JP2005320400A - Aqueous emulsion of modified vinylcyclohexane copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous emulsion of a modified vinylcyclohexane copolymer, having a high safety to environment and also giving a film having a good molding property, heat resistance, solvent resistance, mechanical characteristics, etc., especially, excellent in bonding property. <P>SOLUTION: The aqueous emulsion of the modified vinylcyclohexane copolymer obtained by blending the following (A) 100 pts.wt. with (B) 0.1-20 pt. wt. and (C) 0.01-20 pt. wt., melting/kneading and dispersing into an aqueous medium, its primer for coating, and coating or printing binder are provided. (A): At least 1 kind of a copolymer selected from a group consisting of a copolymer of ethylene with vinylcyclohexane, a copolymer of ethylene with an α-olefin and vinylcyclohexane and a copolymer of the α-olefin with vinylcyclohexane. (B): At least 1 kind of a compound having at least 1 kind of an unsaturated group and at least 1 kind of a polar group in the same molecule. (C): An organic peroxide. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an aqueous emulsion. More specifically, a modified vinylcyclohexane copolymer aqueous solution that is highly safe to the environment and has good moldability, heat resistance, solvent resistance, mechanical properties, etc., and in particular provides a film with excellent adhesion. It relates to an emulsion.

  Polyolefin resins are relatively inexpensive and have good moldability, heat resistance, solvent resistance, mechanical properties, appearance, etc., and thus are processed into various molded products and used in many fields. Furthermore, in order to obtain a material having superior characteristics, it is blended with a different polymer to form a polymer alloy, combined with various inorganic materials to form a composite material, and laminated with a metal to form a laminated material. That is known.

  However, since the polyolefin resin does not have a polar group, there may be a problem in adhesiveness, paintability, printability, or the like, and the adhesiveness with an inorganic material or a metal may not be good. Also, it is not compatible with engineering plastics such as polyester resins, polyamide resins, polyphenylene sulfide resins, polyphenylene oxide resins, etc., having different polar polymers, and polymer alloys blended with polyolefin resins and different polymers having polar groups are In some cases, impact resistance, mechanical strength, etc. may be low, or the molded product surface may be peeled off.

As a method for solving the above problem, it is known to use an emulsion for adhesion between a polyolefin resin and a different polymer, an inorganic material or a metal.
For example, in JP-A-7-82423, as an aqueous olefin-based thermoplastic resin emulsion that gives a film excellent in static stability and excellent in transparency, vinyl ester, α, β-unsaturated carboxylic acid, An interface comprising a copolymer of a monomer and an olefin selected from the group consisting of a metal salt of α, β-carboxylic acid and an α, β-unsaturated carboxylic acid ester with water and a specific structural formula It describes an olefinic thermoplastic aqueous emulsion produced by heating together with an activator to a temperature not lower than the melting point of the olefinic thermoplastic resin and melting after stirring.

  JP-A-2003-160621 includes a repeating unit derived from α-olefin and / or ethylene and a specific vinyl compound as a resin having improved adhesion to a substrate such as an olefin resin. A modified olefin copolymer obtained by graft polymerization of an alkenyl aromatic hydrocarbon and / or an unsaturated carboxylic acid to the olefin copolymer is described.

JP-A-7-82423 JP 2003-160621 A

Even in the resins described in each of the above publications, the film has high environmental safety, good moldability, heat resistance, solvent resistance, mechanical properties, etc., and further improved adhesion There is a need for water-based emulsions that provide a high yield.
Under such circumstances, the object of the present invention is to provide a film that is highly safe to the environment and has good moldability, heat resistance, solvent resistance, mechanical properties, etc., and particularly excellent adhesion. It is to provide a modified vinylcyclohexane copolymer aqueous emulsion.

