing conjugated diene polymer by a conventional method are suitable.

Two or more of the conjugated dienes may be used in combination, and a vinyl monomer such as styrene, acrylonitrile, methyl (meth) acrylate, vinyl acetate, or an α-olefin such as ethylene, propylene or isobutylene, It may be copolymerized in an amount of 30% by weight or less.
Further, in the copolymer containing these vinyl-based monomers and α-olefins, for example, the copolymer is subjected to oxidative decomposition treatment with ozone or the like, and then subjected to reduction treatment with lithium aluminum hydride or the like to give a hydroxyl group at the terminal. It is also possible to produce a copolymer by adding to the above and hydrogenate the obtained copolymer by a conventional method.

Further, as the hydroxyl group-containing conjugated diene polymer, a part thereof includes polyethylene glycol, polypropylene ether glycol, polytrimethylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and ethylene oxide. Polyether type such as block or random copolymer of propylene oxide, block or random copolymer of ethylene oxide and tetrahydrofuran, polyester type such as polycaprolactone polyol, polyethylene adipate polyol, polybutylene adipate polyol, 1,6-hexane polycarbonate It may be replaced with a diol compound such as a polycarbonate type such as a polyol.

The hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer is preferably a primer containing a structural repeating unit represented by the following formula (I) or / and (II).

[0020]

[Chemical 3]

[In the formulas (I) and (II), R represents a hydrogen atom or a methyl group. The conjugated diene of the hydroxyl group-containing conjugated diene polymer is more preferably 1,3-butadiene, and the conjugated diene polymer may be 1,3-butadiene 1,2-adduct and 1,4-butadiene. It is preferable that the constitutional repeating unit with the adduct is contained at a ratio of 0 to 40 mol% of the former and 100 to 60 mol% of the latter, and the former 10
35 mol% and the latter 90 to 65 mol% are more preferable, and the former 15 to 30 mol% and the latter 8
It is particularly preferable that the content is 5 to 70 mol%. If the 1,2-addition product exceeds the above range and the 1,4-addition product falls below the above range, the material strength as a primer or the like tends to decrease.

In the present invention, the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer preferably has a hydrogenation ratio of 98% or more in view of heat resistance and humidity resistance as a primer and the like. , 100% is more preferable. Further, the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer, in terms of the strength of the material as a primer, etc.,
The number average molecular weight is preferably 500 to 10,000, more preferably 800 to 8,000,
It is particularly preferably 1,000 to 5,000.

From the viewpoint of the strength of the material such as the primer, the average number of hydroxyl groups bonded per molecule is 1 or more, which is determined based on the multiplier of the number average molecular weight and the hydroxyl group content (wt%). It is preferable that the number is 1.5, more preferably 1.5 or more, and particularly preferably 1.8 or more. From the viewpoint of adhesiveness and the like, it is preferably 8 or less, more preferably 2.5 or less. [Organic Solvent] The organic solvent added in the present invention is insoluble in water, and preferably has a solubility in water of 1% by weight or less at 20 ° C. (the amount soluble in 100 g of water at 20 ° C. is 1 g or less). . The solubility in water is preferably small, preferably 0.1% by weight or less, and more preferably 0.05% by weight or less.

It is considered that this organic solvent acts on the interface between water and the polyolefin derivative to make the oil droplets of the polyolefin derivative spherical, to minimize the surface area of the oil droplets, and to stabilize the emulsion. By this function, an emulsion is easily formed in the pre-emulsification before the emulsification treatment, and the viscosity of the polyolefin derivative which is a high-viscosity liquid or a solid at room temperature can be reduced, so that the dispersion effect is easily applied in the subsequent emulsification treatment. Conceivable. Further, even in the emulsion after the emulsification treatment, it is considered that these organic solvents stabilize the emulsion by the above-mentioned function.

On the other hand, since the organic solvent and the hydrocarbon compound having high solubility in water cannot dissolve the above-mentioned function because they are soluble in water, an emulsion is not formed by pre-emulsification and dispersed by the subsequent emulsification treatment. It is considered that the effect becomes difficult to take and that the emulsion stabilizing effect cannot be obtained even after the emulsification treatment. Further, when a water-soluble substance having a solubility in water of 20 ° C. of several% by weight is used, the boundary surface between water and oil droplets is easily disturbed and the life of the emulsion is shortened. It is considered that is dissolved in the water from the oil droplets and the polyolefin derivative is likely to precipitate.

