JP2003261685A - Aqueous emulsion of hydrogenated derivative of hydroxyl-containing conjugated diene polymer, method for producing the same, and laminate using the same - Google Patents

Abstract

(57) [Problem] To provide an aqueous emulsion having excellent storage stability even at a low concentration. The hydrogenated derivative of a conjugated diene polymer having a hydroxyl group is at least one selected from the group consisting of sodium alkyl sulfate, sodium alkylbenzene sulfonate and a nonionic surfactant having an HLB value of 14 or more as an emulsifier. An aqueous emulsion which is emulsified and produced by a method comprising the following steps. (1) A step of dissolving or suspending a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer in a water-insoluble organic solvent, mixing this with an emulsifier, and water to prepare a mixed solution having the following weight ratio. Hydrogenated derivatives of hydroxyl group-containing conjugated diene polymers:
Organic solvent = 100: 5 or more, water: hydrogenated derivative of conjugated diene polymer containing hydroxyl group + organic solvent = 100: 20-
400 (2) a step of emulsifying the mixture obtained in the above step with a high-pressure jetting disperser. (3) A step of removing the organic solvent in the aqueous emulsion after emulsification.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous emulsion of a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer, a method for producing the same, and a laminate using the same.

[0002]

2. Description of the Related Art Conventionally, olefin polymers such as ethylene resins, rubbers, and propylene resins have excellent molding processability, mechanical properties, water vapor barrier properties, chemical resistance, electrical properties, etc. Making full use of it, automobile parts, home appliances parts,
It is widely used as a building material, etc., but it has the drawback that it is inferior in adhesiveness to other materials, paintability, printability, etc. because it is non-polar.

As a method for improving these drawbacks of the olefin polymer, generally, the surface of the molded product of the olefin polymer is chemically or electrically treated by solvent treatment, flame treatment, corona discharge treatment, plasma treatment or the like. A method of oxidizing by treatment or a method of forming a primer layer by subjecting the surface of the molded body to a primer treatment is used. Among them, the latter primer treatment method has advantages that it does not require complicated steps and facilities, has little variation in treatment effect, and can be applied to a molded body having a complicated shape. Various polyolefin derivatives are used as the primer, and among them, hydrogenated derivatives of conjugated diene-based polymers such as polybutadiene and polyisoprene having a hydroxyl group have excellent adhesiveness.

However, the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer is usually in the form of a solid or a highly viscous liquid, so that it is generally used as a solution of an organic solvent as a primer. On the other hand, in the present situation, there is a strong demand for a primer that does not use an organic solvent because of problems such as working environment and environmental pollution. In order to meet these demands, various methods of using an aqueous emulsion as a primer have been investigated, but all of them have a problem in long-term storage stability as an emulsion. For example, in order to improve the storage stability and the like, JP-A No. 11-269206 discloses that an organic solvent solution of a modified polyolefin and an emulsifier aqueous solution are mixed and emulsified by stirring under specific conditions to remove the solvent. There has been proposed a method for producing an aqueous emulsion of modified polyolefins. But this method
It is not always effective for hydrogenated derivatives of hydroxyl group-containing conjugated diene polymers.

In particular, when spraying a water-soluble emulsion as a primer on a substrate, the concentration of the emulsion should be 5 to control the film thickness of the primer.
%, But if the concentration of the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer is reduced to 5% or less by the conventional method, the emulsion will disintegrate or the oil with a low specific gravity will be used. The drops gathered at the top and were not always stable. For example, an emulsion of hydrogenated polybutadiene polyol or polyisoprene polyol has a large particle size and has a problem in long-term storage stability in a dilute solution having a concentration of 5% or less. In addition, in order to improve the stability at this low concentration, it has been attempted to increase the number of surfactants, but in that case, when used as a primer, this added surfactant becomes an obstacle. , Was a factor that reduces the adhesive strength.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and is an emulsion of a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer, in which the concentration of the emulsion is 5% or less. However, it is an object of the present invention to provide an aqueous emulsion excellent in storage stability, a method for producing the same, and a laminate using the same.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have dissolved or suspended a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer in a water-insoluble organic solvent, This is mixed with an emulsifier and water, the resulting mixed solution is emulsified, and then the organic solvent is removed. By emulsifying the mixed solution of a specific composition with a high-pressure jet disperser, the concentration of the emulsion is 5%. The present invention has been achieved by finding that an aqueous emulsion having excellent storage stability can be produced even when the amount is below.