As a result of intensive studies, the present inventors have found that the present invention can solve the above-mentioned problems, and have completed this.
That is, the present invention
A modified vinylcyclohexane copolymer obtained by blending (B) 0.1 to 20 parts by weight and (C) 0.01 to 20 parts by weight with respect to 100 parts by weight of the following (A) and melt-kneading. The present invention relates to a modified vinylcyclohexane copolymer aqueous emulsion dispersed in an aqueous medium, and a coating primer, a paint or a printing binder using the same.
(A): at least one copolymer selected from the group consisting of a copolymer of ethylene and vinylcyclohexane, a copolymer of ethylene, α-olefin and vinylcyclohexane, and a copolymer of α-olefin and vinylcyclohexane. Polymer.
(B): at least one compound having (i) at least one unsaturated group and (ii) at least one polar group in the same molecule (C): organic peroxide

  According to the present invention, a modified vinylcyclohexane copolymer having high safety to the environment and having a good moldability, heat resistance, solvent resistance, mechanical properties, etc., and particularly providing a film with excellent adhesiveness. A combined aqueous emulsion and a coating primer, paint or printing binder using the same can be obtained.

  The copolymer used as (A) in the present invention is a copolymer of ethylene and vinylcyclohexane, a copolymer of ethylene, α-olefin and vinylcyclohexane, and a copolymer of α-olefin and vinylcyclohexane. And at least one copolymer selected from the group consisting of: Examples of the α-olefin include ethylene, propylene, butene, pentene, hexene, octene, and decene.

  The content of vinylcyclohexane contained in the copolymer used as (A) is preferably 1 mol% to 90 mol% from the viewpoint of increasing the graft amount and improving the fluidity, More preferably, it is 1 mol%-50 mol%, More preferably, it is 1 mol%-30 mol%.

The compound used as (B) in the present invention is at least one compound having (i) at least one unsaturated group and (ii) at least one polar group in the same molecule.
(I) The at least one unsaturated group is a carbon-carbon double bond or a carbon-carbon triple bond.

  (Ii) The at least one polar group is, for example, an amide bond contained in a polyamide resin, a carboxyl group or an amino group present at a chain end, and a functional group showing affinity or chemical reactivity, and more specifically Include carboxyl group, ester group, amino group, amide group, imide group, nitrile group, epoxy group, hydroxyl group, isocyanate ester group, and carboxylic acid compound, acid amide compound, acid azide compound, acid halide, acid anhydride And functional groups derived from carboxylic acid compounds, acid amide compounds, acid azide compounds, acid halide salts, and the like.

  Examples of compounds used as (B), that is, compounds having (i) at least one unsaturated group and (ii) at least one polar group in the same molecule include, for example, unsaturated carboxylic acids and unsaturated carboxylic acids. Derivatives, unsaturated epoxy compounds, unsaturated alcohols, unsaturated amines, unsaturated isocyanates and the like can be mentioned.

More specifically,
(1) Maleic acid, maleic anhydride, fumaric acid, maleimide, maleic hydrazide, methyl nadic anhydride, dichloromaleic anhydride, maleic amide, itaconic acid, itaconic anhydride, glycidyl (meth) acrylate, 2-hydroxyethyl Methacrylate, allyl glycidyl ether,

（ただし、上記の式中、Ｒは脂肪族基、または、芳香族基を示す。） (2) a reaction product of maleic anhydride and diamine, for example, compounds having a structure represented by the following formula:

(In the above formula, R represents an aliphatic group or an aromatic group.)

(3) Natural oils such as soybean oil, tung oil, castor oil, linseed oil, hemp seed oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, coconut oil, olive oil, coconut oil, sardine oil,
(4) Epoxidized natural fats and oils,

(5) Acrylic acid, butenoic acid, crotonic acid, vinyl acetic acid, methacrylic acid, pentenoic acid, angelic acid, tiglic acid, 2-pentenoic acid, 3-pentenoic acid, α-ethylacrylic acid, β-methylcrotonic acid, 4 -Pentenoic acid, 2-hexene, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, α-ethylcrotonic acid, 2,2-dimethyl-3-butenoic acid, 2-heptenoic acid, 2- Octenoic acid, 4-decenoic acid, 9-undecenoic acid, 10-undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid, 4-tetradecenoic acid, 9-tetradecenoic acid, 9-hexadecenoic acid, 2-octadecenoic acid, 9- Octadecenoic acid, eicosenoic acid, docosenoic acid, erucic acid, tetracosenoic acid, mycolic acid, 2,4-hexadienoic acid, diallylacetic acid, geranium acid, 2,4-decadi Acid, 2,4-dodecadienoic acid, 9,12-hexadecadienoic acid, 9,12-octadecadienoic acid, hexadecatrienoic acid, eicosadienoic acid, eicosatrienoic acid, icosatetraenoic acid, ricinoleic acid, Unsaturated carboxylic acids such as eleostearic acid, oleic acid, eicosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacosenoic acid, octacosenoic acid, traacontenoic acid Acids,
(6) An ester compound, acid amide compound or anhydride of the above unsaturated carboxylic acid,

(7) Allyl alcohol, crotyl alcohol, methyl vinyl carbinol, allyl carbinol, methyl propenyl carbinol, 4-penten-1-ol, 10-undecen-1-ol, propargyl alcohol, 1,4-pentadiene -3-ol, 1,4-hexadien-3-ol, 3,5-hexadien-2-ol, 2,4-hexadien-1-ol,

(8) 3-butene-1,2-diol, 2,5-dimethyl-3-hexene-2,5-diol, 1,5-hexadiene-3,4-diol, 2,6-octadiene-4,5 -Unsaturated alcohols such as diols,
(9) Unsaturated amines in which the OH groups of the unsaturated alcohols are substituted with —NH ₂ groups,

(10) Polymers such as butadiene and isoprene having a low molecular weight (for example, those having an average molecular weight of about 500 to 10,000),
(11) A product obtained by adding maleic anhydride or phenols to a high molecular weight product (for example, having an average molecular weight of 10,000 or more),
(12) An amino group, a carboxyl group, a hydroxyl group, an epoxy group or the like introduced into a high molecular weight body (for example, an average molecular weight of 10,000 or more)
(13) Allyl isocyanate and the like.

  The compound used as (B), that is, as a compound having (i) at least one unsaturated group and (ii) at least one polar group in the same molecule, preferably maleic anhydride, maleic acid, fumaric acid, Itaconic anhydride, itaconic acid, glycidyl (meth) acrylate, and 2-hydroxyethyl methacrylate.

  Further, the compound used as (B), that is, the compound having (i) at least one unsaturated group and (ii) at least one polar group in the same molecule has two or more of the same kind of unsaturated groups or It may have two or more different kinds of unsaturated groups, and may have two or more kinds of polar groups of the same kind or two or more kinds of different kinds of polar groups.

  A compound used as (B), that is, a compound having (i) at least one unsaturated group and (ii) at least one polar group in the same molecule may be used alone or at least two kinds. May be used in combination.

  The compounding amount of the compound (B) is selected from the group consisting of a copolymer of ethylene and vinylcyclohexane, a copolymer of ethylene, α-olefin and vinylcyclohexane, and a copolymer of α-olefin and vinylcyclohexane. It is 0.1-20 weight part with respect to 100 weight part of at least 1 type of copolymer (A), Preferably it is 0.5-10 weight part.

  If the compounding amount of the compound (B) is less than 0.1 parts by weight, the graft amount of the compound (B) to the copolymer (A) may be reduced and sufficient adhesive strength may not be obtained. If the blending amount exceeds 20 parts by weight, the unreacted compound (B) remaining in the modified vinylcyclohexane copolymer increases, and sufficient adhesive strength may not be obtained.

  The compound used as (C) in the present invention is an organic peroxide, and the organic peroxide (C) used in the present invention is from the viewpoint of improving the graft amount and from preventing the decomposition of the resin. An organic peroxide having a decomposition temperature of 50 to 210 ° C., preferably having a half-life of 1 minute. In addition, an organic peroxide having an action of extracting protons from the copolymer (A) after decomposition to generate radicals is preferable.

  Examples of the organic peroxide having a decomposition temperature of 50 to 210 ° C. with a half-life of 1 minute include diacyl peroxide compounds, dialkyl peroxide compounds, peroxyketal compounds, alkyl perester compounds, and carbonate compounds. . A dialkyl peroxide compound, a diacyl peroxide compound, a carbonate compound, and an alkyl perester compound are preferable.

  Specific examples of the organic peroxide (C) include dicetyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and bis (4-t-butylcyclohexyl). ) Peroxydicarbonate, diisopropyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, dimyristyl peroxycarbonate, 1,1,3,3-tetramethylbutyl neodecanoate, α-cumyl peroxyneodecano Ate, t-butylperoxyneodecanoate, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1 -Bis (t-butylperoxy) cyclododecane, t-hexy Peroxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t -Butyl peroxyacetate, 2,2-bis (t-butylperoxy) butene, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butyl Peroxyisophthalate, dicumyl peroxide, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, , 3-bis (t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, di-t-butylpero Side, p- menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, and the like.

The compounding quantity of an organic peroxide (C) is 0.01-20 weight part with respect to 100 weight part of said copolymers (A), Preferably it is 0.05-10 weight part.
Further, when the compound (B) and the organic peroxide (C) are blended with the copolymer (A) and melt-kneaded to obtain a modified vinylcyclohexane copolymer, styrene is optionally added. Or vinyl aromatic compounds such as divinylbenzene. The compounding quantity of a vinyl aromatic compound is 0-15 weight part with respect to 100 weight part of said copolymers (A), Preferably it is 0-7 weight part.

  In addition, the modified vinylcyclohexane copolymer used in the present invention may be blended with known additives generally added to polypropylene resins, such as antioxidants, heat stabilizers, neutralizing agents, and the like. .

As a method for producing a modified vinylcyclohexane copolymer, it is used for melting and kneading using an extruder, mixing resins, mixing a resin and a solid additive, or mixing a resin and a liquid additive. And various known methods.
Preferable examples include a method in which all or some of the respective components are arbitrarily combined, mixed together or separately by a Henschel mixer, a ribbon blender or the like to obtain a uniform mixture, and then the mixture is melt-kneaded. Is mentioned.

Examples of the method for melt-kneading the mixture include known melt-kneading methods using a Banbury mixer, a plast mill, a Brabender plastograph, a uniaxial or biaxial extruder, and the like.
Preferably, from the viewpoint that continuous production is possible and productivity is improved, a method of melt-kneading using a single-screw or twin-screw extruder, specifically, component (A), component (B) And the component (C) are sufficiently premixed in advance, and the resulting mixture is melt-kneaded by supplying it from a supply port of a single-screw or twin-screw extruder.

The temperature (for example, the cylinder temperature of the extruder) of the melt-kneading part of the extruder is usually 50 to 300 ° C. from the viewpoint of improving the graft amount and preventing the decomposition of the resin, preferably 80-270 ° C. And it is preferable to divide the part which performs the melt kneading of the extruder into two stages of the first half and the latter half, and set the temperature of the melt kneading higher than the temperature of the first half.
The time for melt-kneading is usually 0.1 to 30 minutes, preferably 0.5 to 5 minutes, from the viewpoint of obtaining a sufficient graft amount and preventing the decomposition of the resin.

As a production method of the modified vinylcyclohexane copolymer aqueous emulsion of the present invention, for example,
(1) A method in which an organic phase obtained by dissolving a modified vinylcyclohexane copolymer in an organic solvent and an aqueous phase obtained by dissolving an emulsifier in water are emulsified and then the organic solvent is distilled off.
(2) A method in which the modified vinylcyclohexane copolymer is stirred in a water medium in the presence of an emulsifier under heating to obtain an emulsion and cooled.

  The organic solvent used in the method (1) is not particularly limited as long as it can dissolve the modified vinylcyclohexane copolymer. Examples thereof include aliphatic hydrocarbon organic solvents such as hexane and heptane; cyclohexane. And alicyclic hydrocarbon organic solvents such as toluene, xylene and other aromatic hydrocarbon organic solvents. These organic solvents may be used alone or in combination of at least two kinds.

  In the method (1), as a method for dissolving the modified vinylcyclohexane copolymer in an organic solvent, the modified vinylcyclohexane copolymer is usually simply dissolved in the organic solvent at a temperature of 5 to 100 ° C. .

  In the method (1), the concentration of the modified vinylcyclohexane copolymer in the organic phase is usually 5 to 50% by weight, where the total amount of the organic phase is 100% by weight.

  In the method (1), examples of the emulsifier include an anionic emulsifier, a cationic emulsifier, a nonionic emulsifier, a dispersion stabilizer, and the like. These may be used alone or in combination of at least two kinds. You may do it.

  Examples of the anionic emulsifier include polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene lauryl ether triethanolamine sulfate, polyoxyethylene lauryl ether ammonium sulfate, sodium alkylbenzene sulfonate, sodium alkyl sulfate, triethanolamine alkyl sulfate, Examples include ammonium alkyl sulfate, sodium naphthalene sulfonate formalin condensate, dialkyl sulfosuccinate or fatty acid soap such as fatty acid sodium, fatty acid potassium, and fatty acid amine.

  Examples of the cationic emulsifier include alkyltrimethylammonium chloride and polyoxyethylene alkylamine.

  Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan alkylate, oxyethylene oxypropylene block copolymer, and polyglycerin ester.

  Examples of the dispersion stabilizer include polymer dispersants such as polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, hydroxypropyl cellulose, sodium polyacrylate, sodium polymethacrylate, and styrene maleic anhydride copolymer. .

  In the method (1), the method for preparing an aqueous phase containing an emulsifier usually includes a method in which an emulsifier is added to water and dissolved. The concentration of the emulsifier in the aqueous phase containing the emulsifier is usually 0.1 to 50% by weight, where the total amount of the aqueous phase is 100% by weight.

  In the step of mixing and emulsifying the organic phase containing the modified vinylcyclohexane copolymer and the aqueous phase containing the emulsifier, the mixing ratio of the organic phase and the aqueous phase is determined from the viewpoint of obtaining a stable emulsion and the resulting modification From the viewpoint of preventing various physical properties of the vinylcyclohexane copolymer aqueous emulsion from being impaired, and from the viewpoint of economic efficiency, the ratio of the emulsifier to the modified vinylcyclohexane copolymer contained in the organic phase is usually 0. It is set to be 5 to 15% by weight, preferably 2 to 10% by weight.

  Examples of a method for mixing and emulsifying an organic phase and an aqueous phase include, for example, an emulsifier having an appropriate shearing force, for example, a method of stirring and mixing using a homogenizer or a colloid mill, an ultrasonic disperser, or the like. Examples thereof include a method of dispersing and mixing, and a method of stirring and mixing is preferable. Moreover, the temperature at the time of emulsification is 5 to 70 degreeC normally.

  Examples of the method for removing the organic solvent from the emulsion obtained by the emulsification step include a method in which the organic solvent is distilled from the emulsion by heating the emulsion under reduced pressure.

  By removing the organic solvent from the emulsion obtained by the emulsification step, a modified vinylcyclohexane copolymer aqueous emulsion can be obtained, and the concentration of the resulting modified vinylcyclohexane copolymer aqueous emulsion can be adjusted as necessary. Then, it can be adjusted to a desired concentration by operations such as heat concentration, centrifugation, and wet separation.

  On the other hand, examples of the emulsifier used in the method (2) include an anionic emulsifier, a cationic emulsifier, a nonionic emulsifier, and a dispersion stabilizer similar to the emulsifier used in the method (1). May be used alone, or at least two of them may be used in combination.

  The emulsifier used in the method (2) is preferably an oxyethyleneoxypropylene block copolymer, particularly from the viewpoint of reducing the particle size of the emulsion.

  The amount of the emulsifier used in the method (2) is from the viewpoint of sufficiently dispersing the modified vinylcyclohexane copolymer and from the viewpoint of reducing the amount of the emulsifier mixed in the modified vinylcyclohexane copolymer aqueous emulsion. From 2 to 50 parts by weight, preferably 4 to 30 parts by weight, based on 100 parts by weight of the modified vinylcyclohexane copolymer.

  The amount of water used as the dispersion medium in the method (2) is determined from the viewpoint of successfully dispersing the modified vinylcyclohexane copolymer in water, and the concentration of the resulting modified vinylcyclohexane copolymer aqueous emulsion is a practical concentration. From the viewpoint of making it, it is usually 50 to 1500 parts by weight, preferably 100 to 500 parts by weight, per 100 parts by weight of the modified vinylcyclohexane copolymer.

  The heating temperature in the method (2) is not lower than the melting point of the modified vinylcyclohexane copolymer and not higher than the decomposition temperature, and is usually 50 to 300 ° C, preferably 120 to 250 ° C.

  The cooling temperature in the method (2) is lower than the softening temperature of the modified vinylcyclohexane copolymer. By cooling to a temperature lower than the softening temperature of the modified vinylcyclohexane copolymer, a fine modified vinylcyclohexane copolymer aqueous emulsion can be obtained without aggregation in the process.

  The median particle diameter of the modified vinylcyclohexane copolymer particles in the modified vinylcyclohexane copolymer aqueous emulsion of the present invention is usually from the viewpoint of coating properties to a substrate, film formability, or emulsion stability. It is 0.01-20 micrometers, Preferably it is 0.1-10 micrometers.

  When the modified vinylcyclohexane copolymer aqueous emulsion of the present invention is applied to a substrate having a low interfacial tension such as polypropylene or polyester, from the viewpoint of increasing wettability, a polyether-modified polydimethylsiloxane is optionally used. It is preferable to add a silicon-based additive such as acetylene glycol-based surfactant. In addition, an emulsifier, a dispersion stabilizer, a thickener, a film forming aid, an antiseptic, a bactericidal agent, and the like may be added as necessary.

  The film of the modified vinylcyclohexane copolymer obtained from the modified vinylcyclohexane copolymer aqueous emulsion of the present invention is excellent in adhesion and blocking resistance, so as a primer or coating agent for polypropylene bumpers, steel plates, aluminum plates, etc. Useful. Further, it is useful as a heat sealing agent for plastic films such as polypropylene, polyethylene, and polyester, paper, aluminum foil, etc., and useful as a fiber treatment agent, and further useful as various binders.

  Hereinafter, although a manufacture example, an example, and a comparative example explain the present invention, these are only illustrations and the present invention is not limited to these examples. In addition, the evaluation method in a manufacture example and the used kneader were shown below.

(1) Maleic acid graft amount 1.0 g of a sample was dissolved in 20 ml of xylene. The sample solution was added dropwise to 300 ml of methanol with stirring to re-precipitate the sample and collected. The collected sample was vacuum-dried (80 ° C., 8 hours), and a film having a thickness of 100 μm was formed by hot pressing. The infrared absorption spectrum of the prepared film was measured, and the amount of grafted maleic acid was quantified from the absorption near 1780 cm ⁻¹ .

(2) Kneading machine A DS1-5GHB-E type kneader kneader manufactured by Moriyama Co., Ltd. was used.

Production Example MFR (150 ° C., 2.16 kgf) = 34, vinylcyclohexane content = 16 mol% of ethylene vinylcyclohexane copolymer A 100 parts by weight, maleic anhydride 2.5 parts by weight, styrene 2.0 parts by weight, dicetyl After adding 0.45 part by weight of peroxydicarbonate and sufficiently premixing, it was supplied from the supply port of the kneader kneader and melt kneaded at 180 ° C. to obtain a sample, and then 1,3-bis (t- Butyl peroxyisopropyl) benzene (0.16 parts by weight), maleic anhydride (2.5 parts by weight), and styrene (2.0 parts by weight) were supplied from the feed port of the kneader kneader and melt kneaded at 250 ° C. A polymer was obtained. Table 1 shows the amount of each component used in the production examples and the maleic acid graft amount.

As the organic peroxide A, 1,3-bis (t-butylperoxyisopropyl) benzene was used. The temperature at which the half-life is 1 minute is 183 ° C.
As the organic peroxide B, dicetyl peroxydicarbonate was used. The temperature at which the half-life is 1 minute is 99 ° C.

Example 1
30 g of the modified vinylcyclohexane copolymer obtained in the production example was dissolved in 250 g of toluene at 80 ° C. for 5 hours. On the other hand, a solution prepared by dissolving 1.5 g of sodium polyoxyethylene lauryl ether sulfate in 150 g of water is prepared, and the two solutions are mixed for 10 minutes at a rotational speed of 12000 rpm using a TK homomixer (M type manufactured by Tokushu Kika Kogyo Co., Ltd.). Stirred to emulsify. The emulsion was heated under reduced pressure to distill off toluene, and then 0.4 g of polyether-modified polydimethylsiloxane was mixed to obtain a modified vinylcyclohexane copolymer aqueous emulsion. The median particle diameter of the copolymer particles in the obtained modified vinylcyclohexane copolymer aqueous emulsion was 1.7 μm, and almost no aggregation separation or creaming was observed, and the copolymer particles were stable. Note that a laser light scattering particle size distribution analyzer (SALD-2000: manufactured by Shimadzu Corporation) was used for the measurement of the median particle size.

Example 2
30 g of the modified vinylcyclohexane copolymer obtained in the production example was dissolved in 250 g of toluene at 80 ° C. for 5 hours. On the other hand, a solution prepared by dissolving 1.5 g of sodium dodecylbenzenesulfonate in 150 g of water was prepared, and the two solutions were mixed and stirred at a rotation speed of 12000 rpm for 10 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd .; M type). And emulsified. This emulsion was heated under reduced pressure to distill off toluene, and then mixed with 0.4 g of polyether-modified polydimethylsiloxane to obtain a modified vinylcyclohexane copolymer aqueous emulsion. The median particle size of the copolymer particles in the obtained modified vinylcyclohexane copolymer aqueous emulsion was 2.5 μm, and almost no aggregation separation or creaming was observed, and the copolymer particles were stable.

Example 3
30 g of the modified vinylcyclohexane copolymer obtained in the production example was dissolved in 250 g of toluene at 80 ° C. for 5 hours. On the other hand, a solution prepared by dissolving 1.5 g of polyoxyethylene lauryl ether sulfate triethanolamine in 150 g of water was prepared, and the two solutions were mixed at a rotational speed of 12000 rpm using a TK homomixer (M type manufactured by Tokushu Kika Kogyo Co., Ltd.). The mixture was mixed and stirred for emulsification. The emulsion was heated under reduced pressure to distill off toluene, and then 0.4 g of polyether-modified polydimethylsiloxane was mixed to obtain a modified vinylcyclohexane copolymer aqueous emulsion. The median particle diameter of the copolymer particles in the obtained modified vinylcyclohexane copolymer aqueous emulsion was 2.2 μm, and almost no aggregation separation or creaming was observed, and the copolymer particles were stable.

Example 4
In a pressure-resistant autoclave having an inner diameter of 95 mm, a height of 245 mm, and an internal volume of 1.5 liters equipped with a turbine-type stirring blade having a diameter of 42 mm as a dispersion tank, 240 g of the modified vinylcyclohexane copolymer obtained in the production example, oxyethyleneoxy 24 g of propylene block copolymer (weight average molecular weight 15500: Pluronic F108: manufactured by Asahi Denka Co., Ltd.) and 336 g of water were charged and sealed. Next, the agitator was started and the temperature in the tank was raised to 180 ° C. while stirring the contents at 500 rpm. The tank gauge pressure at this time was 9 kg / cm ² G. After maintaining the temperature in the tank at 180 ° C. and stirring for 15 minutes, the contents are cooled to 50 ° C. while stirring and taken out from the dispersion tank, and 2.0 g of polyether-modified polydimethylsiloxane is mixed and mixed with modified vinylcyclohexane. A combined aqueous emulsion was obtained. The median particle size of the copolymer particles in the obtained modified vinylcyclohexane copolymer aqueous emulsion was 3.3 μm, and almost no aggregation separation or creaming was observed, and the copolymer particles were stable.

Comparative Example 1
Instead of 30 g of the modified vinylcyclohexane copolymer obtained in the production example, 30 g of ethylene vinylcyclohexane copolymer A having MFR (150 ° C., 2.16 kgf) = 34 and vinylcyclohexane content = 16 mol% was used. An ethylene-vinylcyclohexane copolymer aqueous emulsion was obtained under the same conditions as in Example 1. The median particle size of the copolymer particles in the obtained ethylene vinylcyclohexane copolymer aqueous emulsion was 2.3 μm.

Comparative Example 2
Instead of 30 g of the modified vinylcyclohexane copolymer obtained in the production example, 30 g of ethylene vinylcyclohexane copolymer A having MFR (150 ° C., 2.16 kgf) = 34 and vinylcyclohexane content = 16 mol% was used. An ethylene vinylcyclohexane copolymer aqueous emulsion was obtained under the same conditions as in Example 2. The median particle diameter of the copolymer particles in the obtained ethylene vinylcyclohexane copolymer aqueous emulsion was 2.6 μm.

Adhesion evaluation Various aqueous emulsions obtained in Examples and Comparative Examples were coated on a polypropylene plate (thickness 5 mm) so that the thickness of the dried film was 10 μm (Nippon Cedars Service Co., Ltd.) The product name was applied using a bar coater No. 16). This was heated and dried in an oven at 120 ° C. for 1 minute to obtain a film. Based on JIS-K5400 (cross-cut peeling tape method test), the obtained film was cut with a grid-like cut with a gap interval of 5 mm, and then a cellophane tape was stuck on the coating film. Next, one to two minutes after the cellophane tape was applied, the tape was peeled off at right angles with one end of the tape, and the adhesion was evaluated. The evaluation criteria were as follows. The results are shown in Table 2.
○: There was no peeling at a glance at the intersection of the cuts and the square.
Δ: The area of peeling was less than 65% of the square area.
X: The area of peeling was 65% or more of the square area.

As shown in Table 2, it turns out that the film | membrane obtained from the modified vinyl cyclohexane copolymer aqueous emulsion of Examples 1-4 is excellent in adhesiveness.
On the other hand, it can be seen that the films obtained from the vinylcyclohexane copolymer aqueous emulsions of Comparative Examples 1 and 2 have insufficient adhesion.

Claims (3)

A modified vinylcyclohexane copolymer obtained by blending (B) 0.1 to 20 parts by weight and (C) 0.01 to 20 parts by weight with respect to 100 parts by weight of the following (A) and melt-kneading. A modified vinylcyclohexane copolymer aqueous emulsion dispersed in an aqueous medium.
(A): at least one copolymer selected from the group consisting of a copolymer of ethylene and vinylcyclohexane, a copolymer of ethylene, α-olefin and vinylcyclohexane, and a copolymer of α-olefin and vinylcyclohexane. Polymer (B): At least one compound having (i) at least one unsaturated group and (ii) at least one polar group in the same molecule (C): Organic peroxide   The (B) is at least one compound selected from the group consisting of maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, glycidyl (meth) acrylate, and 2-hydroxyethyl methacrylate. Modified vinylcyclohexane copolymer aqueous emulsion.   A primer for coating, a binder for coating or printing, using the aqueous emulsion of the modified vinylcyclohexane copolymer according to claim 1.