Further, the organic solvent is preferably a liquid at the storage temperature of the emulsion. It is preferably liquid at 40 ° C, and more preferably liquid at 20 ° C. If the emulsion is not liquid at the storage temperature, it becomes difficult to keep the oil droplets of the emulsion spherical during storage. Further, it is preferably liquid even at the emulsification temperature. This is because, if the boiling point is exceeded during the emulsification treatment, it will volatilize during the emulsification treatment and will not be able to exist in the oil droplets of the emulsion.

Further, in the temperature range from room temperature to the emulsification temperature (for example, 20 to 100 ° C.), the mixture of the olefin derivative and the organic solvent is a homogeneous solution (a transparent solution is preferable, but a homogeneous state is maintained even in a suspension solution). It is preferable that it is possible). This is because if this mixture is not a uniform solution, the dispersing effect of the emulsifying machine is less likely to be exerted. Therefore, as the organic solvent, it is preferable to select and use an organic solvent having a high compatibility with the polyolefin derivative so as to form a uniform solution in the temperature range. The emulsification temperature is not higher than the boiling point of water. However, in the present invention, it is preferable to emulsify at 60 ° C or higher, so that at least 20 to 60 ° C or lower is a homogeneous solution.

The organic solvent may be any of hydrocarbons, halogenated hydrocarbons and non-hydrocarbons as long as it is insoluble in water. The hydrocarbon may be any of aliphatic hydrocarbons, aromatic hydrocarbons and alicyclic hydrocarbons. Good. Examples of organic solvents include
Toluene, cyclohexane, n-hexane and the like can be mentioned, with preference given to toluene. Examples of the organic solvent include those having an isoprene skeleton such as terpinolene and limonene for the purpose of stabilizing the emulsion and imparting a scent at the same time. Among them, terpinolene is preferable. Two or more organic solvents may be used in combination.

The amount of the organic solvent added is 0.2% by weight or more and 5% by weight or less based on the total amount of the aqueous emulsion.
It is preferably 1% by weight or more and 3% by weight or less, more preferably 2% by weight or less. If less than 0.2% by weight, 40
Creaming phenomenon is likely to occur when stored above ℃. On the other hand, if it exceeds 5% by weight, the amount of emulsifier to be used increases and the adhesive strength is reduced when it is used as a primer. Furthermore, add an organic solvent such as toluene to 5
If it is added in excess of weight%, the odor of the organic solvent becomes so strong that it is not practical. When two or more organic solvents are used in combination, the total content is 0.2 to 5% by weight. [Emulsifier] As the emulsifier used in the present invention, a known emulsifier can be used, but it is usually one or more selected from the group consisting of sodium alkylsulfate and sodium alkylbenzenesulfonate. In particular, when a hydrogenated product of a hydroxyl group-containing conjugated diene polymer is used as the polyolefin derivative, it is particularly preferable to use these emulsifiers. Aqueous emulsions using these surfactants,
It has excellent storage stability, high adhesion and low viscosity.

The alkyl group in sodium alkylsulfate preferably has 10 to 30 carbon atoms, more preferably 12 to 18 carbon atoms. This alkyl group may be linear or branched. Two or more of these alkyl groups may be used in combination. The alkyl group in sodium alkylbenzene sulfonate preferably has 10 to 20 carbon atoms, and has 1 carbon atom.
Those of 0 to 16 are more preferable. This alkyl group may be linear or branched. Two or more of these alkyl groups may be used in combination.

From the viewpoint of storage stability of the aqueous emulsion and viscosity as a primer, the amount of the emulsifier added is preferably 5 to 40 parts by weight, and 10 to 20 parts by weight based on 100 parts by weight of the polyolefin derivative. More preferably, it is part. Further, as the aqueous emulsion of the present invention, other anionic, cationic, nonionic emulsifiers or polymer surfactants may be used in combination within a range that does not impair the effects of the present invention, and further, viscosity adjustment Agents, thickeners, defoaming agents, etc., and also an emulsion or / and a hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer, an antioxidant, a heat stabilizer, an ultraviolet absorber, It may contain a light stabilizer, an antistatic agent, a flame retardant, a coloring agent, a filler and the like. [Method for Producing Aqueous Emulsion] The aqueous emulsion of the present invention is produced by mixing the polyolefin derivative, the organic solvent, the emulsifier, and water and emulsifying the mixture. Generally, before the emulsification treatment, an organic solvent and a polyolefin derivative are mixed to prepare a uniform solution (a transparent solution is preferable, but a suspension solution may be uniform), and an emulsifier aqueous solution is mixed therewith for pre-emulsification. , Emulsify with an emulsifying machine. If the organic solvent is added after emulsification, the organic solvent is not taken into the oil droplets of the emulsion and floats at the top of the emulsion, not only suppressing the creaming phenomenon at high temperature but also smoothing when applied as a primer, It becomes a cause of impairing transparency.

At this time, the amount of the polyolefin derivative charged is usually 1 with respect to the total amount of water and the polyolefin derivative.
Approximately 50% by weight. The emulsifier is used in an amount of usually 5 to 40 parts by weight, preferably 10 to 20 parts by weight, based on 100 parts by weight of the polyolefin derivative. Pre-emulsification is
If it can be emulsified, it may be shaken by hand, but if necessary, a stirring type emulsifying machine or the like may be used.

The emulsification is usually carried out by shear mixing a mixed solution of a polyolefin derivative, an organic solvent, an emulsifier and water, but if necessary, further cavitation action and / or collision is applied. For example, emulsification is performed by applying a shearing force with an emulsifying machine of a method of stirring with a high-speed rotary blade (for example, a stirring machine such as a three-one motor, a homomixer manufactured by Tokushu Kakoki Co., Ltd., a CLEARMIX manufactured by M Technique Co., Ltd.) and shear mixing. Alternatively, a high-pressure pump is used to flow out, the flow path is sharply narrowed to increase the flow velocity, and then collided with an object (for example, Gaurin valve homogenizer), or the flow path is divided into two parts and merged again to collide. It is emulsified by an emulsifying machine of a system in which it is jetted to a low pressure part (for example, Ultimaizer manufactured by Sugino Machine Co., Ltd., Ultramicromizer manufactured by Special Kakoki Co., Ltd.). Usually, under a pressure of about 10 to 100 MPa, at a flow rate of about 100 to 300 m / sec, shearing force, cavitation action, and / or collision are applied to emulsify. Two or more of these emulsification methods may be used in combination, and in the present invention, the latter method among these emulsification methods is particularly preferred. The temperature at that time is 60 ° C. in order to soften the polyolefin derivative, particularly the hydrogenated derivative of the hydroxyl group-conjugated diene polymer.
The temperature is preferably set to the above, and more preferably set to 80 ° C. or higher. [Production of Laminate] The aqueous emulsion of the present invention is suitable as a primer as an adhesive when laminating another material on the surface of an olefin polymer, or as a primer for an adhesive. The coating layer formed of the aqueous emulsion is formed on the surface of the olefin polymer.

Specific examples of the olefin polymer include ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene and the like having 2 to 8 carbon atoms. Homopolymers of α-olefins to the extent of those α-olefins with ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl -1
-Pentene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene, 1-octadecene, and other α-olefins having about 2 to 18 carbon atoms, vinyl acetate, ( Resins such as (meth) acrylic acid, copolymers with (meth) acrylic acid ester, etc., specifically,
For example, ethylene homopolymers such as branched low-density polyethylene and linear high-density polyethylene, ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-propylene-1-butene copolymers, ethylene- 4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-heptene copolymer, ethylene-1-octene copolymer, ethylene-vinyl acetate copolymer, ethylene- (meta ) Acrylic acid copolymer, ethylene- (meth) methyl acrylate copolymer, ethylene- (meth) acrylic acid ethyl copolymer, ethylene- (meth) acrylic acid- (meth) acrylic acid methyl copolymer, etc. Propylene such as ethylene resin, propylene homopolymer, propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer System resin and 1-butene homopolymer, 1-butene - ethylene copolymer, 1-butene - 1-butene-based resins such as propylene copolymers.

The olefin resin used in the present invention has a density of 0.850 to 0.960 g / cm.
³ is preferable and 0.890-0.930 g / c
m and even more preferably ^3. Also, JIS K7210
The melt flow rate measured with a 21.18 N load in accordance with the above is 190 ° C. for ethylene resins and the like, 230 ° C. for propylene resins, and 0.01-200.
g / 10 min is preferable, and 0.1-100 g / 1
More preferably, it is 0 minutes.

As the olefin polymer in the present invention, ethylene and propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 4- Methyl-1-hexene, 1
-Heptene, 1-octene, 1-decene and the like having 3 to 10 carbon atoms
Binary or ternary or higher copolymers with about 10 α-olefins, and further 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6 -Methyl-1,5-heptadiene, 1,4-
Octadiene, 7-methyl-1,6-octadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 5-iso Rubber such as a ternary or quaternary or higher copolymer obtained by copolymerizing a non-conjugated diene such as propenyl-2-norbornene, specifically, for example, ethylene-propylene copolymer, ethylene-1-butene copolymer , Ethylene-
Examples thereof include rubbers such as 1-hexene copolymer, ethylene-1-octene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-1-butene-nonconjugated diene copolymer.

In the present invention, the ethylene-α-olefin copolymer rubber has an ethylene content of 50 to 90.
It is preferably in the range of 55% by weight, more preferably 55 to 75% by weight. Also, according to ASTM D1646, Mooney viscosity [ML _{1 + 4} (100
[Deg.] C)] is preferably 30 to 250, and 50 to 15
It is more preferably 0.

The olefin polymer in the present invention is preferably a mixture of the olefin polymer resin and the olefin polymer rubber, and the like, and the olefin polymer resin is 0 to 70% by weight and the olefin. It is preferably composed of 100 to 30% by weight of the polymer rubber, more preferably 10 to 60% by weight of the former resin and 90 to 40% by weight of the latter rubber, and 20 to 5 of the former resin.
Particularly preferred is one consisting of 0% by weight and the latter rubber of 80 to 50% by weight.

Further, the olefin polymer in the present invention may be a mixture of other thermoplastic resin, rubber or the like, and further, if necessary, an antioxidant, a heat stabilizer, an ultraviolet ray. Absorber, light stabilizer, antiblocking agent,
Lubricants, antistatic agents, antifogging agents, neutralizing agents, dispersants, flame retardants,
It may contain a colorant, a crosslinking agent, a softening agent, an antibacterial agent, an antifungal agent, a conductivity-imparting agent, a filler and the like.

The surface of the olefin polymer in the laminate of the present invention means an extrusion-molded product, a compression-molded product, an injection-molded product, a hollow-molded product, etc. of the above-mentioned olefin-based polymer, as well as thermoforming, stretching and crosslinking thereof. , The surface of various molded products that have been subjected to secondary molding such as foaming, and the coating layer is formed by coating the surface of the above-mentioned aqueous emulsion and drying.

Examples of the coating method include knife coating, roll coating, spraying, brush coating and dipping. The coating amount is 0 in terms of solid content in terms of adhesiveness. It is preferably 0.02 to 25 g / m ^2, and more preferably 0.5 to 5 g / m ² . When the aqueous emulsion contains a curing agent for a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer and the coating layer on the surface of the olefin polymer is cured, it is usually 50 to 200 ° C. after the coating. Heat to the temperature of.

In the laminate of the present invention, for example, directly on a coating layer of a polyolefin derivative such as a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer, or via an adhesive layer provided thereon, for example, , Polyamide-based resin, ethylene-vinyl acetate copolymer saponified product, polyester-based resin, polycarbonate-based resin, polystyrene-based resin, acrylic resin or other thermoplastic resin film or sheet,
Woven or non-woven fabrics, other molded products, sheets of various thermosetting resins, and metal foils or sheets of aluminum or the like, paper, etc. are laminated by pressure bonding or the like to form a desired laminate.

[0043]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The polyolefin derivative, emulsifier, emulsifier, and average particle size measuring machine used in the following examples and comparative examples are shown below. <Polyolefin derivative>P-1; number average molecular weight 2,800, hydroxyl group content 1.4
2.3% average number of hydroxyl groups per molecule, which is calculated based on weight% and a multiplier of number average molecular weight and hydroxyl group content 2.3
, 1,2-adduct / 1,4-adduct = 20 mol% / 8
Hydrogenated derivative having a hydrogenation rate of 98% or more of 1,3-polybutadiene containing 0 mol% of hydroxyl group (“Polytail H” manufactured by Mitsubishi Chemical Corporation). P-2; number average molecular weight 4,000, hydroxyl group content 1.5
3.7% of average number of hydroxyl groups per molecule, which is determined based on weight% and the multiplier of number average molecular weight and hydroxyl group content.
A hydrogenated derivative having a hydrogenation rate of 98% or more of individual hydroxyl group-containing polyisoprene (“Epol” manufactured by Idemitsu Petrochemical Co., Ltd.). <Emulsifier> Sodium dodecylbenzene sulfonate (99% active ingredient manufactured by Tokyo Kasei Co., Ltd.) <Emulsifier> M-Technique Co., Ltd. CLEARMIX Gaurin valve homogenizer <Average particle size> Measured using Nikkiso "Microtrac UPA" . Example 1 A solution A was prepared by mixing 30 parts by weight of Polytail H and 2 parts by weight of toluene at 70 ° C. 70 parts by weight of demineralized water and 3 parts by weight of sodium dodecylbenzene sulfonate were mixed at 70 ° C. to prepare solution B. Mix solution A and solution B at 70 ° C,
After processing at 20,000 rpm for 2 minutes with CLEARMIX manufactured by M Technique Co., Ltd., it was processed for 10 minutes at a pressure of 25 MPa using a valve homogenizer manufactured by Gaulin.
Upon cooling, an aqueous emulsion was obtained (processing temperature 60 ° C. or higher). The average (50%) particle size of the aqueous emulsion immediately after preparation was measured. Further, as a high temperature storage stability test, the aqueous emulsion was put in a constant temperature layer at 40 ° C., and creaming, layer separation and the like were visually observed. The results are shown in the table-
Shown in 1. (Solution A) Polytere H 30 parts by weight Toluene 2 parts by weight (Solution B) Demineralized water 70 parts by weight Sodium dodecylbenzene sulfonate 3 parts by weight Examples 2-3, Comparative Examples 1-5 Table 1 in place of the above toluene An aqueous emulsion was prepared and evaluated in the same manner as in Example 1 except that the addition amount of each of the organic solvents shown was changed. The results are shown in Table-1. still,
Table 2 shows the solubilities (20 ° C.) of water in the organic solvents used in Examples and Comparative Examples.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

INDUSTRIAL APPLICABILITY The present invention can provide an aqueous emulsion which is excellent in stability at high temperature and is particularly suitable for use as a primer, a method for producing the same, and a laminate using the same.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/01 C08J 3/03 CES 5/41 F term (reference) 4F006 AA12 AA13 AA14 AB12 AB13 AB63 AB66 BA01 CA00 DA04 4F070 AA06 AA40 AA74 AB01 AB02 AC32 AC33 AC50 AE00 AE14 CA03 CB01 CB12 4J002 BB051 BB11W BB12W BB15W BL01W BP02W EA016 EA026 EA056 EV187 EV237 FD206 FD317 GJ01 HA07 4J100 AS02P BA03H EA07 GC22 HA01 HA03 HA29 HA56 HA61 HB02 HC17 HC39 JA01

Claims (11)

[Claims] 1. An aqueous emulsion of a polyolefin derivative, comprising an emulsifier and a water-insoluble organic solvent in an amount of 0.2% by weight or more and 5% by weight or less. 2. The aqueous emulsion according to claim 1, wherein the water-insoluble organic solvent is an organic solvent having a solubility in water of 1% by weight or less at 20 ° C. 3. The aqueous emulsion according to claim 1, wherein the polyolefin derivative is a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer. 4. The aqueous emulsion according to claim 3, wherein the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer contains a constitutional repeating unit represented by the following formula (I) or / and (II). . [Chemical 1] [In the formulas (I) and (II), R represents a hydrogen atom or a methyl group. ] 5. The hydroxyl group-containing conjugated diene polymer is 1,
The constitutional repeating unit of the 1,2-adduct of 3-butadiene and the 1,4-adduct is 0-40 mol% of the former, 100 of the latter.
The aqueous emulsion according to claim 3 or 4, which is contained in a proportion of -60 mol%. 6. The aqueous emulsion according to claim 1, wherein the emulsifier is one or more selected from the group consisting of sodium alkylsulfate and sodium alkylbenzenesulfonate. 7. The method according to claim 1, which is used as a primer.
7. The aqueous emulsion according to any one of 6. 8. A solution comprising a polyolefin derivative, a water-insoluble organic solvent of 0.2% by weight or more and 5% by weight or less, an emulsifier, and water is shear-mixed at 60 ° C. or more to emulsify. A method for producing an aqueous emulsion. 9. The method for producing an aqueous emulsion according to claim 8, wherein the water-insoluble organic solvent is an organic solvent having a solubility in water of 1% by weight or less at 20 ° C. 10. The method for producing an aqueous emulsion according to claim 9, wherein collision and cavitation effects are applied in addition to the shear mixing. 11. The surface of the olefin-based polymer according to claims 1 to 7.
A laminated body comprising a coating film layer formed of the aqueous emulsion according to any one of 1.