That is, the gist of the present invention is that the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer is sodium alkylsulfate, sodium alkylbenzenesulfonate and HLB.
A water-based emulsion produced by a method including the following steps, wherein the water-based emulsion is emulsified with at least one selected from the group consisting of nonionic surfactants having a value of 14 or more, as an emulsifier. Exist. (1) A step of dissolving or suspending a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer in a water-insoluble organic solvent, mixing this with an emulsifier and water, and preparing a mixed solution having the following weight ratio.

Hydrogenated derivative of hydroxyl group-containing conjugated diene polymer: Organic solvent = 100: 5 or more Water: Hydrogenated derivative of hydroxyl group-containing conjugated diene polymer +
Organic solvent = 100: 20-400 (2) A step of emulsifying the mixed liquid obtained in the above step with a high-pressure jet disperser. (3) A step of removing the organic solvent in the aqueous emulsion after emulsification.

Another subject matter of the present invention resides in the above aqueous emulsion, wherein the water-insoluble organic solvent is an organic solvent having a solubility in water of 1% by weight or less at 20 ° C. Another gist of the present invention resides in the above aqueous emulsion, wherein the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer contains a structural repeating unit represented by the following formula (I) or / and (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 a step of diluting the emulsion obtained in the step (3) with water so that the concentration of the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer in the aqueous emulsion is 5% by weight or less ( It exists in the said aqueous emulsion manufactured by the method containing 4). Another subject of the invention lies in the aqueous emulsion used as primer.

Another subject matter of the present invention lies in a method for producing the above-mentioned aqueous emulsion. Another subject matter of the present invention resides in a laminated body characterized in that a coating layer is formed on the surface of an olefin polymer by the aqueous emulsion.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION [Method for producing aqueous emulsion]
The aqueous emulsion of the present invention includes (1) a step of mixing the components, (2) a step of emulsifying with a high-pressure jet disperser,
(3) A step of removing the organic solvent, and the method is included. The details will be described below. (1) Step of Mixing Each Component A hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer is mixed with an organic solvent, and this is mixed with an emulsifier and water. <Hydrogenated Derivative of Hydroxyl Group-Containing Conjugated Diene Polymer> In the aqueous emulsion of the present invention, as the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer, known compounds can be used, but the conjugated diene system having a hydroxyl group at the end is mainly used. A hydrogenated derivative of a polymer, for example, butadiene, isoprene, chloroprene, conjugated diene such as 1,3-pentadiene, by radical polymerization using a hydroxyl group-containing radical polymerization initiator such as hydrogen peroxide, In addition, a conjugated diene-based polymer having a hydroxyl group at the terminal is prepared, or a living polymer having an alkali metal bonded at the terminal is produced using an anionic polymerization catalyst such as an alkali metal, and then reacted with an epoxy compound or formaldehyde. To obtain a conjugated diene-based polymer having a hydroxyl group at the end, The hydroxyl group-containing conjugated diene polymer is one produced by hydrogenating a conventional manner. Among them, in the present invention, the former radical polymerization method is preferable.

In this case, two or more kinds of the conjugated dienes may be used in combination, and styrene, acrylonitrile,
Vinyl-based monomers such as methyl (meth) acrylate and vinyl acetate, or α-olefins such as ethylene, propylene and isobutylene 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 is, for example, polyethylene glycol, polypropylene ether glycol, polytrimethylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol or 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 in the present invention is represented by the following formula (I) or / and
It is preferable that it contains a structural repeating unit represented by (II).

[0018]

[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 in the present invention is preferably 1,3-butadiene, and the conjugated diene polymer is 1,3-butadiene 1,2-adduct. It is preferable that the former and the latter contain 100 to 60 mol% of the constituent repeating unit with the 1,4-adduct, and the former 10 to 3 mol%.
5 mol% and the latter 90 to 65 mol% are more preferable, and the former 15 to 30 mol% and the latter 85.
It is particularly preferable that the content is in the range of ˜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 material strength as a primer and the like, 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 (weight%). 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.

The hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer is usually used in an amount of 1 to 50 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of water. <Organic Solvent> The organic solvent used 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.
Below). The solubility in water is preferably low, preferably 0.1% by weight or less, more preferably 0.1% by weight or less.
It is not more than 05% by weight. It is considered that this organic solvent acts on the interface between water and the polyolefin derivative to make the oil droplets made of the polyolefin derivative spherical, minimize the surface area of the oil droplets, and stabilize the emulsion. By this action, in the pre-emulsification before the emulsification treatment, an emulsion is easily formed, and the viscosity of the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer that is a high-viscosity liquid or solid at room temperature can be reduced, It is considered that the high-pressure jet disperser of (3) is likely to have a dispersion effect.

On the other hand, an organic solvent having a high solubility in water cannot dissolve the above-mentioned function because it dissolves in water, so that an emulsion is not formed in the pre-emulsification, and thereafter it is emulsified by a high-pressure jet disperser. At this time, the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer that is a high-viscosity liquid or solid is clogged in the nozzle of the high-pressure jet disperser,
It is considered that sufficient emulsification cannot be achieved. or,
If the solubility in water at 20 ° C is several% by weight, the interface between water and oil droplets tends to be disturbed and the life of the emulsion is shortened. Furthermore, a trace amount of an organic solvent dissolves in water to cause a hydroxyl group-containing conjugated diene. The hydrogenated derivative of the polymer is dissolved from the oil droplets into water, the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer is likely to be deposited, and the pre-emulsion is hardly formed. The organic solvent that can be used in the present invention may be any of hydrocarbons, halogenated hydrocarbons and non-hydrocarbons as long as it is insoluble, and the hydrocarbons are any of aliphatic hydrocarbons, aromatic hydrocarbons and alicyclic hydrocarbons. But it's okay. Examples thereof include toluene, n-hexane, cyclohexane, and the like, with toluene being preferred.

The organic solvent must be used in an amount of 5 parts by weight or more based on 100 parts by weight of the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer. Below that, the effect of the organic solvent is not obtained so much. On the other hand, if the organic solvent is added too much in order to lower the viscosity, more emulsifying agent is needed for emulsification, which eventually lowers the adhesive strength when used as a primer.

Further, the total amount of the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer and the organic solvent is 20 to 400 parts by weight, preferably 20 to 300 parts by weight, and more preferably 20 to 100 parts by weight of water. The optimum emulsion is obtained when used in the range of 200 parts by weight. If the total amount of the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer and the organic solvent with respect to water is too large, the emulsion becomes creamy at the time of emulsification, and at the same time shearing of the emulsifying machine is not taken,
When using the high-pressure jet type homogenizer, the processing liquid cannot be sent by the high-pressure pump. Further, when the total amount of the hydrogenated derivative of the hydroxyl group-containing conjugated diene copolymer and the organic solvent is too small, the emulsion particle size becomes large and the emulsion stability deteriorates. <Emulsifier> The emulsifier used in the present invention is It is at least one selected from the group consisting of sodium alkylsulfate, sodium alkylbenzenesulfonate, and a nonionic surfactant having an HLB value of 14 or more. With other emulsifiers, it is difficult to obtain an aqueous emulsion having a high adhesive strength, excellent storage stability, and low viscosity.

The alkyl group in sodium alkylsulfate preferably has 10 to 30 carbon atoms, and 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.

Nonionic surfactants having an HLB value of 14 or more include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, potyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxy. Examples thereof include propylene alkyl ether, and among them, polyoxyethylene alkyl ether is preferable.

The amount of the emulsifier depends on the amount of the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer and the amount of the organic solvent used, but is preferably 2 with respect to 100 parts by weight of the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer. -30 parts by weight. If it is less than this range, a stable emulsion cannot be obtained, and if it exceeds this range, the viscosity is too high or the adhesive performance when used as a primer is impaired.

If desired, other anionic, cationic or nonionic surfactants may be used in combination. <Other additive components> Material strength as a primer,
In order to improve heat resistance, resistance to moist heat, etc., it may contain a curing agent capable of curing a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer, and as the curing agent, a polyvalent isocyanate compound, Examples thereof include alkyl etherified amino resins, epoxy compounds, silane compounds, and metal chelate compounds.

Examples of the polyvalent isocyanate compound include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, Octamethylene diisocyanate, aliphatic polyisocyanate such as lysine diisocyanate, cyclohexane diisocyanate,
Isophorone diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate, 4,4'-
Alicyclic polyvalent isocyanate such as dicyclohexylmethane diisocyanate, p-phenylene diisocyanate,
Tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, 4,
Aromatic polyvalent isocyanates such as 4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, etc., and trimers, water adducts, or low molecular weight polyol adducts thereof. Etc.

As the alkyl etherified amino resin,
For example, a resin obtained by reacting an amino compound such as urea, melamine, or benzoguanamine with formaldehyde to form a methylol, and then etherifying with a lower alcohol such as methanol or butanol, specifically, an n-butyl etherified urea resin, Examples thereof include i-butyl etherified urea resin, methyl etherified melamine resin, and n-butyl etherified benzoguanamine resin.

Specific examples of the epoxy compound include bisphenol A type epoxy resin and the like, and examples of the silane compound include acetoxysilane, alkoxysilane, ketoxime silane, aminosilane, aminoxysilane and the like, and metal. Examples of the chelate compound include alkoxides such as titanium, zirconium, and aluminum, acetylacetonate, and acylate.

When a curing agent is contained, the curing accelerator may be further contained. Examples of the curing accelerator include a tertiary amine and an organic tin in the case of a curing agent of a polyvalent isocyanate compound. In the curing agent of epoxy compound, compounds such as tertiary amine, phenol,
Examples of the silane compound curing agent include organic acids and organic tin compounds.

The content of the curing agent is determined according to the content of the hydroxyl group in the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer in the aqueous emulsion. Generally, it is based on 1 mol of the hydroxyl group in the aqueous emulsion. Then, the isocyanate group in the case of the polyvalent isocyanate compound or the alkoxy group in the case of the alkyl etherified amino resin is 0.
The amount is preferably in the range of 5 to 1.5 mol, and these curing agents are preferably contained in the aqueous emulsion as a single emulsion or the like.

Further, the aqueous emulsion of the present invention may further contain a viscosity modifier, a thickener, a defoaming agent, etc. within a range that does not impair the effects of the present invention, an antioxidant, a heat stabilizer. Agent, UV absorber, light stabilizer, antistatic agent, flame retardant,
It may contain a colorant, a filler, and the like. <Preparation of mixed solution> First, a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer is dissolved or suspended in an organic solvent to prepare a uniform solution. This homogeneous solution is usually 50-80
Prepare by heating to ℃. The homogeneous solution is preferably transparent, but a homogeneous suspension solution may be used. For that purpose, it is preferable to select an organic solvent having high compatibility with the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer.

Next, an emulsifier and water are mixed with this homogeneous solution. Usually, an emulsifier aqueous solution is prepared and mixed. The emulsifier aqueous solution is usually prepared by heating at 50 to 80 ° C.
The homogeneous solution of the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer and the organic solvent and the aqueous emulsifier solution are usually prepared by heating the homogeneous solution and the aqueous emulsifier solution, respectively, and then mixing without cooling. <Pre-emulsification> Usually, before emulsifying with a high pressure jet disperser,
Pre-emulsify. The pre-emulsification may be performed by hand shaking as long as it can be emulsified, but if necessary, it is carried out by a stirring type disperser, preferably an emulsifying machine of a type of stirring with a high-speed rotary blade (for example, CLEARMIX manufactured by M Technique Co., Ltd.). (2) Step of emulsifying with high-pressure jet disperser The mixed liquid prepared in step (1) is put into a high-pressure jet disperser to emulsify.

In the present invention, the high-pressure jet disperser means
It means an emulsifying machine that disperses (emulsifies) by spraying an emulsion raw material liquid at a pressure of 10 MPa or more. The higher the pressure, the better, and preferably 20 MPa or more, but usually 100 MPa or less in consideration of the resistance of the emulsifier. The high-pressure jet disperser that can be used in the present invention, for example, using a high-pressure pump to flow out, sharply narrow the flow path to increase the flow velocity, and then collide with an object, or divide the flow path into two and It corresponds to an emulsifier of a system in which they are merged, collided, and ejected to a low-pressure portion. An example of the former is Gaur
A valve homogenizer manufactured by In, and examples of the latter include an Ultimizer manufactured by Sugino Machine Co., Ltd., and an Ultra Micromizer manufactured by Tokushu Kakoki Co., Ltd. Usually 100 to 30
At a flow velocity of about 0 m / sec, shearing force, cavitation action, and / or collision are applied to emulsify.

For emulsification, two or more high-pressure jet type dispersers may be used in combination, or an emulsifying machine other than the high-pressure jet type disperser may be used in combination. Examples of other emulsifiers include an emulsifier of a type in which a high-speed rotary blade is stirred to apply a shearing force, for example, a stirrer such as a three-one motor, a homomixer manufactured by TK Co., a CLEARMIX manufactured by M Technique Co. The emulsification temperature is preferably 60 ° C. or higher, and more preferably 80 ° C. or higher. (3) Step of removing organic solvent After emulsification, the organic solvent in the emulsion is removed. Usually, vacuum distillation is carried out until the content of the organic solvent in the emulsion becomes 2% by weight or less. If the amount of residual solvent in the emulsion exceeds 2% by weight, the organic solvent odor will remain in the emulsion, and the hygiene of work when used as a primer,
It can be an environmental issue. The concentration of the organic solvent in the emulsion is preferably as low as possible, preferably 1% by weight or less, and most preferably 0%. (4) Water-diluting step When it is necessary to reduce the emulsion concentration, the emulsion obtained in the previous step is diluted with water. In the case of spray coating as a primer, it is usually diluted so that the emulsion concentration (the concentration of the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer in the emulsion) is 5% by weight or less. [Manufacturing Method of Laminated Body] The aqueous emulsion of the present invention is an adhesive for laminating other materials on the surface of an olefin polymer,
Alternatively, it is suitable as a primer as an adhesive undercoat, and the laminate of the present invention has a coating layer formed by the aqueous emulsion on the surface of an olefin polymer.

Here, as the olefin polymer, specifically, for example, 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 olefinic 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-based polymer in the present invention is preferably a mixture of the olefin-based polymer resin and the olefin-based polymer rubber, etc., and the olefin-based 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 or the like. 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-based 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, and further 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 the coating layer of the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer, or via an adhesive layer provided thereon, for example,
Films or sheets of various thermoplastic resins such as polyamide resin, saponified ethylene-vinyl acetate copolymer, polyester resin, polycarbonate resin, polystyrene resin, acrylic resin, woven or non-woven fabric, and other molded products Etc., and 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.

[0048]

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 hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer, emulsifier, emulsifier, and average particle size measuring machine used in the following Examples and Comparative Examples are shown below. <Hydrogenated Derivative of Hydroxyl Group Conjugated Diene Polymer> P
-1; number average molecular weight 2,800, hydroxyl group content 1.4% by weight, average number of hydroxyl groups bonded per molecule 2.3 determined based on a multiplier of number average molecular weight and hydroxyl group content 2.3
, 1,2-adduct / 1,4-adduct = 20 mol% / 8
A hydrogenated derivative having a hydrogenation rate of 0% by mole of hydroxyl group-containing 1,3-polybutadiene of 98% or more (“Polytail H” manufactured by Mitsubishi Chemical Corporation).

P-2: number-average molecular weight of 4,000, hydroxyl group content of 1.5% by weight, average number of hydroxyl groups bonded per molecule of 3.7 determined based on the multiplier of number-average molecular weight and hydroxyl group content of 3.7. Hydrogenation rate of individual hydroxyl-containing polyisoprene 9
8% or more hydrogenated derivative ("Epol" manufactured by Idemitsu Petrochemical Co., Ltd.). <Emulsifier>S-1; sodium dodecyl benzene sulfonate (manufactured by Tokyo Kasei Kogyo Co., Ltd. active ingredient 99%) S-2; alkyl (C ₁₂ -C ₁₆₎ Sodium sulfate (manufactured by Kao Corporation EMAL 40P active ingredient 37%) S-3 Polyoxyethylene alkyl ether (Emulgen 1118S-70 HLB18 manufactured by Kao 70% active ingredient) S-4; Polyoxyethylene nonylphenyl ether (Emulgen 220 HLB7.8 active ingredient manufactured by Kao 98%) <Emulsifier> M- 1; M-Technique Co., Ltd. CLEARMIX M-2; Gaurin's valve homogenizer <average particle size>Nikkiso's"MicrotracUP"
It was measured using "A". Example 1 100 parts by weight of Polytail H was added to 400 parts by weight of toluene.
Solution A was prepared by dissolving at 0 ° C. A solution B was prepared by dissolving 10 parts by weight of sodium dodecylbenzene sulfonate in demineralized water at 70 ° C. Solution A and solution B were mixed at 70 ° C. The mixed solution was treated with M Technique's CLEARMIX at 20,000 rpm for 2 minutes, and then Gaurin
A pre-emulsion was obtained by treating with a valve homogenizer manufactured by the same company under a pressure of 25 MPa for 10 minutes (temperature of 60 ° C. or higher) and cooling. Subsequently, 45 ° C, 150 torr
An aqueous emulsion was prepared by removing the toluene by vacuum distillation at. For confirmation, the amount of residual solvent in the obtained aqueous emulsion was measured, and the residual solvent was 1
It was confirmed that the content was not more than weight%. The average (50%) particle size of the emulsion was measured and diluted with demineralized water until the solid content of the emulsion was 5% by weight. The storage stability of the diluted solution at room temperature was visually evaluated. (Solution A) Polytere H 100 parts by weight Toluene 400 parts by weight (Solution B) Demineralized water 250 parts by weight Sodium dodecylbenzene sulfonate 10 parts by weight Examples 2-7 and Comparative Examples 1-6 Liquid compositions are shown in Table-1. An aqueous emulsion was prepared and evaluated in the same manner as in Example 1 except that the content was changed to. The results are shown in Table-1. Comparative Example 7 An aqueous emulsion was prepared in the same manner as in Example 2 except that the treatment with Gaurin valve homogenizer was not performed and the treatment was performed with M-Technique Clearmix while cooling to about 20 to 30 ° C. And evaluated. The results are shown in Table-1.

[0050]

[Table 1]

[0051]

The aqueous emulsion produced by the method of the present invention has excellent storage stability even when the emulsion concentration is low, and is suitable for primer applications.

Claims (11)

[Claims] 1. A hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer, wherein the hydrogenated derivative is at least one selected from the group consisting of sodium alkylsulfate, sodium alkylbenzenesulfonate and a nonionic surfactant having an HLB value of 14 or more. An aqueous emulsion produced by a method including the following steps. (1) A step of dissolving or suspending a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer in a water-insoluble organic solvent, mixing this with an emulsifier and water, and preparing a mixed solution having the following weight ratio. Hydrogenated derivative of hydroxyl group-containing conjugated diene polymer: Organic solvent = 100: 5 or more Water: Hydrogenated derivative of hydroxyl group-containing conjugated diene polymer +
Organic solvent = 100: 20-400 (2) A step of emulsifying the mixed liquid obtained in the above step with a high-pressure jet disperser. (3) A step of removing the organic solvent in the aqueous emulsion after emulsification. 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 hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer as described above, wherein the hydrogenated derivative contains a structural repeating unit represented by the following formula (I) or / and (II). Aqueous emulsion. [Chemical 1] [In the formulas (I) and (II), R represents a hydrogen atom or a methyl group. ] 4. 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 any one of claims 1 to 3, which is contained in a proportion of -60 mol%. 5. The aqueous emulsion according to claim 1, wherein the content of the organic solvent in the aqueous emulsion in the step (3) is 2% by weight or less. 6. The step (4) of diluting the aqueous emulsion obtained in the step (3) with water so that the concentration of the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer in the aqueous emulsion is 5% by weight or less. Claim 1 manufactured by a method including
The aqueous emulsion according to any one of 1 to 5. 7. The method according to claim 1, which is used as a primer.
7. The aqueous emulsion according to any one of 6. 8. The olefin polymer surface 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. 9. A hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer, wherein the hydrogenated derivative is at least one selected from the group consisting of sodium alkylsulfate, sodium alkylbenzenesulfonate and a nonionic surfactant having an HLB value of 14 or more. A method for producing an aqueous emulsion, wherein the method comprises the steps of: (1) A step of dissolving or suspending a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer in a water-insoluble organic solvent, mixing this with an emulsifier and water, and preparing a mixed solution having the following weight ratio. Hydrogenated derivative of hydroxyl group-containing conjugated diene polymer: Organic solvent = 100: 5 or more Water: Hydrogenated derivative of hydroxyl group-containing conjugated diene polymer +
Organic solvent = 100: 20-400 (2) A step of emulsifying the mixed liquid obtained in the above step with a high-pressure jet disperser. (3) A step of removing the organic solvent in the aqueous emulsion after emulsification. 10. The water-insoluble organic solvent is an organic solvent having a solubility in water of 1% by weight or less at 20 ° C.
The method for producing an aqueous emulsion according to 1. 11. A step (4) of diluting the aqueous emulsion obtained in the step (3) with water to adjust the concentration of the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer in the aqueous emulsion to 5% by weight or less. The method for producing an aqueous emulsion according to claim 9 or 10, which comprises: