JP6910783B2 - Dispersion - Google Patents

Description

The present invention relates to a dispersion.

Dispersions such as emulsions and suspensions (particularly aqueous dispersions) are often used in various fields such as adhesives. For example, Patent Document 1 describes an aqueous resin composition containing an acid-modified chlorinated polyolefin that can be used as an adhesive or a primer. However, such an aqueous resin composition did not adhere to the adherend with sufficient strength, or could not adhere the adherends to each other with sufficient strength. Further, Patent Document 2 describes an aqueous emulsion having excellent adhesiveness, which contains a chlorinated rubber having a chlorine atom content of 45% by weight or more, a compound having one or more polymerizable groups, and water. Has been done. However, such an aqueous emulsion did not always have sufficient adhesiveness when used after long-term storage.

Japanese Unexamined Patent Publication No. 2007-31473 International Publication No. 2015/194611

An object to be solved by the present invention is to provide a dispersion liquid that exhibits excellent adhesiveness even when used after long-term storage.

[1] A dispersion liquid containing water as a dispersion medium and a chlorinated rubber as a dispersoid and a compound having a polymerizable group.
The total amount of the chlorinated rubber and the compound having a polymerizable group is 1 to 60% by weight in the total of the chlorinated rubber, the compound having a polymerizable group and water.
A 30 mL dispersion is poured into a 100 mL container and stirred for 1 minute under the conditions of a rotation speed of 800 rpm and a rotation speed of 2,000 rpm using a rotation / revolution stirrer to prepare a measurement sample, and 20 mL of the measurement sample is placed in a cylinder having a diameter of 25 mm. Backscattered light by pouring into a sample cell in the shape of a sample, irradiating the measurement sample in the sample cell with incident light having a wavelength of 880 nm, and detecting the backward scattered light from the measured sample at a position of 45 ° with respect to the incident light. Intensity (%) measurement was started within 10 minutes of preparation of the measurement sample, and backscattering measured 30 minutes after the start of measurement at each of the top, middle and bottom of the measurement sample in the sample cell. The maximum value α (%) in the absolute value of the amount of change in the backward scattered light intensity (%) measured 24 hours after the start of the measurement with respect to the light intensity (%) is the following formulas (I) to (III):
α (upper part) <20 (I)
α (middle part) <5 (II)
α (bottom) <10 (III)
[In the formula, α (upper part) indicates the maximum value α (%) in the upper part of the measurement sample, α (intermediate part) indicates the maximum value α (%) in the middle part of the measurement sample, and α ( The bottom) indicates the maximum value α (%) at the bottom of the measurement sample, and the top, middle, and bottom of the measurement sample each indicate the height of the measurement sample in the sample cell excluding the meniscus portion from above. The part of the measurement sample divided by 1/3 is shown. ]
Dispersion that meets the requirements of.
[2] The dispersion liquid according to the above [1], wherein the chlorine atom content in the chlorinated rubber is 45% by weight or more.
[3] The dispersion according to the above [1] or [2], wherein the amount of chlorinated rubber is 1 to 30 parts by weight with respect to a total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group.
[4] The dispersion liquid according to any one of the above [1] to [3], wherein at least a part of the chlorinated rubber is dissolved in a liquid dispersoid.
[5] The dispersion according to any one of the above [1] to [4], wherein at least a part of the compound having a polymerizable group is liquid at 23 ° C. and atmospheric pressure.
[6] The dispersion liquid according to the above [5], wherein at least a part of the chlorinated rubber is dissolved in a compound having a polymerizable group which is liquid at 23 ° C. and atmospheric pressure.
[7] The dispersion liquid according to any one of the above [1] to [3], wherein the dispersoid is a liquid.
[8] The dispersion liquid according to any one of the above [1] to [7], wherein the compound having a polymerizable group is a compound having an ethylenically unsaturated bond.
[9] The dispersion liquid according to any one of the above [1] to [8], which further contains a surfactant.
[10] The dispersion liquid according to any one of the above [1] to [9], which further contains a photopolymerization initiator.
[11] The dispersion liquid according to any one of the above [1] to [10], which further contains a fluorescent whitening agent.
[12] The dispersion liquid according to any one of the above [1] to [11], which further contains a leveling agent.
[13] The dispersion liquid according to any one of the above [1] to [12], wherein the median diameter of the dispersoid in the dispersion liquid based on the volume is 10 μm or less.
[14] The dispersion according to any one of the above [1] to [13], wherein the chlorinated rubber is a chlorinated rubber having no carboxy group and a carboxylic acid anhydride structure.
[15] A coating film formed from the dispersion liquid according to any one of the above [1] to [14].
[16] The cured product of the coating film according to the above [15].
[17] A laminate in which the first base material, the cured product according to the above [16], the adhesive layer, and the second base material are laminated in this order.
[18] The laminate according to the above [17], wherein the first base material is an olefin polymer or an ethylene-vinyl acetate copolymer.

The dispersion liquid of the present invention can be adhered to an adherend with sufficient strength even if it is used after long-term storage.

<Dispersion>
The dispersion liquid of the present invention contains water as a dispersion medium, and contains a chlorinated rubber and a compound having a polymerizable group as a dispersoid. The dispersion liquid of the present invention is useful as an aqueous adhesive, a primer, or a raw material thereof.

The dispersion of the present invention may be a suspension (suspension) in which the dispersion is solid, an emulsion in which the dispersion is liquid, and a part of the dispersion is solid. It may be a dispersion liquid in which the remaining dispersoid is liquid. The dispersion of the present invention is preferably an emulsion in which the dispersoid is liquid, or a dispersion in which some of the dispersoids are solid and the remaining dispersoid is liquid, more preferably. An emulsion in which the dispersoid is liquid.

In the dispersion liquid of the present invention, it is preferable that at least a part of the chlorinated rubber is dissolved in the liquid dispersoid. Here, the fact that at least a part of the chlorinated rubber is dissolved in the liquid dispersoid means that when the dispersion liquid is filtered through a filter having a pore size of about 0.50 μm, at least a part of the chlorinated rubber is contained in the filtrate. Means that it is included. The chlorinated rubber contained in the filtrate is preferably 1 part by weight or more, more preferably 10 parts by weight or more, still more preferably 30 parts by weight or more, based on 100 parts by weight of the chlorinated rubber contained in the dispersion before filtration. , More preferably 70 parts by weight or more. It is particularly preferred that all of the chlorinated rubber is dissolved in the liquid dispersoid (ie, that all of the chlorinated rubber is contained in the filtrate).

In the dispersion of the present invention, it is preferable that at least a part of the compound having a polymerizable group is liquid at 23 ° C. and under atmospheric pressure, and all the compounds having a polymerizable group are at 23 ° C. and under atmospheric pressure. It is more preferable that it is liquid. In this embodiment, at least a part of the chlorinated rubber is a compound having a polymerizable group that is liquid at 23 ° C. and atmospheric pressure (hereinafter, may be abbreviated as "a compound having a polymerizable group that is liquid"). It is preferably dissolved in, and more preferably all of the chlorinated rubber is dissolved in a liquid compound having a polymerizable group.

When at least a part of the chlorinated rubber is dissolved in a liquid compound having a polymerizable group, a mixture of the chlorinated rubber and a liquid compound having a polymerizable group is filtered with a filter having a pore size of about 0.50 μm. It means that at least a part of the chlorinated rubber is contained in the filtrate when filtered. The chlorinated rubber contained in the filtrate is preferably 1 part by weight or more, more preferably 10 parts by weight or more, still more preferably 30 parts by weight or more, based on 100 parts by weight of the chlorinated rubber contained in the dispersion before filtration. , More preferably 70 parts by weight or more. It is particularly preferred that all of the chlorinated rubber is dissolved in the liquid dispersoid (ie, that all of the chlorinated rubber is contained in the filtrate).

The mixing temperature at the time of preparing a mixture of the chlorinated rubber and the compound having a polymerizable group is usually 25 to 100 ° C., and the mixing time is preferably as short as possible. Examples of the mixer used for this purpose include a Banbury mixer, a Henschel mixer, a homomixer and the like.

The total amount of the chlorinated rubber and the compound having a polymerizable group is 1 to 60% by weight, preferably 3 to 30% by weight, more preferably 5 in the total amount of the chlorinated rubber, the compound having a polymerizable group and water. ~ 15% by weight. When the total amount of the chlorinated rubber and the compound having a polymerizable group is within the above range, the adhesiveness is improved.

For the dispersion of the present invention, 30 mL of the dispersion is poured into a 100 mL container and stirred for 1 minute under the conditions of a rotation speed of 800 rpm and a rotation speed of 2,000 rpm using a rotation / revolution stirrer to prepare a measurement sample of 20 mL. The measurement sample is poured into a cylindrical sample cell having a diameter of 25 mm, the measurement sample in the sample cell is irradiated with incident light having a wavelength of 880 nm, and the backward scattered light from the measurement sample is emitted at a position of 45 ° with respect to the incident light. The measurement of the backward scattered light intensity (%) by detection is started within 10 minutes from the preparation of the measurement sample, and after the measurement is started at each of the upper part, the middle part and the bottom part of the measurement sample in the sample cell. The maximum value α (%) in the absolute value of the amount of change in the backward scattered light intensity (%) measured 24 hours after the start of the measurement with respect to the backward scattered light intensity (%) measured 30 minutes later is the following formula ( I)-(III):
α (upper part) <20 (I)
α (middle part) <5 (II)
α (bottom) <10 (III)
[In the formula, α (upper part) indicates the maximum value α (%) in the upper part of the measurement sample, α (intermediate part) indicates the maximum value α (%) in the middle part of the measurement sample, and α ( The bottom) indicates the maximum value α (%) at the bottom of the measurement sample, and the top, middle, and bottom of the measurement sample each indicate the height of the measurement sample in the sample cell excluding the meniscus portion from above. The part of the measurement sample divided by 1/3 is shown. ]
One of the features is that it meets the requirements of. In the present invention, the boundary between the upper part and the middle part of the measurement sample and the boundary between the middle part and the bottom part of the measurement sample are both included in the middle part of the measurement sample. The dispersion liquid of the present invention satisfying such requirements can be adhered to an adherend with sufficient strength even when used after long-term storage.

A series of operations including the preparation of the measurement sample and the measurement of the backscattered light intensity (%) are carried out in an environment of 24-26 ° C. using an apparatus placed in an environment of 24-26 ° C. For the preparation of the measurement sample (that is, the stirring of the dispersion liquid by the rotation / revolution stirrer), the dispersion liquid that has been allowed to stand for 1 hour or more in an environment of 24 to 26 ° C. is used.

Examples of the rotation / revolution stirrer for preparing the measurement sample include "rotation / revolution mixer Awatori Rentaro ARE-310" manufactured by Shinky Co., Ltd. As an apparatus for measuring the amount of change in the backscattered light intensity (%) of the measurement sample, for example, "Tabiscan TOWER" manufactured by Formulation Co., Ltd. can be mentioned.

The "backscattered light intensity (%)" means "the detected backscattered light intensity (%) with respect to the intensity of the irradiated incident light". The "change amount of the backward scattered light intensity (%) measured 24 hours after the start of the measurement with respect to the backward scattered light intensity (%) measured 30 minutes after the start of the measurement" is defined as "measurement. It means "the difference between the backward scattered light intensity (%) measured 30 minutes after the start and the backward scattered light intensity (%) measured 24 hours after the start of the measurement". The "maximum value in absolute value" means "the maximum value in a plurality of the absolute values calculated at each of the upper part, the middle part and the bottom part of the measurement sample in the sample cell".

The volume-based median diameter of the dispersoid in the dispersion is preferably 10 μm or less, more preferably 0.01 to 5 μm, still more preferably 0.01 to 2 μm, even more preferably 0.01. It is ~ 1 μm. When the median diameter is within the above range, the static stability of the dispersion is good.

The volume-based median diameter of the dispersoid means a particle size at which the value of the integrated particle size distribution is 50% based on the volume. This median diameter can be measured with a laser diffraction particle size measuring device LA-950V2 manufactured by HORIBA, Ltd.

<Chlorinated rubber>
Chlorinated rubber means chlorinated natural rubber or synthetic rubber. The chlorinated rubber may be one type or two or more types. In addition, in this specification, "rubber" means "uncrosslinked rubber" unless otherwise specified.

Some chlorinated rubbers with low crystallinity do not have a melting point. The chlorinated rubber used in the present invention may be a chlorinated rubber having a melting point or a chlorinated rubber having no melting point. It is preferable to use chlorinated rubber having a melting point. The melting point of the chlorinated rubber is preferably 100 ° C. or higher, more preferably 200 ° C. or higher, still more preferably 240 ° C. or higher, preferably 350 ° C. or lower, and more preferably 300 ° C. or lower. The melting point of chlorinated rubber can be measured by a differential scanning calorimetry (DSC). Examples of the DSC device include DSC-60Plus manufactured by Shimadzu Corporation.

The chlorine atom content of the chlorinated rubber is preferably 45% by weight or more, more preferably 45 to 85% by weight, still more preferably 55 to 80% by weight.

As the chlorinated rubber, it is preferable to use one that does not have a carboxy group and a carboxylic acid anhydride structure. When the dispersion liquid of the present invention containing such a chlorinated rubber is used as an aqueous adhesive, a primer or a raw material thereof, the concern about deterioration of the water resistance of the coating film is extremely small and effective.

The chlorinated rubber is not particularly limited as long as it is a chlorinated natural rubber or synthetic rubber, and for example, chlorinated natural rubber, chlorinated butadiene rubber, chlorinated butyl rubber, chlorinated isoprene rubber, butadiene / chlorinated cyclic conjugate. Diene adduct, chlorinated butadiene styrene copolymer, brominated poly (2,3-dichloro-1,3-butadiene) and α-haloacrylonitrile-co-2,3-dichloro-1,3-butadiene copolymer And so on. Chlorinated rubber synthesized from a raw material containing a monomer having 4 or more carbon atoms is preferable. The chlorinated rubber is more preferably at least one selected from the group consisting of chlorinated natural rubber, chlorinated isoprene rubber and chlorinated butadiene rubber, and more preferably chlorinated natural rubber, chlorinated isoprene rubber or chlorinated butadiene. It is rubber.

As a method for chlorinating natural rubber or synthetic rubber, a conventionally known method can be adopted. For example, a method of dissolving natural rubber or synthetic rubber in a chlorinated organic solvent such as carbon tetrachloride or monochlorobenzene or an organic solvent such as toluene and blowing chlorine gas; a state in which natural rubber or synthetic rubber is suspended or emulsified in water. Method of blowing chlorine gas in Examples thereof include a method of directly chlorinating the material. Further, the coagulated solidified natural rubber or synthetic rubber may be dissolved in an organic solvent and then chlorinated, or the coagulated solidified natural rubber or synthetic rubber may be dissolved in an organic solvent and then emulsified and dispersed to volatilize the solvent. It can also be chlorinated in a fresh state. When chlorinating natural rubber, chlorine gas can be blown into the latex-like natural rubber to chlorinate it. For example, polyisoprene, a surfactant, and an acid such as hydrochloric acid, sulfuric acid, or nitric acid are added to water, emulsified, and then chlorine gas is blown into the water to obtain uniformly chlorinated polyisoprene.

The polystyrene-equivalent weight average molecular weight (Mw) of the chlorinated rubber is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, particularly preferably 10,000 or more, and preferably 10,000 or more. It is 400,000 or less, more preferably 200,000 or less. This Mw can be measured by gel permeation chromatography (GPC). When the dispersion liquid of the present invention containing a chlorinated rubber having such Mw is used as an aqueous adhesive, a primer or a raw material thereof, sufficient adhesive strength can be ensured and the viscosity is excessively increased. It is possible to sufficiently secure the adhesiveness to the adherend by suppressing the above.

As the chlorinated rubber, for example, a commercially available product, a known method, or a rubber produced according to the method can be used. Examples of commercially available products include Supercron (registered trademark) CR-10, CR-20 (Nippon Paper Industries, Ltd.), Pergut S-5, Pergut S-10, Pergut S-20, Pergut S-40, and Pergut S. -90, Pergut S-130, Pergut S-170 (Covestro), Alloprene (registered trademark) R10, R20, R40 (manufactured by ICI UK) and the like. Known methods include, for example, the method described in Japanese Patent No. 2660478.

The amount of chlorinated rubber is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, still more preferably 5 to 20 parts by weight, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. It is a department.

The amount of chlorinated rubber is preferably 0.01 to 18% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.%, In total of the chlorinated rubber, the compound having a polymerizable group and water. It is 2 to 5% by weight.

<Compounds with polymerizable groups>
As the compound having a polymerizable group, only one kind may be used, or two or more kinds may be used in combination. Further, the polymerizable group contained in the compound may be one or two or more. Further, the compound may have only one type of polymerizable group, or may have two or more types of polymerizable groups. Examples of the polymerizable group include a vinyl group, an allyl group, a propenyl group, a vinylidene group, a vinylene group, a (meth) acrylic group, a (meth) acryloyl group, a vinyl ether group, a vinylbenzyl ether group, and a (meth) acrylicoxy. Group, (meth) acrylamide group, styryloxy group, styrylamide group, isocyanate group, thioisocyanate group, carboxyl group, alcoholic or phenolic hydroxyl group, silanol group, epoxy group, glycidyl group, cyclic ether group (eg, oxetane group) ) And other ring-opening polymerizable groups. In the present specification, "(meth) acrylic" means "acrylic and methacrylic", and "(meth) acryloyl" means "acryloyl and methacrylic". Other expressions of "(meta)" have the same meaning.

The compound having a polymerizable group is preferably at least one selected from the group consisting of a compound having an ethylenically unsaturated bond, an epoxy compound, and an oxetane compound, and more preferably a compound having an ethylenically unsaturated bond. .. The number of ethylenically unsaturated bonds in the compound having an ethylenically unsaturated bond is preferably 1 to 3, more preferably 1 to 2.

Examples of the compound having one ethylenically unsaturated bond include heterocyclic ethylenically unsaturated compounds (for example, N-vinyl-nitrogen-containing heterocycles such as N-vinylpyrrolidone, N-vinylpyridine and N-vinylcaprolactam. Compounds, heterocyclic (meth) acrylates such as morpholin (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and glycidyl (meth) acrylate), N-vinylformamide, N-vinylacetamide, dialkylaminoethyl (meth) acrylate ( For example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate), N, N'-dimethylacrylamide, alkoxy (poly) alkylene glycol (meth) acrylate (eg, methoxyethylene (meth) acrylate, ethoxy-diethylene glycol (eg, methoxyethylene (meth) acrylate, ethoxy-diethylene glycol). Meta) acrylate, methoxypolyethylene (meth) acrylate, butoxypolyethylene (meth) acrylate, etc.), alkyl (meth) acrylate (for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i- Propyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, Isodecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, stearyl (meth) acrylate, cetyl (meth) acrylate, behenyl (meth) acrylate, etc. ), Hydroxyl group-containing (meth) acrylate (eg, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy Ethyl-2-hydroxyethylphthalic acid, glycerin mono (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentandiol mono (meth) acrylate, 2-hydroxyethyl (meth) acryloyl Phosphate, neopentyl glycol mono (meth) acrylate, polypropylene glyco Lumono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol-propylene glycol mono (meth) acrylate, etc.), poly ε-caprolactone mono (meth) acrylate, mono [2- (meth) acryloyloxyethyl] acid Phosphate, halogen-containing (meth) acrylates (eg, tolfluoroethyl (meth) acrylates, 2,2,3,3-tetrafluoropropyl (meth) acrylates, perfluorooctylethyl (meth) acrylates, N, N, N- Trimethyl-N- (2-hydroxy-3methacryloyloxypropyl) -ammonium chloride, etc.), silicone-containing (meth) acrylate (eg, (meth) acrylic-modified organopolysiloxane, 3- (meth) acrylicoxypropyltrimethoxysilane, 3- (Meta) acrylic oxypropyltriethoxysilane, 3- (meth) acrylicoxypropylmethyldimethoxysilane, 3- (meth) acrylicoxypropylmethyldiethoxysilane, etc.), unsaturated carboxylic acid glycidyl ester-containing (meth) acrylate (For example, glycidyl (meth) acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, etc.), Acrylate vinyl compounds (eg vinyl acetate, vinyl propionate, vinyl butylate, vinyl methyl ether, vinyl ethyl ether, allylglycidyl ether, etc.), unsaturated amides or unsaturated imides (eg, acrylamide, methacrylicamide, diacetone (meth) ) Acrylate, α-chloroacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, N- (meth) acryloylphthalimide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylicamide and maleimide, etc.) , Acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and mono at the end of polymers (eg, polystyrene, polymethyl acrylate, polymethyl methacrylate, poly n-butyl acrylate, poly n-butyl methacrylate, polysilicone, etc.) Examples thereof include macromonomers having an acryloyl group or a monomethacryloyl group.

Examples of the compound having one ethylenically unsaturated bond and having a cyclic structure include (meth) acrylate having an alicyclic skeleton (for example, cyclohexyl (meth) acrylate, 4 (1,1-dimethylethyl)). Cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, norbornylmethyl (meth) acrylate, phenylnorbonyl (meth) acrylate, cyanonol Bornyl (meth) acrylate, menthyl (meth) acrylate, fentyl (meth) acrylate, adamantyl (meth) acrylate, dimethyl adamantyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] deca-8-yl (Meta) Acrylate, Tricyclo [5.2.1.0 ^2,6 ] Deca-4-methyl (Meta) Acrylate, Cyclodecyl (Meta) Acrylate, 2- (Meta) Acryloyloxyethyl Hexahydrophthalic Acid, Isobornyl ( Meta) acrylate, Bornyl (meth) acrylate, Dicyclopentadiene (meth) acrylate, Dicyclopentenyloxyalkyl (meth) acrylate, Tricyclodecanyloxyethyl (meth) acrylate, Isobolmiloxyethyl (meth) acrylate, etc.) , Aralkyl (meth) acrylate (eg, benzyl (meth) acrylate, o-phenylphenol glycidyl ether (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc.), phenoxyalkyl (meth) acrylate (eg, 2-Phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, etc.), alkylphenoxymethyl (meth) acrylate (eg, nonylphenoxyethyl (meth) acrylate, etc.), phenoxy (poly) alkylene glycol (meth) acrylate (eg, , Phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, etc.), alkylphenoxy (poly) alkylene glycol (meth) acrylate (eg, nonylphenoxypolyethylene glycol (meth) acrylate, paracumyl Phenoxyethylene glycol (meth) acrylate, etc.), hydroxyl group and alicyclic skeleton Alternatively, an aromatic skeleton-containing (meth) acrylate (eg, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2-hydroxy-o-phenylphenolpropyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 2 -Hydroxy-3-phenoxypropyl (meth) acrylate, etc.), aromatic vinyl compounds (eg, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m- Chlorstyrene, p-chlorostyrene, p-methoxystyrene, vinyl benzoate, etc.) can be mentioned.

Examples of the compound having two ethylenically unsaturated bonds include di (meth) acrylate of 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate and polyoxyalkylene glycol di. (Meta) acrylate (eg, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol Di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol-propylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate ) Acrylic, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9- Nonandiol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, alkoxylated neopentyl glycol di (meth) acrylate , Tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, alkoxylated hexanediol di (meth) acrylate, pentanediol di ( Meta) acrylate, 3-methyl-pentanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylpropan di (meth) acrylate, pentaerythritol di (meth) acrylate, etc.), silicone-containing (meth) acrylate (for example) , (Meta) acrylic-modified organopolysiloxane, etc.), and diacetone acrylic amide and the like.

Examples of the compound having two ethylenically unsaturated bonds and having a cyclic structure include di (meth) acrylates (for example, 2,) of an alkylene oxide (for example, ethylene oxide, propylene oxide, etc.) adduct of bisphenol A. 2-Bis (2-hydroxyethoxyphenyl) propane di (meth) acrylate, etc.), di (meth) acrylate having a bridging ring hydrocarbon group (eg, cyclohexanedimethanol di (meth) acrylate, tricyclodecandy) Di (meth) acrylate of methylol (eg, tricyclodecanedimethanol di (meth) acrylate), dicyclopentadiene di (meth) acrylate, etc.), bifunctional epoxy resin (meth) acrylic acid adduct (eg, 2) , 2-Bis (glycidyloxyphenyl) propane (meth) acrylic acid adduct, bisphenol A diglycidyl ether methacrylic acid adduct, etc.).

Examples of the compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. Dipentaerythritol Hexa (meth) acrylate, ditrimethylolpropane tetraacrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, tris (acryloyloxy) isocyanurate, tris (2-acryloyloxyethyl) isocia Nurate, tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, tri (meth) acrylate of tris (hydroxypropyl) isocyanurate, triallyl trimellitic acid, triallyl isocyanurate, and silicone-containing (meth) acrylate. (For example, (meth) acrylic-modified organopolysiloxane, etc.) and the like.

The compound having an ethylenically unsaturated bond preferably has 5 to 25 carbon atoms, more preferably 6 to 23 carbon atoms, and even more preferably 8 to 20 carbon atoms.

Examples of the epoxy compound include phenylglycidyl ether, p-tert-butylphenylglycidyl ether, butylglycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, and 1 , 2-Epoxydodecane, Epichlorohydrin, 1,2-Epoxydecane, Styrene oxide, Cyclohexene oxide, 3-Methacryloxymethylcyclohexene oxide, 3-Acryloyloxymethylcyclohexene oxide, 3-Vinylcyclohexene oxide, Bisphenol A diglycidyl Ether, neopentyl glycol diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, water Additive bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, bis (3,4-epoxy- 6-Methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxiside , Ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4 -Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylpropan triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradeca Examples thereof include diene dioxide, limonene dioxide, 1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxycyclooctane and the like.

As the epoxy compound, aromatic epoxides and alicyclic epoxides are preferable, and alicyclic epoxides are more preferable, from the viewpoint of excellent curing speed.

Examples of the oxetane compound include 2-hydroxymethyl-2-methyloxetane, 2-hydroxymethyl-2-ethyloxetane, 2-hydroxymethyl-2-propyloxetane, 2-hydroxymethyl-2-butyloxetane, 1,4. -Bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene and the like can be mentioned.

The compound having a polymerizable group may be either a solid or a liquid at 23 ° C. and atmospheric pressure, and is preferably a liquid.

The amount of the compound having a polymerizable group in the dispersion liquid of the present invention is preferably 70 to 99 parts by weight, more preferably 75 to 97 parts by weight, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. It is by weight, more preferably 80 to 95 parts by weight.

The compound having a polymerizable group is preferably a mixture of a compound having a polymerizable group and not having a cyclic structure and a compound having a polymerizable group and a cyclic structure.

Compounds having a polymerizable group and not having a cyclic structure are preferably 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, 1,6-hexane. At least one selected from the group consisting of diol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10-decanediol di (meth) acrylate, more preferably dodecyl (meth) acrylate. , And at least one selected from the group consisting of 1,6-hexanediol di (meth) acrylate, more preferably at least one selected from the group consisting of dodecyl methacrylate and 1,6-hexanediol dimethacrylate. be.

The compound having a polymerizable group and a cyclic structure is preferably at least selected from the group consisting of 2-phenoxyethylene glycol (meth) acrylate, 2-phenoxydiethylene glycol (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate. One, more preferably at least one selected from the group consisting of 2-phenoxyethylene glycol (meth) acrylate and tricyclodecanedimethanol di (meth) acrylate, and even more preferably 2-phenoxyethylene glycol methacrylate. , And at least one selected from the group consisting of tricyclodecanedimethanol di (meth) acrylate.

When the compound having a polymerizable group is a mixture of a compound having a polymerizable group and not having a cyclic structure and a compound having a polymerizable group and a cyclic structure, it has a polymerizable group and is cyclic. The amount of the non-structural compound is preferably 0.4 to 50% by weight, more preferably 1 to 25% by weight, still more preferably 3 in the total of the chlorinated rubber, the compound having a polymerizable group and water. The amount of the compound having a polymerizable group and a cyclic structure, which is ~ 25% by weight, is preferably 0.01 to 30% by weight, more preferably 0.01 to 30% by weight, in the total of the chlorinated rubber, the compound having a polymerizable group and water. 0.1 to 15% by weight, more preferably 0.2 to 5% by weight.

When the compound having a polymerizable group is a mixture of a compound having a polymerizable group and not having a cyclic structure and a compound having a polymerizable group and a cyclic structure, it has a polymerizable group and is cyclic. The amount of the compound having no structure is preferably 40 to 99% by weight, more preferably 60 to 97% by weight, still more preferably 80 to 95% by weight, based on the total amount of the compounds having a polymerizable group. The amount of the compound having a polymerizable group and the cyclic structure is preferably 1 to 60% by weight, more preferably 3 to 40% by weight, still more preferably, in the total amount of the compounds having a polymerizable group. Is 5 to 20% by weight.

<Water>
The water contained in the dispersion liquid of the present invention is not particularly limited, and for example, tap water or deionized water is used.

<Other ingredients>
The dispersion liquid of the present invention may contain water, chlorinated rubber and other components different from the compound having a polymerizable group. As for other components, only one kind may be used, or two or more kinds may be used in combination. Other components include, for example, polymerization inhibitors, surfactants, photopolymerization initiators, light stabilizers, UV curable oligomers, fluorescent whitening agents, leveling agents, basic compounds, organic solvents, cross-linking agents, photoenhancing agents. Sensitives, other resins or rubbers different from chlorinated rubbers, phenol-based stabilizers, phosphite-based stabilizers, amine-based stabilizers, amide-based stabilizers, anti-aging agents, weather-resistant stabilizers, preservatives, anti-settling agents , Antioxidants, heat stabilizers, rocking agents, thickeners, antifoaming agents, viscosity modifiers, weathering agents, pigment dispersants, antistatic agents, lubricants, nucleating agents, flame retardants, oils, dyes, curing agents Transition metal compounds such as titanium oxide (rutyl type) and zinc oxide; pigments such as carbon black; glass fibers, carbon fibers, potassium titanate fibers, walastonite, calcium carbonate, calcium sulfate, talc, glass flakes, barium sulfate , Clay, kaolin, fine powder silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, and inorganic or organic fillers such as Celite; and the like. For each of these, only one type may be used, or two or more types may be used in combination.

<Polymerization inhibitor>
The polymerization inhibitor is not particularly limited, and a known polymerization inhibitor can be used. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, a monoesterified product of hydroquinone, N-nitrosodiphenylamine, phenothiazine, 4-t-butylcatechol, N-phenylnaphthylamine, 2,6-di-t-butyl-p-. Methylphenol, 2,5-di-t-butylhydroquinone, 1,4-benzoquinone, 2,6-di-t-butyl-1,4-benzoquinone, methyl-p-benzoquinone, 2,5-diphenyl-p- Examples thereof include benzoquinone, 4-methoxyphenol, chloranyl, pyrogallol, 2-oxydiphenylamine, phenothiazine and the like.

Examples of commercially available polymerization inhibitors include Kinopower QS-10, Kinopower QS-20, Kinopower QS-30, Kinopower QS-40, Kinopower QS-W10 (manufactured by Kawasaki Kasei Chemicals Co., Ltd.), Metoquinoneflakes, and Nonflex Alba. MH, TBH, PBQ, tolucinone, TBQ (manufactured by Seiko Kagaku Co., Ltd.) and the like can be mentioned.

The polymerization inhibitor has an effect of enhancing the storage stability of the dispersion and ensuring curability. In consideration of such actions, the amount of the polymerization inhibitor in the dispersion is preferably 0.005 to 0.4 weight based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. Parts, more preferably 0.01 to 0.4 parts by weight, even more preferably 0.01 to 0.3 parts by weight, still more preferably 0.02 to 0.3 parts by weight, even more preferably 0.02 to parts by weight. It is 0.2 parts by weight, particularly preferably 0.035 to 0.2 parts by weight. As the polymerization inhibitor, a polymerization inhibitor that dissolves in a compound having a liquid polymerizable group is preferable.

<Surfactant>
The surfactant is preferably one that acts as an emulsifier. Examples of the surfactant include cationic, anionic, amphoteric or nonionic surfactants, and preferably anionic or nonionic surfactants. The surfactant may be used alone or in combination of two or more.

Examples of the anionic surfactant include amino acid condensates of higher fatty acids such as sodium fatty acid such as sodium palmitate, sodium ether carboxylate such as sodium polyoxyethylene lauryl ether carboxylate, sodium lauroyl sarcosin, and sodium N-lauroyl glutamate. , Higher alkyl sulfonates, higher fatty acid ester sulfonates such as lauric acid ester sulfonates, dialkyl sulfosuccinates such as dioctyl sulfosuccinate, higher fatty acid amide sulfonates such as oleic acid amide sulfonic acid, dodecylbenzene sulfone Alkylaryl sulfonates such as sodium acid and diisopropylnaphthalene sulfonate, formalin condensates of alkylaryl sulfonate, higher alcohol sulfates such as pentadecane-2-sulfate, dipolyoxyethylene dodecyl ether phosphate and the like. Polyoxyethylene alkyl phosphate ester, lignin sulfonate, polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate, polyoxyethylene nonylpropenylphenyl ether ammonium sulfate, bis (polyoxyethylene polycyclic phenyl ether) bismethacrylate sulfate Ester salt, alkylallyl succinate sulfonic acid sodium salt, polyoxyalkylene alkenyl ether ammonium sulfate, 2-sodium sulfoethyl methacrylate, alkoxypolyethylene glycol maleic acid ester, higher alcohol sulfate ester salt, higher carboxylate, alkylbenzene sulfonate , Polyoxyethylene alkyl sulfate salt, polyoxyethylene alkyl phenyl ether sulfate salt and vinyl sulfosuccinate, poly (meth) sodium acrylate, poly (meth) ammonium acrylate, (meth) acrylate- (meth) acrylate. Examples thereof include copolymers, styrene-maleic acid copolymers, ammonium salts of styrene-maleic acid copolymers, ammonium salts of styrene-maleic acid half ester copolymers, sodium carboxymethyl sulfonic acid and sodium formalin sulfonate naphthalene sulfonate.

Examples of the cationic surfactant include alkylamine hydrochlorides such as dodecylamine hydrochloride, alkylquaternary ammonium salts such as alkyldimethylbenzylammonium salt, alkylisoquinolinium salt, and dialkylmorpholinium salt, and benzethonium chloride. And alkylammonium salts such as polyalkylvinylpyridinium salt, dodecyltrimethylammonium salt and cetyltrimethylammonium salt, alkylpyridium salts such as cetylpyridium salt and decylpyridium salt, oxyalkylenetrialkylammonium salt, dioxyalkylenedialkylammonium salt, Examples thereof include allyltrialkylammonium salts, diallyldialkylammonium salts, and polydiallyldimethylammonium chlorides.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene lanolin alcohol, polyoxyethylene alkylphenol formalin condensate, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene glyceryl monofatty acid. Estel, polyoxypropylene glycol monofatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene castor oil derivative, polyoxyethylene fatty acid ester, higher fatty acid glycerin ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene polyoxypropylene Block polymer, polyoxyethylene fatty acid amide, alkylolamide, polyoxyethylene alkylamine, polyoxyethylene alkanediol, alkoxypolyethylene glycol methacrylate, polyoxyethylene alkylphenyl ether, polyethylene glycol fatty acid ester, polyoxyethylene fatty acid amide, polyalkylene Examples thereof include polyamine alkylene oxide adduct, polyalkylene polyimine alkylene oxide adduct, polyvinylpyrrolidone, dicyandiamide polyalkylene polyamine condensate, polyethylene glycol, polyvinyl alcohol and the like.

Examples of the amphoteric tenside include N-laurylalanine, N, N, N-trimethylaminopropionic acid, N, N, N-trihydroxyethylaminopropionic acid, N-hexyl-N, N-dimethylaminoacetic acid, and the like. Examples thereof include 1- (2-carboxyethyl) pyrimidinium betaine, lecithin, lauryl betaine and lauryldimethylamine oxide.

Examples of commercially available surfactants include Emar 0, Emar 10G, Emar 2F paste, Emar 20C, Emar E-27C, Emar 270J, Emar E-27C, Neoperex GS, Neoperex G-15, Neoperex G. -25, Neoperex G-65, Latemul PD-104, Perex OT-P, Perex TR, Perex SS-L, Perex SS-H, Demor N, Demor EP, Emargen 102KG, Emargen 104P, Emargen 105, Emargen 106, Emargen 108, Emargen 404, Emargen 130K, Emargen 147, Emargen LS-106, Emargen LS-110, Emargen A-60, Emargen 109P, Emargen 350, Latemuru PD-420, Leodor 430V, Emanon 1112, Emanon CH-25, Amit 102, Acetamine 86, Coatamine 24P, Anchtor 24B, Neoperex No. 6 Powder, Latemuru E-1000A, Perex OT-P, Emargen LS-114, Emargen 210P, Emargen 220, Emargen 306P, Emargen 320P, Emargen 408, Emargen 409PV, Emargen 420, Anchor 86B and Anchor 20BS (manufactured by Kao), Neugen EA-177, Neugen XL-40, Neugen TDS-30, Neugen TDX-80, Neugen LP-80, DKS NL-15, DKS NL-50, DKS NL-80, DKS NL-110, DKS NL-180, Neugen TDS-70, Neugen TDS-100, Neugen ET-83, Neugen ET-160, Neugen YX-400, Hytenol NF-08, Hytenol 227L, Plysurf A212C, Plysurf A210D, Neocol P, Monogen Y-100 , Catiogen TML, Aqualon KH-10, Aqualon KH-1025, Aqualon HS-10, Aqualon RN-20, Aqualon RN-30, Pittscol K-17L and Pittscol V-7154 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adeca Pluronic F108, Adeca Pluronic L-61, Adeca Pluronic 17R-2 (manufactured by ADEKA) Eleminor JS-20, Eleminor RS-3000, Sanmorin OT-70 and Caribon EN-200 (manufactured by Sanyo Kasei Kogyo), Clarepovar PVA- 103, Clarepoval PVA-105, Clarepoval PVA-117, Clarepoval PVA-217, Clarepoval PVA-205, Clarepoval PVA-203, Clarepoval PVA-210, Clarepoval PVA-235, Clarepoval PVA-403, Clarepoval PVA-405, Clarepoval PVA-417, Clarepoval M-205, Clarepoval MP-203, Clarepoval KL-506 and Clarepoval KL-318 (manufactured by Clare), Akumalim AKM-511-60, Akumalim AKM -0531, Polystar OM, Pronon # 102 (manufactured by Nichiyu Co., Ltd.) and the like can be mentioned.

The dispersion of the present invention preferably contains a surfactant. When the dispersion liquid of the present invention contains a surfactant, the amount thereof is preferably 1 part by weight or more, preferably 30 parts by weight, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. Below, it is more preferably 15 parts by weight or less, still more preferably 10 parts by weight or less.

<Photopolymerization initiator>
A photopolymerization initiator is a compound that produces an active species by the action of light. Examples of the photopolymerization initiator include a photoradical generator that generates an active radical by the action of light, a photoacid generator that generates an acid by the action of light, and a photobase generator that generates a base by the action of light. Be done.

Examples of the photoradical generator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, sulfonic acid derivatives, onium salts (iodonium salts and sulfonium salts, etc.), carboxylic acid esters and the like. ..

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, 4-methylbenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert). -Butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone and the like.

Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). ) Butane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1 -[4- (2-Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methylpropiophenone and 2-hydroxy-2-methyl-1- [4-( 1-Methylvinyl) phenyl] Propane-1-one oligomers and the like.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxy). Naftyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (fran-2-yl) ethenyl] -1 , 3,5-Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like can be mentioned.

As the photoradical generator, a commercially available one can be used. Examples of commercially available photoradical generators include Irgacure (registered trademark) 1173, 907, 184, 651, 819, 250, 2959, 127, 754 and 369 (BASF Japan Co., Ltd.) and Sakeol (registered trademark). ) BZ, Z and BEE (Seiko Kagaku Co., Ltd.), Kayacure (registered trademark) BP100 (Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), ADEKA PUTMER SP-152 and SP -170 (ADEKA Corporation), TAZ-A and TAZ-PP (Nippon Shibel Hegner Co., Ltd.), TAZ-104 (Sanwa Chemical Co., Ltd.), MBF (BASF Japan Co., Ltd.) and the like can be mentioned. These photoradical generators may be used alone or in combination. Specific examples of the combination include Irgacure® 500 (1-hydroxy-cyclohexyl-phenyl-ketone / benzophenone: 50/50%) and Irgacure® 1700 (bis (2,6-dimethoxybenzoyl) -2). , 4,4-trimethylpentylphosphine oxide / 2-hydroxy-2-methylphenylpropan-1-one: 25/75%) and Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethylpentylphosphine oxide / 1-hydroxycyclohexyl-phenylketone: 25/75%) (BASF Japan Co., Ltd.) and the like.

Examples of the photoacid generator include sulfonic acid derivatives, onium salts, dicarboxylic acid imides and the like.

Examples of the sulfonic acid derivative include disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, trifluoromethylsulfonates, benzoinsulfonates, and sulfonates of 1-oxy-2-hydroxy-3-propyl alcohol. Species, pyrogallol trisulfonates, benzyl sulfonates and the like. Specifically, diphenyldisulfone, ditosyldisulfone, bis (phenylsulfonyl) diazomethane, bis (chlorophenylsulfonyl) diazomethane, bis (xysilylsulfonyl) diazomethane, phenylsulfonylbenzoyldiazomethane, bis (cyclohexylsulfonyl) methane, benzointosylate. 1,2-Diphenyl-2-hydroxypropyl tosylate, 1,2-di (4-methylmercaptophenyl) -2-hydroxypropyl tosylate, pyrogallol methyl sulfonate, pyrogallol ethyl sulfonate, 2,6-dinitrophenyl methyl tosi Examples thereof include lat, ortho-nitrophenylmethyl tosylate, and para-nitrophenyl tosylate.

Examples of onium salts include tetrafluoroborate (BF ^4- ), hexafluorophosphate (PF ^6- ), hexafluoroantimonate (SbF ^6- ), hexafluoroarsenate (AsF ^6- ), and hexachloroantimonate (asF 6-). SbCl ^6- ), tetraphenylborate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluoromethylphenyl) borate, perchlorate ion (ClO ^4- ), trifluoromethanesulfonic acid ion (CF ₃ SO ^3- ), Examples thereof include sulfonium salts and iodonium salts having anions such as fluorosulfonic acid ion (FSO ^3- ), toluene sulfonic acid ion, trinitrobenzene sulfonic acid anion, and trinitrotoluene sulfonic acid anion.

Examples of the sulfonium salt include triphenylsulfonium hexafluoroacylnate, triphenylsulfonium hexafluoroborate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluobenzyl) borate, methyldiphenylsulfonium tetrafluoroborate, and methyldiphenylsulfonium. Tetrax (pentafluorobenzyl) borate, dimethylphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenylnaphthylsulfonium hexafluoroarsenate, tritoylsulfonium hexafluorophosphate, anisyldiphenylsulfonium hexa Hexafluolantimonate, 4-butoxyphenyldiphenylsulfonium tetrafluoroborate, 4-butoxyphenyldiphenylsulfoniumtetrakis (pentafluorobenzyl) borate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, tris (4-phenoxyphenyl) sulfonium hexafluoro Phosphate, Di (4-ethoxyphenyl) Methyl Sulfonium Hexafluoroarsenate, 4-Acetylphenyldiphenylsulfonium Tetrafluoroborate, 4-Acetylphenyldiphenylsulfonium Tetrakiss (Pentafluorobenzyl) Borate, Tris (4-thiomethoxyphenyl) Sulfonium Hexa Fluorophosphate, di (methoxysulfonylphenyl) methylsulfonium hexafluoroantimonate, di (methoxynaphthyl) methylsulfonium tetrafluoroborate, di (methoxynaphthyl) methylsulfonium tetrax (pentafluorobenzyl) borate, di (carbomethoxyphenyl) methylsulfonium Hexafluorophosphate, (4-octyloxyphenyl) diphenylsulfonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, tris (dodecylphenyl) sulfonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, 4 − Acetamide phenyldiphenylsulfonium tetrafluoroborate, 4-acetamidophenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, dimethylna Futylsulfonium hexafluorophosphate, trifluoromethyldiphenylsulfonium tetrafluoroborate, trifluoromethyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, phenylmethylbenzylsulfonium hexafluorophosphate, 10-methylphenoxatiinium hexafluorophosphate, 5- Methylthiantrenium hexafluorophosphate, 10-phenyl-9,9-dimethylthioxanthenium hexafluorophosphate, 10-phenyl-9-oxothioxanthenium xantenium tetrafluoroborate, 10-phenyl-9-oxothio Xanthenium tetrakis (pentafluorobenzyl) borate, 5-methyl-10-oxothiatrenium tetrafluoroborate, 5-methyl-10-oxothiatrenium tetrakis (pentafluorobenzyl) borate, and 5-methyl-10,10- Examples thereof include dioxothiatrenium hexafluorophosphate.

Examples of the iodonium salt include (4-n-decyloxyphenyl) phenyliodonium hexafluoroantimonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluoroantimonate, and [4- ( 2-Hydroxy-n-tetradecyloxy) phenyl] phenyliodonium trifluorosulfonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluorophosphate, [4- (2-hydroxy-n-) Tetradecyloxy) Phenyl] Phenyliodonium tetrakis (pentafluorophenyl) borate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium hexafluorophosphate, bis (4-t) -Butylphenyl) iodonium trifluorosulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium Hexafluorophosphate, bis (dodecylphenyl) iodonium trifluoromethylsulfonate, di (dodecylphenyl) iodonium hexafluoroantimonate, di (dodecylphenyl) iodonium trifurate, diphenyliodonium bisulfate, 4,4'-dichlorodiphenyliodonium bisul Fate, 4,4'-dibromodiphenyliodonium bisulfate, 3,3'-dinitrodiphenyliodonium bisulfate, 4,4'-dimethyldiphenyliodonium bisulfate, 4,4'-bissuccinimide diphenyliodonium bisulfate, 3-nitro Diphenyliodonium bisulfate, 4,4'-dimethoxydiphenyliodonium bisulfate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, (4-octyloxyphenyl) phenyliodonium tetrakis (3,5-bis-trifluoromethyl) Phenyl) Borate and the like can be mentioned.

Examples of other onium salts include aromatic diazonium salts such as p-methoxybenzenediazonium hexafluoroantimonate.

Commercially available onium salts include, for example, Sun Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-L150, SI-L160, SI. -L110, SI-L147 (above, manufactured by Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990 (above, manufactured by Union Carbide), ADEKA PUTMER SP-150, SP- 151, SP-170, SP-171, SP-172 (above, ADEKA), Irgacure 261, Irgacure250 (BASF), CI-2481, CI-2624, CI-2369, CI-2064 (above, Japan) Soda), CD-1010, CD-1011, CD-1012 (all manufactured by Sartmer), DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM- 301, NAI-100, NAI-101, NAI-105, NAI-106, SI-100, SI-101, SI-105, SI-106, PI-105, NDI-105, BENZOIN TOSYLATE, MBZ-101, MBZ -301, PYR-100, PYR-200, DNB-101, NB-101, NB-201, BBI-101, BBI-102, BBI-103, BBI-109 (all manufactured by Midori Kagaku Co., Ltd.), PCI-061T , PCI-062T, PCI-020T, PCI-022T (above, manufactured by Nippon Kayaku Co., Ltd.), IBPF, IBCF (manufactured by Sanwa Chemical Co., Ltd.) CD1012 (manufactured by Sartmer), IBPF, IBCF (above, manufactured by Sanwa Chemical Co., Ltd.) ), BBI-101, BBI-102, BBI-103, BBI-109 (all manufactured by Midori Kagaku Co., Ltd.), UVE1014 (manufactured by General Electronics Co., Ltd.), RHODORSIL-PI2074 (manufactured by Rhodia), WPI-113, WPI-116 (Manufactured by Wako Junyakusha) and the like.

It is also described in J. Polymer Science: Part A: polymer Chemistry, Vol.31, 1473-1482 (1993) and J. Polymer Science: Part A: polymer Chemistry, Vol.31, 1483-1491 (1993). Diaryliodonium salts that can be produced by the method can also be used. These may be used alone or in combination of two or more.

Examples of dicarboxylic acid imides include N- (methylsulfonyloxy) naphthalene-1,8-dicarboxyimide, N- (tosyloxy) naphthalene-1,8-dicarboxyimide, and N-[(trifluoromethyl) sulfonyl). Oxy] Naphthalene-1,8-dicarboxyimide, N- (camfersulfonyloxy) naphthalene-1,8-dicarboxyimide, N- (phenylsulfonyloxy) succinimide, N- (tosyloxy) succinimide, N-[(tri) Fluoromethyl) Sulfonyloxy] Sulfonylimide, N- (Camfersulfonyloxy) Sulfinimide, N-[(Trifluoromethyl) Sulfonyloxy] phthalimide, N-[(Trifluoromethyl) Sulfonyloxy] -cis-5-norbornene-endo- Examples thereof include 2,3-dicarboxyimide.

Examples of the photobase generator include an acyclic acyloxyimino compound, an acyclic carbamoyloxime compound, a carbamoyl hydroxylamine compound, a carbamic acid compound, a formamide compound, an acetamide compound, a carbamate compound, a benzyl carbamate compound, and a nitrobenzyl carbamate compound. Examples thereof include sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, α-lactone ring derivative compounds, amineimide compounds, and phthalimide derivative compounds. These may be used alone or in combination of two or more.

When the dispersion of the present invention contains a photopolymerization initiator, the amount thereof is preferably from the viewpoint of stability, reactivity and odor with respect to a total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group. It is 0.01 parts by weight or more, preferably 40 parts by weight or less, more preferably 20 parts by weight or less, still more preferably 10 parts by weight or less, still more preferably 5 parts by weight or less.

<Light stabilizer>
Examples of the light stabilizer include an ultraviolet absorber and a hindered amine-based light stabilizer. The light stabilizer may be used alone or in combination of two or more.

Examples of the ultraviolet absorber include salicylic acids (eg, phenylsalicylate, pt-butylphenylsalicylate, p-octylphenylsalicylate, etc.) and benzophenones (eg, 2,4-dihydroxybenzophenone, 2-hydroxy-). 4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy Benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, etc.), benzotriazoles (eg, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5') -Tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'- Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5' -Ditert-amylphenyl) benzotriazole, 2-{(2'-hydroxy-3', 3 ", 4", 5 ", 6"-tetrahydrophthalimidemethyl) -5'-methylphenyl} benzotriazole, etc.), Triazines (eg, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6- Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2,4-dihydroxyphenyl-4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl)- 4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-Triazine, 2- [2-Hydroxy-4- (2-Hydroxy-3-butyloxypropoxy) Phenyl] -4,6-Bis (2,4-Dimethylphenyl) Enyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-Triazine, etc.), and oxalic acid anhydrides (eg, N- (2-ethylphenyl) -N'-(2-ethoxy-5-t-butylphenyl) oxalate diamide, N- (2-ethyl). Phenyl) -N'-(2-ethoxy-phenyl) oxalic acid diamide, 2-ethoxy-2'-ethyl-oxalic acid bisanilide, oxalic acid diamides having an aryl group optionally substituted on the nitrogen atom, etc. ) Etc. can be mentioned.

Examples of hindered amine-based light stabilizers include ester group-containing piperidines (eg, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine). , 4-Acryloyloxy-2,2,6,6-tetramethylpiperidine, etc.), ether group-containing piperidines (eg, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2) , 2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, etc.), amide group-containing piperidines (eg 4- (phenylcarbamoyloxy) -2,2,6 , 6-Tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene-1,6-dicarbamate, etc.), and high molecular weight piperidine polycondensates (eg, succinate). Dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2 6,6-Pentamethyl-4-piperidinol and tridecyl alcohol condensate, etc.) and the like.

When the dispersion liquid of the present invention contains a light stabilizer, the amount thereof is preferably 0.01 parts by weight or more, preferably 15 parts by weight, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. It is less than or equal to parts by weight, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less.

<UV curable oligomer>
Examples of the ultraviolet curable oligomer include urethane acrylate oligomer, epoxy acrylate oligomer, polyester acrylate oligomer and the like. The UV curable oligomers may be used alone or in combination.

Commercially available urethane acrylate oligomers can be used. Examples of commercially available urethane acrylate oligomers include CN929, CN965, CN968, CN981A75, CN985B88, CN991, CN970AH75, CN975, CN992, CN994 and CN9165 (manufactured by Sartmer), U-4HA and U-6HA (Shin-Nakamura Chemical Co., Ltd.). ), AH-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

Commercially available epoxy acrylate oligomers can be used. Examples of commercially available epoxy acrylate oligomers include CN116, CN120B60, CN120M50, CN131B, CN132, CN137, CN152, and CN2102E (manufactured by Sartmer).

Commercially available polyester acrylate oligomers can be used. Examples of commercially available polyester acrylate oligomers include CN292, CN2259, CN2262, CN2270, CN2271E, CN2272, CN2273, CN2276, CN2279, CN2285, CN2298, CN2300, CN2301, CN2302, CN2303, and CN2304 (manufactured by Sartmer). Be done. These polyester acrylate oligomers may be used alone or in combination.

When the dispersion liquid of the present invention contains an ultraviolet curable oligomer, the amount thereof is preferably 0.01 parts by weight or more, preferably 0.01 parts by weight or more, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. It is 20 parts by weight or less, more preferably 15 parts by weight or less, still more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less.

<Optical brightener>
Examples of the optical brightener include dialkylaminocoumarin, bisdimethylaminostilbene, bismethylaminostilbene, 4-alkoxy-1,8-naphthalenedicarboxylic acid-N-alkylimide, bisbenzoxazolylethylene, 1,4. -Bis (2-benzoxazolyl) naphthalene, dialkylstilbene and the like can be mentioned. Examples of commercially available fluorescent whitening agents include Kayahor 3BS Liq. , Kayahor TAC Liq. , Kayaphor HBC Liq. , Kayalight B, Kayaphor AS 150, Kayaphor CR 200, Kayaphor JB Liq. , Mikawahite ATN conc. (Manufactured by Nippon Kayaku Co., Ltd.), TINOPAL OB, TINOPAL NFW Liquid (manufactured by BASF), Hakkol P, Hakkol PHD, Hakkol RF, Hakkol PSR, Hakkol PSR-B, Hakkol CHP-B, Hakkol CHP-B, Hakkol D, Hakkol BE conc, Hakkol SG conc 150, Hakkol TH-100, Hakkol S-100, Hakkol RX-1, Hakkol OW-11, Hakkol OW-10extra, Hakkol KIP H / C, Hakkol KIP H / C Examples thereof include Hakkol PMS H / C (manufactured by Showa Chemical Industry Co., Ltd.), Nikkafluor SB conc, Nikkafluor KB, Nikkafluor OB, Nikkabright CX H / C (manufactured by Nippon Kayaku Kogyo Co., Ltd.) and the like. The fluorescent whitening agent may be used alone or in combination of two or more.

When the dispersion liquid of the present invention contains a fluorescent whitening agent, the amount thereof is preferably 0.01 parts by weight or more, preferably 0.01 parts by weight or more, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. It is 5 parts by weight or less, more preferably 3 parts by weight or less, and further preferably 1 part by weight or less.

<Leveling agent>
Examples of the leveling agent include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), BYK300, BYK306, BYK310, BYK320, BYK330, BYK346, BYK349, BYK-333, BYK-345, BYK-347, BYK-348, BYK-378 (manufactured by Big Chemie Japan), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (manufactured by Shinetsu Chemical Industry Co., Ltd.), Surflon SC-101, Surfron KH-40 (manufactured by AGC Seimi Chemical Co., Ltd.), Futergent 222F, Futergent 251 and FTX-218 (manufactured by Neos), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (manufactured by Mitsubishi Materials), Megafuck F- 171 (Made by ADEKA), SN Wet 366, Nopco 38-C, SN Disper Sand 5468, SN Disper Sand 5034, SN Disper Sand 5027, SN Disper Sand 5040, SN Disper Sand 5020 (San Nopco) Fluoroalkyl benzenesulfonate, full Oralkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkylammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylamino Sulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, poly Oxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyo Examples thereof include xyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, alkyldiphenyl ether disulfonate and the like.

When the dispersion liquid of the present invention contains a leveling agent, the amount thereof is preferably 1 part by weight or more, preferably 20 parts by weight or less, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. , More preferably 10 parts by weight or less, still more preferably 5 parts by weight or less.

<Basic compound>
Examples of the basic compound include ammonia, organic amine compounds and metal hydroxides. The basic compound is preferably an ammonia or organic amine compound.

Examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, and the like. Examples thereof include 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine and N-ethylmorpholine. Of these, N, N-dimethylethanolamine is preferable.

Examples of the metal hydroxide include lithium hydroxide, potassium hydroxide, sodium hydroxide and the like.

When the dispersion of the present invention contains a basic compound, the amount thereof is preferably 0.01 parts by weight or more, preferably 20 parts by weight, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. It is less than or equal to parts by weight, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less.

<Organic solvent>
Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; methanol. , Ethanol, n-propanol, isopropyl alcohol and alcohols such as n-butanol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether and 3-methoxy-3. Glycols such as −methyl-1-butanol; Cellsolves such as methyl cellosolve, cellosolve, butyl cellosolve, dioxane, MTBE (methyl tertiary butyl ether) and butyl carbitol; ethylene glycol monomethyl ether acetate, PMA (propylene glycol monomethyl ether acetate) , Glycol esters such as diethylene glycol monobutyl ether acetate and diethylene glycol monoethyl ether acetate and the like. These may be used alone or in combination of two or more.

The amount of the organic solvent in the dispersion of the present invention is preferably 0 to 100 parts by weight, more preferably 0, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group, from the viewpoint of odor and the like. It is ~ 50 parts by weight, more preferably 0 to 30 parts by weight, and even more preferably 0 to 10 parts by weight. It is particularly preferable that the dispersion liquid of the present invention does not contain an organic solvent.

<Crosslinking agent>
The inclusion of the cross-linking agent tends to further improve the adhesiveness, the water resistance of the adhesive layer and the solvent resistance of the adhesive layer. Examples of the cross-linking agent include epoxy compounds, polyisocyanate compounds (particularly aliphatic polyisocyanate compounds), oxazoline compounds, aziridine compounds, carbodiimide compounds, active methylol compounds, active alkoxymethyl compounds, metal chelate, hydrazide compounds, and hydrazines. Examples include compounds. Among these, an aliphatic polyisocyanate compound, a carbodiimide compound, an oxazoline compound, a hydrazide compound, and a hydrazine compound are preferable. Of these, aqueous (water-soluble or water-dispersible) ones are more preferable. These cross-linking agents may be used alone or in combination.

Examples of the polyisocyanate compound include hexamethylene diisocyanate (HDI), 4,4'-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), and oligomers or polymers thereof. Specific examples thereof include Sumijour® N3200, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547, 44V10 made of Sumika Cobestro Urethane. , 44V20 and E 21-1, Death Module (registered trademark) manufactured by Sumitomo Cobestro Urethane Co., Ltd. N3100, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547 And DA-L, E14 and E22, Baihijour® 304 and XP2655 manufactured by Sumitomo Cobestro Urethane, Basonat (BASONAT® PLR8878 and HW-100) manufactured by BASF, and Takeda Pharmaceutical Company Limited. Examples thereof include Takeda (registered trademark) WD720, WD725 and WD730, and Duranate (registered trademark) WB40-100, WB40-80D and WX-1741 manufactured by Asahi Kasei Kogyo Co., Ltd.

Specific examples of the carbodiimide compound include Nisshinbo Chemical Co., Ltd .: carbodilite (SV-02, V-02, V-02-L, V-04, E-01, E-02) and the like.

Specific examples of the hydrazide compound include Otsuka Chemical Co., Ltd .: ADH (adipic acid dihydrazide), SDH (sebacic acid dihydrazide), DDH (dodecandiohydrazide), IDH (isophthalic acid dihydrazide), SAH (salicylic acid hydrazide) and the like. Be done.

Specific examples of the hydrazine compound include Otsuka Chemical Co., Ltd .: hydrazine monohydrochloride, hydrazine dihydrochloride, hydrazine monobromide, hydrazine carbonate and the like.

When the dispersion liquid of the present invention contains a cross-linking agent, the amount thereof is preferably 0.01 parts by weight or more, preferably 30 parts by weight, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. Parts or less, more preferably 15 parts by weight or less, still more preferably 10 parts by weight or less, still more preferably 5 parts by weight or less.

<Photosensitizer>
The photosensitizer can be appropriately selected according to the wavelength to be enhanced. The effective excitation wavelength range of the photosensitizer is usually 450 nm or less, preferably 250 to 380 nm. Examples of the photosensitizer include triethanolamine, triisopropanolamine, 4,4-diethylaminobenzophenone, 2-dimethylaminoethyl benzoate, ethyl 4-dimethylaminoethyl benzoate and isoacyl 4-dimethylaminobenzoate. Can be mentioned.

When the dispersion of the present invention contains a photosensitizer, the amount thereof is preferably 0.01 parts by weight or more, preferably 0.01 parts by weight or more, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. It is 15 parts by weight or less, more preferably 10 parts by weight or less, still more preferably 5 parts by weight or less.

<Other resin or rubber>
The dispersion liquid of the present invention may contain another resin or rubber different from the chlorinated rubber as long as the effect of the present invention is not impaired. As for other resins or rubbers, only one type may be used, or two or more types may be used in combination. In the present specification, the term "rubber" means an elastomer having elasticity, and the term "resin" means a thermoplastic resin or a thermosetting resin having no elasticity.

Other resins or rubbers include, for example, ethylene-vinyl ester copolymers, styrene-maleic acid copolymers, resins and modified products having structural units derived from α-olefins having 2 to 20 carbon atoms, and (meth) acrylics. Co-resin, polystyrene, polyvinyl acetate, polyurethane, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-vinylidene chloride Polymer, vinylidene chloride- (meth) acrylic acid ester copolymer, vinylidene chloride-acrylonitrile copolymer, resin having structural units derived from chlorinated α-olefin having 2 to 20 carbon atoms, polyurea, acrylonitrile-butadiene -Sterite copolymer, chloroprene resin, acid-modified chloroprene resin, butyl rubber, brominated butyl rubber, modified rubber, styrene- (meth) acrylic acid copolymer, synthetic rubber, natural rubber, styrene-butadiene copolymer, polybutadiene , Poly (meth) acrylonitrile, poly (meth) acrylamide, polyester, modified polyamide, epoxy resin, styrene-based block copolymer and oligomers thereof. The other resin or rubber may be in the form of a solid (eg, resin or rubber powder) or in the form of an emulsion.

The ethylene-vinyl ester copolymer is a copolymer containing an ethylene unit and a vinyl ester unit. Examples of the vinyl ester unit include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl ester of a tertiary carboxylic acid having 8 to 10 carbon atoms, and so-called vinyl versaticate (for example, manufactured by Shell Chemical Co., Ltd., trade name: Veova (). Examples thereof include units derived from alkyl acid vinyl esters such as registered trademark) 10).

The ethylene-vinyl ester copolymer may contain a unit derived from a monomer copolymerizable with ethylene and vinyl ester in addition to the ethylene unit and the vinyl ester unit. Examples of this monomer include vinyl halides such as vinyl chloride, monomers having a functional group such as a small amount of amide group, and (meth) acrylic acid ester.

Among the ethylene-vinyl ester copolymers, an ethylene-vinyl acetate copolymer (hereinafter, may be abbreviated as "EVA") is preferable.

The ethylene-vinyl acetate copolymer has different properties depending on the vinyl acetate content and the like, but various vinyl acetate content and shapes (films, blocks, fibers, foams) can be used. The ethylene-vinyl acetate copolymer may contain olefin units other than the ethylene unit. Examples of the ethylene-vinyl acetate copolymer containing other olefin units include an ethylene-octene-vinyl acetate copolymer, an ethylene-butene-vinyl acetate copolymer, and an ethylene-propylene-vinyl acetate copolymer. Be done.

Examples of the ethylene-vinyl ester copolymer include VINNOL E15 / 45, E15 / 45M, E15 / 48A, H15 / 42, H15 / 50, H11 / 59, H14 / 36, H40 / 50, H40 / 55, and H40. / 60, H30 / 48M (Wacker Chemie AG) and the like.

The ethylene-vinyl ester copolymer may be in the form of an emulsion. Such an emulsion may be produced by emulsion polymerization of the monomers constituting the ethylene unit and the vinyl ester unit, or a commercially available emulsion may be used. Examples of ethylene-vinyl ester copolymer emulsions include Sumikaflex® 201HQ, 303HQ, 355HQ, 400HQ, 401HQ, 408HQ, 410HQ, 450HQ, 455HQ, 456HQ, 460HQ, 465HQ, 467HQ, 7400HQ, 470HQ, 478HQ, 510HQ, 520HQ, 710, 752, 755, SDX-5100, 801HQ, 808HQ, 830, 850HQ, 900HL and 3950 (above, manufactured by Sumitomo Chemical Co., Ltd.), Vanflex OM-4000 and OM-4200 (above, Kuraray Co., Ltd.), Polysol® EVA AD-2, AD-3, AD-4, AD-5, AD-51, AD-56, AD-59 and P-900 (Showa High Polymer Co., Ltd.) (Manufactured by Denka Co., Ltd.), Denka EVA Tex (registered trademark) # 20, # 30, # 40M, # 60, # 81 and # 82 (all manufactured by Denka Co., Ltd.) and the like.

Examples of the styrene-maleic acid copolymer include Alastair 700 and 703S (manufactured by Arakawa Chemical Industry Co., Ltd., SMA (registered trademark) 1000, SMA (registered trademark) 2000, SMA (registered trademark) 3000 (Cray Valley'). s) and the like. Examples of the styrene-maleic acid copolymer emulsion include VE-1122 (Starlight PMC Co., Ltd.) and the like.

The resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms may be a homopolymer, a random copolymer, a block copolymer, or a graft copolymer. Further, it may be one having a low molecular weight or a high molecular weight with a peroxide or the like.

Examples of α-olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene. , 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptene, 1-octadecene, 1-nonadecene, 1-eicosene, vinylcyclohexane and the like. Of these, ethylene and propylene are preferable.

Examples of the resin having a structural unit derived from α-olefin having 2 to 20 carbon atoms include polyethylene (PE), high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and linear chain. Α-Olefin homopolymers such as low density polyethylene, ultrahigh molecular weight polyethylene and polypropylene (PP), isotactic (isotactic) polypropylene, syndiotactic polypropylene and atactic polypropylene; ethylene-propylene copolymer, propylene-1 Α-Olefin copolymers such as −butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer and ethylene-1-hexene copolymer; and α having 2 to 20 carbon atoms. Examples thereof include a copolymer of a-olefin and a monomer copolymerizable with the α-olefin. Further, the copolymer of the α-olefin having 2 to 20 carbon atoms and the monomer copolymerizable with the α-olefin may contain one type of unit derived from each, or each of them. It may contain two or more types of units derived from.

Examples of the monomer copolymerizable with the α-olefin having 2 to 20 carbon atoms include α, β-unsaturated carboxylic acid and its anhydride, a metal salt of α, β-unsaturated carboxylic acid, α, β. -Unsaturated carboxylic acid esters, vinyl esters, vinyl ester saponified products, cyclic olefins, vinyl aromatic compounds, polyene compounds (dienes, etc.), (meth) acrylonitrile, vinyl halides, amides, and billinidene halides, etc. Be done. These may be used alone or in combination for copolymerization.

Examples of α, β-unsaturated carboxylic acids and their anhydrides include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, monomethyl maleate, and monoethyl maleate. , Maleic acid half ester, maleic acid half amide, itaconic acid half ester, itaconic acid half amide and the like. Of these, acrylic acid, methacrylic acid, maleic acid and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable.

Examples of the metal salt of α, β-unsaturated carboxylic acid include salts of monovalent metals such as lithium, sodium and potassium, and salts of polyvalent metals such as magnesium, calcium and zinc. Specific examples include sodium and magnesium salts of (meth) acrylic acid.

Examples of the α, β-unsaturated carboxylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, and 2-hydroxyethyl acrylate. Examples thereof include dimethyl maleate and esterified products of methacrylic acid and alcohol. Of these, methyl (meth) acrylate and ethyl (meth) acrylate are preferable.

Examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versaticate and the like. Of these, vinyl acetate is preferable.

Examples of the vinyl ester saponified product include vinyl alcohol obtained by saponifying vinyl ester with a basic compound or the like.

Examples of the cyclic olefin include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1 , 2-Dihydrodicyclopentadiene, 5-chloronorbornene, cyclopentene, cyclohexene, cycloheptene, vinylcyclohexane and the like.

Examples of vinyl aromatic compounds include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene and Examples include vinylnaphthalene.

Examples of the polyene compound include linear or branched aliphatic conjugated polyene compounds, alicyclic conjugated polyene compounds, aliphatic non-conjugated polyene compounds, alicyclic non-conjugated polyene compounds and aromatic non-conjugated polyene compounds. Can be mentioned. These may have substituents such as an alkoxy group, an aryl group, an aryloxy group, an aralkyl group and an aralkyloxy group.

Examples of the aliphatic conjugated polyene compound include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, 2-. Examples thereof include methyl-1,3-decadene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-octadiene and 2,3-dimethyl-1,3-decadien.

Examples of the alicyclic conjugated polyene compound include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclohexadiene, and 2-chloro-. Examples thereof include 1,3-butadiene, 2-chloro-1,3-pentadiene and 2-chloro-1,3-cyclohexadiene.

Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,9-decadien, 3,3-dimethyl-1,4-hexadiene, and 5-ethyl. -1,4-Heptadien, 4-methyl-1,4-octadien, 5-methyl-1,4-octadien, 4-ethyl-1,4-octadien, 4-methyl-1,4-nonadien, 5-methyl Examples thereof include -1,4-decadien, 6-methyl-1,6-undecadien and 4-ethylidene-12-methyl-1,11-pentadecaziene.

Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexane, vinylcyclohexene, 5-vinyl-2-norbornene, 1,4-divinylcyclohexane, 1-isopropenyl-3-vinylcyclopentane, methyltetrahydroindene and the like. Be done.

Examples of the aromatic non-conjugated polyene compound include divinylbenzene and vinylisopropenylbenzene.

Examples of the copolymer having a structural unit derived from α-olefin having 2 to 20 carbon atoms include an ethylene-acrylic acid copolymer and an ethylene unsaturated carboxylic acid copolymer such as an ethylene-methacrylic acid copolymer. Ionomer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylate in which some or all of the carboxyl groups of the ethylene-unsaturated carboxylic acid copolymer are neutralized with the metal. Methyl copolymer, ethylene-isobutyl acrylate copolymer, ethylene-unsaturated carboxylic acid ester copolymer such as ethylene-n-butyl acrylate copolymer, ethylene-isobutyl acrylate-methacrylic acid copolymer, ethylene Examples thereof include ethylene-unsaturated carboxylic acid ester such as n-butyl acrylate-methacrylic acid copolymer, unsaturated carboxylic acid copolymer and ionomer in which some or all of the carboxyl groups thereof are neutralized with the above metal.

Examples of the modified product of the resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms include α, β-unsaturated carboxylic acids and the like using a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms. Examples thereof include modified products obtained by denaturing with.

The modification rate with α, β-unsaturated carboxylic acids and the like is preferably 0.1 to 10% by weight, based on 100% by weight of the resin having a structural unit derived from α-olefin having 2 to 20 carbon atoms before modification. It is more preferably 02 to 5% by weight, still more preferably 0.2 to 4% by weight.

Examples of α, β-unsaturated carboxylic acids include α, β-unsaturated carboxylic acids (maleic acid, itaconic acid, citraconic acid, etc.) and α, β-unsaturated carboxylic acid esters (methyl maleate, methyl itaconic acid, etc.). , Methyl citraconic acid, etc.), α, β-unsaturated carboxylic acid anhydride (maleic anhydride, itaconic anhydride, citraconic anhydride, etc.). For the modification of the resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, only one kind of α, β-unsaturated carboxylic acids may be used, or two or more kinds thereof may be used in combination. ..

For a modified resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, the resin is modified by melting the resin and then adding α, β-unsaturated carboxylic acids and the like to the melt. The resin can be produced by dissolving the resin in an organic solvent such as toluene or xylene and then adding α, β-unsaturated carboxylic acids or the like to the solution to modify the resin.

The chlorination rate of the chlorinated resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms is preferably 5 to 80% by weight with respect to 100% by weight of the copolymer before modification. It is more preferably 40 to 75% by weight, still more preferably 55 to 70% by weight.

Chlorination of a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms is a mixture obtained by dissolving or dispersing a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms in an organic solvent. This can be done by a method of blowing chlorine gas into the resin.

Examples of the resin having a structural unit derived from α-olefin having 2 to 20 carbon atoms and its modified product include Melsen (registered trademark) HH-6410M, H-6051, H-6960, H-6820 and H-6822X. (Tosoh Co., Ltd.), Eval (registered trademark) L171B, F171B, H171B, E105B and G156B (Clare Co., Ltd.), Soanol (registered trademark) D2908, DT2904, DC3212, DC3203, E3808, ET3803, A4412, AT4403, BX , 16DX, D2908H4 and A4412H4 (Nippon Synthetic Chem Industry Co., Ltd.), Soaredin (registered trademark) PG505 (Nippon Synthetic Chem Industry Co., Ltd.), NISSO (registered trademark) PB (Nippon Sotatsu Co., Ltd.), Polytail (registered trademark) ) H (Mitsubishi Chemical Co., Ltd.), Epaul (registered trademark) (Idemitsu Kosan Co., Ltd.), OREVAC (registered trademark) G1821, OE808 and OE825 (Alchema Co., Ltd.), LOTADAR MAH2210, 3200, P3 3200, 3210 , 4210, 6200, 3410, 3430 and 4720 (Alchema Co., Ltd.), BONDINE (registered trademark) LX4110, HX8210, TX8030, HX8290, HX8410 and AX8390 (Alchema Co., Ltd.), OREVAC (registered trademark) T9314, T9318 and G18211. (Alchema Co., Ltd.), Umex (registered trademark) 2000 (Sanyo Kasei Kogyo Co., Ltd.), Aurolen (registered trademark) 100S and 200T (Nippon Synthetic Chemical Industry Co., Ltd.) and the like.

The resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms and a modified product thereof may be in the form of an emulsion. Such an emulsion may be produced by emulsifying a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms and a modified product thereof, or a commercially available one may be used. Examples of emulsions of resins having structural units derived from α-olefins having 2 to 20 carbon atoms and modified products thereof include Arrowbase (registered trademark) SA-1200, SB-1200, SE-1200, and SB-1010 (Unitica). (Co., Ltd.), Aptolock (registered trademark) BW-5550 (Mitsubishi Chemical Co., Ltd.), Aurolen (registered trademark) AE-202, AE-301 (Nippon Paper Industries, Ltd.), Aquatex (registered trademark) EC -1200, EC-1700, AC-3100, MC-4400, HA-1100, 909 (Chuo Rika Kogyo Co., Ltd.) and the like can be mentioned.

Examples of the resin having a structural unit derived from a chlorinated α-olefin having 2 to 20 carbon atoms include Eraslen (registered trademark) 401A and 303B (Showa Denko Co., Ltd.), Hardlen (registered trademark) CY-9122P, and the like. CY-9124P, HM-21P, M-28P, F-2P, F-6P, F-69, 13-LP, 13-LLP, 14-LWP, 14-WL-P, 15-LP, 15-LLP, 16-LP, DX-526P, DX-530P and BS-40 (Toyobo Co., Ltd.), and Supercron (registered trademark) 803L, 803MW, 814HS, 390S, HE-305, HE-505, HE-510, Examples thereof include HE-515, HE-910, HE-915, HE-1070, HE-1200, HP-205, HP-215 and HP-620 (Nippon Paper Chemicals Co., Ltd.).

The resin having a structural unit derived from a chlorinated α-olefin having 2 to 20 carbon atoms may be in the form of an emulsion. Such an emulsion may be produced by emulsifying a resin having a structural unit derived from a chlorinated α-olefin having 2 to 20 carbon atoms, or a commercially available one may be used. Emulsions of resins having structural units derived from chlorinated α-olefins having 2 to 20 carbon atoms include, for example, Haadren® EW-5303, EH-801, EW-5504, EZ-1000 and EZ-. 2000 (Toyobo Co., Ltd.), Supercron (registered trademark) E-604, E-480T and E-415 (Nippon Paper Chemicals Co., Ltd.) and the like can be mentioned.

The polyurethane may be foamed polyurethane or non-foamed polyurethane, but is preferably non-foamed polyurethane. Among the non-foamed polyurethanes, water-soluble or water-dispersible polyurethanes are preferable. Commercially available polyurethane can be used. Examples of commercially available polyurethane include Nippon Polyurethane Industry Co., Ltd. 3110, 3116, 3016, 3113, 3124, 3126, 3230 (Nippon Polyurethane Industry Co., Ltd.). Commercially available water-soluble or water-dispersible polyurethanes include, for example, Dispacol® U-42, U-53, U-54, U-56, KA-8484, KA-8584, KA-8755, KA-. 8756 and KA-8766 (Sumitomo Cobestro Urethane Co., Ltd.), Hydran (registered trademark) HW-111, HW-311, HW-333, HW-350, HW-337, HW-374, AP-20, AP- 60LM and AP-80 (DIC Co., Ltd.), Upren® UXA-306, UXA-307, Permarin UA-150, Permarin UA-200, Permarin UA-300, Permarin UA-310 and Eucoat UWS-145 ( Sanyo Kasei Kogyo Co., Ltd., Superflex (registered trademark) 107M, 110, 126, 130, 150, 160, 210, 300, 361, 370, 410, 420, 460, 500M, 700, 750, 820 and 860 ( Dai-ichi Kogyo Seiyaku Co., Ltd., and Adeka Bontita (registered trademark) HUX-401, HUX-420A, HUX-380, HUX-561, HUX-210, HUX-822, HUX-895 and HUX-830 ((() ADEKA Corporation) and the like.

Polyvinyl chloride can be obtained by suspension polymerization or bulk polymerization of vinyl chloride. Examples of the polyvinyl chloride include hard polyvinyl chloride, semi-hard polyvinyl chloride, soft polyvinyl chloride and the like. A soft polyvinyl chloride is preferable. Examples of polyvinyl chloride include Kanevinyl S-400, PSH-180, PSL-180 Kaneka Corporation) and the like. Examples of the polyvinyl chloride emulsion include Vinibran 701, 700, 711 (Nissin Chemical Industry Co., Ltd.) and the like.

Chlorinated polyvinyl chloride is obtained by chlorinating polyvinyl chloride by a chlorination method such as a gas phase or a liquid phase. Examples of polyvinyl chloride include homopolymers of vinyl chloride and copolymers of vinyl chloride and other monomers. Examples of other monomers include ethylene, propylene, alkyl vinyl ether, vinylidene chloride, vinyl acetate, acrylic acid ester, maleic acid ester and the like. Examples of the chlorinated polyvinyl chloride include Sekisui PVC-HA (Sekisui Chemical Co., Ltd.).

Examples of polyvinylidene chloride include Saran X05253-16 (manufactured by Dow Chemical Co., Ltd.) and a resin for Saran Wrap (registered trademark) (manufactured by Asahi Kasei Corporation). Examples of the polyvinylidene chloride emulsion include Diofan 193D, A736, A036, A050, A063, B204, A115 (manufactured by Solvay) and the like.

Examples of the vinyl chloride-vinylidene chloride copolymer include IXAN SGA-1 (manufactured by Solvay) and the like.

Examples of the vinylidene chloride- (meth) acrylic acid ester copolymer include IXAN PVS-109, 801 and 815, Diofan A586, A602 and A610 (manufactured by Solvay).

The chloroprene-based resin is a homopolymer of chloroprene or a copolymer of chloroprene and another monomer. Examples of other monomers include isoprene, butadiene, dichlorobutadiene, styrene, acrylonitrile, acrylic acid esters, methacrylic acid esters, acrylic acid, methacrylic acid, itaconic acid and the like.

The acid-modified chloroprene-based resin can be obtained by graft-copolymerizing the above-mentioned chloroprene-based resin with at least one selected from α, β-unsaturated carboxylic acid and its anhydride. Examples of the α, β-unsaturated carboxylic acid and its acid anhydride include those exemplified as a modified product of a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms.

Examples of the chloroprene-based resin and the acid-modified chloroprene-based resin include Skyprene (registered trademark) G-42, G-40S, G-55, G-40, S-1, G-40T, B-30S, and Y-. 31 (Tosoh Co., Ltd.), Showprene (registered trademark) W, AF, WHV, WXJ, WB (Showa Denko KK), and Denka chloroprene (registered trademark) A-30, A-70, A-90, A -91, M-130L, DCR-11 (Denka Co., Ltd.) and the like can be mentioned. Emulsions of chloroprene-based resins and acid-modified chloroprene-based resins include, for example, Skyperene® GFL-820, GFL-890, GFL-280, LA-502, LA-660, SL-360, SL-390 and SL-590 (Tosoh Co., Ltd.), Shoprene (registered trademark) 115, 571, 572, 650, 671A, 750, SD78 and SD77S (Showa Denko KK), and Denka Chloroprene (registered trademark) LA-50 and LC. -501 (Denka Co., Ltd.) and the like can be mentioned.

Examples of the brominated butyl rubber include JSR BROMOBUTYL 2255 and 2244 (manufactured by JSR Corporation) and exonbromobutyl 2255 (manufactured by ExxonMobil Chemical Co., Ltd.).

Examples of the modified rubber include a chlorinated or brominated modified copolymer of a copolymer of isomonoolefin and paramethylstyrene, and examples of a commercially available product include Expro50 (manufactured by Exxon).

Examples of the styrene-based block copolymer include a block copolymer composed of a diene block and a styrene block. Specifically, both styrene-butadiene block copolymer (SB), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-butadiene-butylene-styrene. Examples thereof include a polymer (SBBS) or a hydrogenated product of these block copolymers, a styrene / isobutylene-styrene triblock copolymer (SIBS), and a styrene-isobutyrene block copolymer (SIB). Such a hydrogenated additive is a block copolymer in which all of the styrene block and the diene block are hydrogenated, or a block copolymer in which only the diene block is hydrogenated, or a part of the styrene block and the diene block. It may be a partially hydrogenated product such as a hydrogenated block copolymer.

In order to further improve the stability of the dispersion liquid, the dispersion liquid of the present invention may contain a water-soluble resin such as polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose and hydroxyethyl cellulose as other resins.

The dispersion liquid of the present invention may contain a tackifier resin as another resin. Examples of such resins include rosins, terpene resins, petroleum-based resins obtained by polymerizing petroleum fractions having 5 carbon atoms and hydrogenated resins thereof, petroleum-based resins obtained by polymerizing petroleum distillates having 9 carbon atoms, and the like. Examples thereof include hydrogenated resins, other petroleum-based resins, kumaron resins, and inden resins. Specifically, for example, rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumalized rosin and their glycerin esters, pentaerythritol esters, methyl esters, triethylene glycol esters, phenolic modified products and Rosin such as the esterified product; terpene polymer, terpene phenol, β-pinene polymer, aromatic-modified terpene polymer, α-pinene polymer, terpene resin such as terpene hydrogenated resin; petroleum having 5 carbon atoms Petroleum-based resins obtained by polymerizing distillates, petroleum-based resins obtained by polymerizing petroleum distillates having 9 carbon atoms and hydrogenated resins thereof; petroleum-based resins such as maleic acid-modified products and fumaric acid-modified products, chlorinated paraffins, etc. Be done.

Examples of terpene resins include YS resin PX, PXN, YS polystar, Mighty Ace, YS resin TO, TR and Clearon P, M, K (Yasuhara Chemical Co., Ltd.), Tamanol 803L, 901 (Arakawa Chemical Industry Co., Ltd.). ), Teltac 80 (Nippon Terpen Chemical Co., Ltd.) and the like. Examples of the terpene resin emulsion include Tamanol E-200NT and E100 (Arakawa Chemical Industry Co., Ltd.).

Examples of the chlorinated paraffin include Empara (registered trademark) 70, 50, AR-500 (Ajinomoto Fine-Techno Co., Ltd.), Toyoparax (registered trademark) 250, 265, 270, 150, A50 (Tosoh Co., Ltd.) and the like. Can be mentioned.

When the dispersion liquid of the present invention contains another resin or rubber, the amount thereof is preferably 0.01 part by weight or more, preferably 0.01 part by weight or more, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. Is 100 parts by weight or less, more preferably 50 parts by weight or less, still more preferably 30 parts by weight or less, and even more preferably 20 parts by weight or less.

<Thickener>
Thickeners can be used to adjust the viscosity of the dispersion. Examples of the thickener include Adecanol (registered trademark) UH-140S, UH-420, UH-438, UH-450VF, UH-462, UH-472, UH-526, UH-530, UH-540, UH. -541VF, UH-550, UH-752 and H-756VF (ADEKA Corporation), and SN thickeners 920, 922, 924, 926, 929-S, A-801, A-806, A-812, A- 813, A-818, 621N, 636, 601 and 603, 612, 613, 615, 618, 621N, 630, 634, 636 and 4050 (San Nopco Ltd.) and the like can be mentioned.

<Manufacturing method of dispersion liquid>
The dispersion liquid of the present invention can be produced by a method as described in Examples described later. Hereinafter, the method for producing the dispersion liquid of the present invention will be described in detail.

A pre-dispersion solution is prepared by mixing and stirring water, a chlorinated rubber, a compound having a polymerizable group, and if necessary, other components (particularly, a surfactant, etc.). The method of pre-dispersion is not particularly limited, and can be carried out using known means and devices. Known devices include, for example, a homomixer. When a homomixer is used, the stirring number is preferably 5,000 to 20,000 rpm, more preferably 8,000 to 20,000 rpm, and the stirring time is preferably 2 to 10 minutes, more preferably 3 It is 10 minutes. It is preferable to start stirring with the mixture at room temperature.

Next, a high-pressure homogenizer is used to homogenize the obtained pre-dispersion liquid. The pressure of the high pressure homogenizer is preferably 40 to 1,000 bar, more preferably 40 to 800 bar. If the pressure is less than 40 bar, the fine dispersion of the dispersoid becomes insufficient, and conversely, if the pressure exceeds 1,000 bar, the fine dispersion of the dispersoid is not improved. The number of homogenization treatments with a high-pressure homogenizer is preferably 2 to 10 times, more preferably 3 to 8 times. If the number of times of the treatment is less than 2, the fine dispersion of the dispersoid is insufficient, and conversely, even if the number of times of the treatment exceeds 10, the fine dispersion of the dispersoid is not improved. It is preferable to cool the pre-dispersion liquid obtained by the homomixer to room temperature and then start the homogenization treatment with a high-pressure homogenizer.

Examples of the high-pressure homogenizer include "LAB1000", "LAB2000", "15MR", "G-MODEL", and "R-MODEL" manufactured by SMT Co., Ltd.

Water may be further added to the dispersion liquid of the present invention produced as described above and stirred to produce a diluted dispersion liquid. Further, another component (for example, a leveling agent) may be further added to the dispersion liquid of the present invention produced as described above and stirred to produce a dispersion liquid containing the other component.

<Use of dispersion>
As described above, the dispersion liquid of the present invention is useful as a water-based adhesive, a primer, or a raw material thereof. The present invention also provides a coating film formed from the dispersion liquid and a cured product of the coating film. The present invention also provides a laminate in which the first base material, the cured product, the adhesive layer, and the second base material are laminated in this order. The first base material is preferably made of an olefin polymer or an ethylene-vinyl acetate copolymer. In the laminate of the present invention, the cured product may be further present between the adhesive layer and the second base material.

As the material of the adherend to which the dispersion liquid of the present invention is applied, or the adherend (including the first base material and the second base material) on which the coating film and the cured product of the present invention are laminated, for example, wood. , Plywood, medium density fiber board (MDF), particle board, fiber board and other wood-based materials; cotton cloth, cotton-containing fiber, linen cloth, rayon and other cellulose-based materials; (1) ethylene homopolymers and copolymers, Olefin-based polymers such as propylene homopolymers and copolymers, (2) styrene homopolymers and copolymers, (3) polycarbonates, (4) acrylonitrile-butadiene-styrene copolymers (ABS resin), (5) Poly (meth) acrylic resin, (6) polyester, (7) polyether, (8) polyvinyl chloride, (9) foamed or non-foamed polyurethane, (10) foamed or non-foamed ethylene-vinyl acetate Plastic materials such as copolymer (EVA), (11) polyamide 6, polyamide iron 66 and other foamed or unfoamed polyamide resins ;; rubber; polyamino acids; natural leather; synthetic leather; ceramic materials such as glass and ceramics. ; And metal materials such as iron, stainless steel, copper, and aluminum. The adherend may be made of one kind of material or may be made of two or more kinds of materials. Further, the adherend may be a kneaded molded product of the plastic material and a filler such as talc, silica, activated carbon, and carbon fiber.

Among the adherends, the dispersion liquid of the present invention includes adhesion between a cellulose-based material and a plastic material, polyvinyl chloride, ethylene-vinyl acetate copolymer, cotton-containing fiber, polyamide-based resin, olefin-based polymer, and polyurethane. , Rubber or crosslinked rubber, and synthetic leather can be suitably used for adhesion. Examples of the shape of these adherends include a film, a sheet, a block shape, and the like, and an adherend in the shape of a film or a sheet is preferable.

Examples of the olefin polymer include resins and modified products having a structural unit derived from α-olefin having 2 to 20 carbon atoms described in <Other resin or rubber>. Further, as the plastic material, for example, the one described in <Other resin or rubber> can be mentioned.

The cotton-containing fiber may be a 100% cotton fiber, or may be a blended fiber of cotton and other natural fibers and / or chemical fibers. Other natural fibers include, for example, wool, silk and hemp. Examples of the chemical fiber include synthetic fiber (for example, polyester fiber, polyamide fiber), semi-synthetic fiber (for example, cellulose fiber such as acetate, protein fiber such as Promix), and regenerated fiber (for example, rayon, etc.). Cellular fibers such as cupra and polynosic) and inorganic fibers (eg, carbon fibers, glass fibers) and the like can be mentioned. Examples of the shape of the cotton-containing fiber include woven fabric, knitted fabric, non-woven fabric, knitted fabric, felt, film or block shape.

Examples of the polyamide-based resin include polyamide 6, polyamide 6, 6, polyamide 4, 6, polyamide 11 and polyamide 12. The shape of the polyamide resin may be any of a film, a block, a fiber, a foam, and the like.

Examples of the rubber or crosslinked rubber include thermoplastic rubber; natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, acronitrile-butadiene rubber, chloroprene rubber and other diene rubbers; butyl rubber, ethylene-propylene rubber. , Ethylene-propylene-diene rubber, silicone rubber, fluororubber and other non-diene rubbers; and crosslinked products thereof. The rubber or the crosslinked rubber may be used alone or in combination of two or more. If necessary, a reinforcing agent such as clay, carbon black or silica, a silane coupling agent, an antiaging agent, a softening agent, zinc oxide, stearic acid, a vulcanization accelerator, a vulcanizing agent, sulfur, etc. may be used in combination. good.

Synthetic leather includes both synthetic leather and artificial leather in a narrow sense. That is, synthetic leather obtained by applying a synthetic resin to a natural or synthetic fabric or the like may be used, or artificial leather obtained by impregnating a fabric such as microfiber (usually a non-woven fabric) with a synthetic resin may be used. Artificial leather obtained by impregnating a cloth (usually a non-woven fabric) with a synthetic resin and further applying the synthetic resin may be used. Examples of these synthetic resins include polyurethane-based resins, polyamide-based resins, and polyamino acid-based resins, and polyurethane-based resins are preferable.

The dispersion liquid of the present invention can be effectively used for adhering adherends such as films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing and shoes. In particular, the dispersion liquid of the present invention is a constituent material (cover) such as a cover, an insole, and an outer sole in footwear such as men's shoes such as sports shoes, town shoes, and business shoes, women's shoes, and industrial work shoes. It is suitable as an adhesive for adhering footwear), a primer, or a raw material thereof. The surface of these adherends may be smooth or may have irregularities. Further, in order to enhance the adhesiveness, the adherend may be surface-treated. Examples of the surface treatment include primer treatment, blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, vapor treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, and formation of an anchor layer.

Next, the method for producing the laminate of the present invention described above will be described.
First, the dispersion liquid is applied to the surface of the first base material, optionally the second base material. The coating may be carried out by a known method. Known methods include, for example, gravure roll coating, reverse roll coating, bar coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating and spatula coating.

The dispersion liquid may be applied and dried only once, or may be applied twice or more. The method of application and drying may be a combination of the same method or a combination of different methods.

After applying the dispersion liquid to the first base material, the coating film may be dried or heat-treated, and then electromagnetic waves may be irradiated. The heating temperature is, for example, about 30 to 150 ° C., preferably about 40 to 80 ° C. The heating time is, for example, about 1 second to 1 hour, preferably about 5 seconds to 30 minutes, and more preferably about 5 seconds to 10 minutes. Before and after the coating film is dried or heat-treated, the coating film may be left to stand (natural drying). It is preferable to irradiate the coating film formed from the dispersion liquid with electromagnetic rays (particularly ultraviolet rays) to form a cured product of the coating film.

When irradiating a coating film with an electromagnetic wave, examples of the light source for that purpose include a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a low-pressure mercury lamp, a xenon lamp, an arc lamp, and a laser. Among these, metal halide lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and low-pressure mercury lamps are preferable. The peak illuminance of electromagnetic beam irradiation is preferably 5 to 2000 mW / cm ² , and more preferably 10 to 2000 mW / cm ² . The cumulative irradiation amount is preferably 20 to 3000 mJ / cm ² , and more preferably 100 to 2500 mJ / cm ² .

The first substrate may be surface treated before the dispersion is applied to the adherend. Examples of the surface treatment include primer treatment, blast treatment, chemical treatment, degreasing treatment, flame treatment, oxidation treatment, vapor treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, and formation of an anchor layer. ..

In the dried coating film, it is preferable that 95% by weight or more of the water contained in the dispersion liquid is removed. By reducing the water content in the coating film in this way, the adhesiveness of the coating film and the cured product obtained from the coating film can be ensured.

The thickness of the coating film after drying is preferably about 0.01 to 300 μm, more preferably about 0.01 to 200 μm, and even more preferably about 0.01 to 50 μm.

Next, a liquid adhesive is applied to at least one of the first base material and the second base material to which the dispersion liquid is applied, and the liquid adhesive is dried or heat-treated. These coating and drying or heat treatment need to be performed only once on at least one of the first base material and the second base material, but even if both are coated with the adhesive and heat-dried one or more times. good. Conditions such as the method of applying the adhesive, the thickness of the coating film after drying, the method of drying or heat treatment, the temperature and time, and the like can be appropriately changed. The same conditions as those for applying the dispersion liquid described above may be selected, or different conditions may be selected.

When the adhesive is applied to both the first base material and the second base material, the same adhesive may be applied to the first base material and the second base material, or different adhesives may be applied. You may. In order to adhere the first base material and the second base material well, it is preferable to use the same adhesive. The adhesive may be the dispersion used above or a commercially available adhesive.

The thickness of the adhesive layer can be appropriately adjusted depending on the composition of the adhesive used, the material and form of the base material, and the like. The thickness of the adhesive layer is preferably about 0.01 to 300 μm, more preferably about 0.01 to 200 μm.

The above-mentioned surface treatment may be applied to the adherend before applying the liquid adhesive to the adherend (the first base material and / or the second base material).

The method of bonding the first base material and the second base material to which the dispersion liquid and / or the adhesive is applied is not particularly limited, and these may be bonded by mechanical operation or manually. Heat, pressure, or both may be applied during bonding. When heating, it is necessary to heat in a temperature range in which the first base material, the second base material, and the adhesive layer do not deteriorate, and the heating temperature is preferably about 120 ° C. or lower, more preferably. It is about 100 ° C. or lower. Heating can be performed using a normal hot air circulation type oven, an infrared heater, a microwave oven, or the like. When pressurized, the pressure is, for example ^{, about 100 g / cm 2} or more, and less than the pressure at which the shapes of the first base material and the second base material are deformed. When heating and / or pressurizing, the time is, for example, about 1 second to 10 days.

Examples of the first base material and the second base material include those similar to those of the adherend described above. The first base material is preferably a base material composed of an olefin polymer or an ethylene-vinyl acetate copolymer. The second base material is preferably a base material selected from the group consisting of polyvinyl chloride, synthetic leather, rubber, cotton-containing fibers and polyolefin-based polymers.

The adhesive layer can be obtained by applying, for example, a liquid polyurethane adhesive, a liquid rubber-based adhesive, a liquid acrylic adhesive, a liquid epoxy adhesive, or the like to remove water, an organic solvent, or the like.

Examples of the liquid polyurethane adhesive include the above-mentioned water-soluble or water-dispersible polyurethane.
Examples of the liquid rubber-based adhesive include natural rubber, chloroprene rubber, styrene-butadiene copolymer rubber (SBR), isobutylene rubber, butyl rubber, styrene-isoprene-styrene block copolymer rubber (SIS), and styrene-butadiene-styrene. Examples thereof include a liquid adhesive containing a rubber component such as a block copolymer rubber (SBS), a butadiene-acrylonitrile copolymer rubber (NBR), and a butadiene rubber (BR). Only one type of rubber component may be used, or two or more types may be used in combination. Further, in addition to these rubber components, an adhesive-imparting resin such as a rosin resin, a terpene resin, or a petroleum resin may be added to the rubber-based adhesive.

The liquid acrylic adhesive includes, for example, a copolymer of an acrylic acid ester and / or a methacrylate ester as an adhesive component, a functional group-containing monomer, and a monomer for the purpose of improving cohesive force. Adhesives can be mentioned. An isocyanate cross-linking agent, a chelate cross-linking agent, an epoxy cross-linking agent, or the like may be added to the liquid acrylic adhesive.

Examples of the acrylate ester include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, and 2-ethylhexyl acrylate. N-octyl acrylate, n-lauryl acrylate and the like can be preferably exemplified. Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate and 2-ethylhexyl methacrylate. N-octyl methacrylate, n-lauryl methacrylate and the like can be preferably exemplified.

Functional group-containing monomers copolymerizable with acrylic acid ester and / or methacrylic acid ester include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid; acrylic. Hydroxyalkyl esters of acrylic acid or methacrylic acid such as hydroxyethyl acid acid, hydroxybropil acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate; acrylamide, methacrylic acid, diacetone (meth) acrylamide, N-methylolacrylamide, N-methylol. N-substituted or unsubstituted acrylamides such as methacrylic acid, N-butoxymethylacrylamide and N-butoxymethacrylate; acrylic acids such as glycidyl methacrylate and glycidyl methacrylate; glycidyl esters of methacrylic acid; acrylonitrile and the like can be preferably exemplified. can.

Examples of the liquid epoxy adhesive include liquid adhesives containing an epoxy resin having one or more epoxy groups per molecule on average. Examples of the epoxy resin include an epoxy resin obtained from bisphenol A and epichlorohydrin, polyglycidyl ether obtained from bisphenol F and epichlorohydrin, or hydrided bisphenol A and epichlorohydrin. In addition, oxazolidone-modified epoxy resin, novolak type epoxy resin, polyfunctional phenol type epoxy resin, various halogenated epoxy resins, glycidyl ester type epoxy resin, polyglycol type epoxy resin, cyclic aliphatic epoxy resin and the like can also be used. .. These epoxy resins may be used alone or in combination of two or more.

Liquid polyurethane adhesives, liquid rubber adhesives, liquid acrylic adhesives and liquid epoxy adhesives may be adhesives in the form of solutions, dispersions or emulsions and are used in the molten state for hot melt adhesives. It may be an agent.

The adhesive constituting the adhesive layer may contain other components (for example, resin) different from the above-mentioned components. Examples of the resin that the adhesive may contain include olefin resin, polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), and polytetrafluoroethylene (PTFE). Examples thereof include acrylonitrile-butadiene-styrene copolymer (ABS resin), AS resin, and modified products of the resin. These may be used alone or in combination of two or more.

Further, examples of the resin that the adhesive may contain include a tackifier resin. Examples of the tackifier resin include rosins, terpene resins, petroleum-based resins obtained by polymerizing petroleum fractions having 5 carbon atoms and hydrogenated resins thereof, petroleum-based resins obtained by polymerizing petroleum distillates having 9 carbon atoms and hydrogens thereof. Examples thereof include additive resins, other petroleum-based resins, kumaron resins, inden resins, and polyurethane resins.

Other components that may be contained in the adhesive include, for example, a surfactant, a photopolymerization initiator, a light stabilizer, an ultraviolet curable oligomer, a fluorescent whitening agent, a leveling agent, a basic compound, and an organic substance. Solvents, cross-linking agents, photosensitizers, phenol-based stabilizers, phosphite-based stabilizers, amine-based stabilizers, amide-based stabilizers, anti-aging agents, weather-resistant stabilizers, anti-settling agents, antioxidants, heat stabilizers , Shaking agents, thickeners, antifoaming agents, viscosity modifiers, weathering agents, pigment dispersants, antistatic agents, lubricants, nucleating agents, flame retardants, oils, dyes, curing agents; titanium oxide (rutyl type) and Transition metal compounds such as zinc oxide; pigments such as carbon black; glass fibers, carbon fibers, potassium titanate fibers, wolastonite, calcium carbonate, calcium sulfate, talc, glass flakes, barium sulfate, clay, kaolin, fine powder silica , Mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, and inorganic or organic fillers such as Celite; and the like.

Hereinafter, the present invention will be described in detail with reference to Examples, etc., but the present invention is not limited by the following Examples, etc. Of course, it is also possible to carry out the above, and all of them are included in the technical scope of the present invention.
In addition, "parts", "%" and "ppm" described below mean "parts by weight", "% by weight" and "ppm by weight", respectively, unless otherwise specified.

The chlorine atom content of the chlorinated rubber is a value measured by a flask combustion-ion chromatograph method.
The median diameter (volume basis) of the dispersoids shown in the table below is a value measured by a laser diffraction particle size measuring device LA-950V2 manufactured by HORIBA, Ltd.

A "rotation / revolution mixer Awatori Rentaro ARE-310" manufactured by Shinky Co., Ltd. was used as a rotation / revolution stirrer for preparing a measurement sample of backscattered light intensity.
As a device for measuring the backscattered light intensity of the measurement sample, "Tabiscan TOWER" manufactured by Formulation Co., Ltd. was used.
Using the rotation / revolution stirrer, a measurement sample is prepared from the dispersions produced in Examples and Comparative Examples described later, measurement is started within 10 minutes from the sample preparation, and the upper part of the measurement sample in the sample cell. The amount of change in the backward scattered light intensity (%) measured 24 hours after the start of the measurement with respect to the backward scattered light intensity (%) measured 30 minutes after the start of the measurement in each of the middle part and the bottom part. The maximum value α in absolute value was calculated and evaluated according to the following criteria. The results are shown in the table below.
◯: All the requirements of the above formulas (I) to (III) are satisfied.
X: Does not satisfy any or all of the requirements of the above formulas (I) to (III).

The chlorinated rubber, the compound having a polymerizable group, the photopolymerization initiator, the surfactant, and the leveling agent used in Examples and Comparative Examples are as follows.
Chlorinated rubber 1: Pergut S20 (Chlorine Co., Ltd., chlorine atom content: 64.5% or more, melting point: 250 ° C., weight average molecular weight (Mw) in terms of polystyrene: 75,000, carboxy group and carboxylic acid anhydride structure Chlorinated rubber that does not exist)
Compound with polymerizable group 1: Dodecyl methacrylate (containing 970 ppm 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound with polymerizable group 2: 1,6-hexanediol dimethacrylate (containing 60 ppm 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound with polymerizable group 3: 2-Phenoxyethylene glycol methacrylate (containing 100 ppm 4-methoxyphenol, Shin-Nakamura Chemical Co., Ltd.)
Compound with polymerizable group 4: Tricyclodecanedimethanol diacrylate (containing 800 ppm 4-methoxyphenol, Shin-Nakamura Chemical Co., Ltd.)
Compound 5 with polymerizable group: Tricyclodecanedimethanol dimethacrylate (containing 300 ppm 4-methoxyphenol, Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization Initiator 1: 2-Hydroxy-2-methylpropiophenone (Tokyo Chemical Industry Co., Ltd.)
Surfactant 1: Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.)
Surfactant 2: Emargen 109P (Kao Corporation)
Basic compound 1: 2- (dimethylamino) ethanol (Tokyo Chemical Industry Co., Ltd.)
Optical brightener: Nikkafluor OB (Nippon Kagaku Kogyosho Co., Ltd.)
Leveling agent 1: BYK-349 (Big Chemie Japan)

<Production Example 1: Production of dispersion liquid E1>
In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux cooling tube, chlorinated rubber 1 (15 parts), compound 1 having a polymerizable group (30 parts), and compound 2 having a polymerizable group (45 parts). ), Compound 3 (10 parts) having a polymerizable group, and photopolymerization initiator 1 (1 part) are charged and stirred at 60 ° C. to prepare a solution (hereinafter referred to as “solution 1”). The solution 1 was cooled to room temperature.

Surfactant 1 (5 parts) was placed in ion-exchanged water (300 parts) and stirred at 60 ° C. to prepare an aqueous solution of surfactant 1 (hereinafter referred to as "solution 2").

At room temperature, solution 2 was added to solution 1 and stirred to prepare a mixture. Then, at room temperature, the obtained mixture was stirred at 16,000 rpm for 5 minutes using TK Robomix (manufactured by PRIMIX Corporation) equipped with a homomixer MARKII to obtain a milky white emulsion. After cooling the dispersion to room temperature, homogenization treatment was performed 4 times at 800 bar using a high-pressure homogenizer "LAB1000" manufactured by SMT Co., Ltd., and the obtained emulsion was filtered through a 200 mesh nylon net. , A dispersion liquid E1 which is an emulsion was obtained. The non-volatile content concentration of the obtained dispersion liquid E1 was 25%.

<Production Examples 2-7: Production of Dispersion Liquids E2 to E7>
Dispersion as an emulsion in the same manner as in Production Example 1 except that the amounts of chlorinated rubber, the compound having a polymerizable group, the photopolymerization initiator, the surfactant, and the ion-exchanged water shown in Table 1 were used. Liquids E2 to E7 were obtained. In Production Example 6, the dispersion liquid E6 was produced using a solution to which the amount of the fluorescent whitening agent shown in Table 1 was added. In Production Example 7, the dispersion liquid E7 was produced without using a photopolymerization initiator.

<Production Examples 8 to 12: Production of Dispersion Liquids E8 to E12>
Production Example 1 except for the amounts of chlorinated rubber, compound having a polymerizable group, photopolymerization initiator, surfactant, and ion-exchanged water shown in Table 1, stirring time with a homomixer, and number of homogenization treatments with a high-pressure homogenizer. In the same manner as above, dispersion liquids E8 to E12, which are emulsions, were obtained. In Production Example 12, the dispersion liquid E12 was produced using a solution to which the amount of the basic compound shown in Table 1 was added.

Types of dispersions produced in Production Examples 1 to 12; Types and amounts of components used (parts); Total amount (%) of chlorinated rubber and compounds having a polymerizable group in the obtained dispersions, chlorination Amount of rubber (%), amount of compound having polymerizable group and no cyclic structure (%), and amount of compound having polymerizable group and cyclic structure (%) (all chlorinated rubber, It is a value with respect to the total of the compound having a polymerizable group and water); stirring time with a homomixer (minutes); number of treatments with a high-pressure homogenizer; and evaluation results of the median diameter (μm) of the dispersoid are shown in Table 1 below. ..

<Examples 1 to 7 and Comparative Examples 1 to 5: Production of water-based adhesives F1 to F12>
The amounts shown in Table 2 are mixed with any of the dispersions E1 to E12, the leveling agent 1 (BYK®-349, Big Chemie Japan), and ion-exchanged water, stirred with a three-one motor, and the emulsion. Water-based adhesives F1 to F12, which are turbid liquids, were obtained.
In Examples 1 to 7 and Comparative Examples 1 to 5 and subsequent examples, a dispersion liquid further containing a leveling agent and suitable as an adhesive is described as "water-based adhesive".

Types of water-based adhesives produced in Examples 1-7 and Comparative Examples 1-5; Type and amount of dispersion used (parts); Leveling agent 1 used and amount of ion-exchanged water (parts); obtained The total amount (%) of the chlorinated rubber and the compound having a polymerizable group in the water-based adhesive, the amount of the chlorinated rubber (%), and the amount of the compound having a polymerizable group and not having a cyclic structure (%). ), And the amount (%) of the compound having a polymerizable group and a cyclic structure (all values relative to the total of chlorinated rubber, the compound having a polymerizable group and water); the median diameter (μm) of the dispersoid; The evaluation results of the amount of change in the backward scattered light intensity are shown in Table 2 below.

<Manufacturing Example 13: Production of Liquid Adhesive 1>
Polyurethane emulsion (Dispacol® U-54, Sumika Cobestro Urethane Co., Ltd.), Isocyanate (Death Module® N3300, Sumika Cobestro Urethane Co., Ltd.), and Leveling Agent 1 The polyurethane emulsion: isocyanate: leveling agent 1 was mixed so that the non-volatile content ratio was 100 parts: 5 parts: 1 part to obtain an adhesive 1 which is an emulsion.

<Example 8: Production of laminate 1>
The water-based adhesive F1 was left at 50 ° C. for 7 days in a blower constant temperature incubator, and then applied to the foam of ethylene-vinyl acetate copolymer (EVA), which is the first base material, using a brush. Weight per unit area of the coating film after drying: Approximately 3 g / m ² ), dried at 70 ° C. for 5 minutes, and exposed to ultraviolet rays with a conveyor-type UV irradiation device (Eigrandage ECS-4011GX, manufactured by Eye Graphics Co., Ltd.). Irradiation gave a laminate of EVA and cured product (lamp: high-pressure mercury lamp, lamp output: 3 kW, lamp height: 110 mm, conveyor speed: 276 m / min, peak illuminance: 250 mW / cm ² , integrated irradiation. Amount: 700 mJ / cm ² (UVICURE PLUS II, UV-A measurement value, FusionUV Systems Japan KK).

Subsequently, the adhesive 1 was applied to the second base material, cotton canvas (Johoku Kogyo Co., Ltd.), using a brush (weight per unit area of the coating film after drying: about 50 g / m ² ). It was oven-dried at 70 ° C. for 5 minutes to obtain a laminate of cotton canvas and an adhesive layer.

Adhesive 1 is applied to the surface of the laminate of EVA and the cured product obtained as described above on the cured product side and the surface of the laminate of the cotton canvas and the adhesive layer on the adhesive layer side, respectively. It was applied using an adhesive (weight per unit area of the coating film after drying: about 50 g / m ² ), and dried in an oven at 70 ° C. for 5 minutes. After that, the adhesive layers of the obtained laminate of EVA, the cured product, and the adhesive layer and the laminate of cotton canvas and the adhesive layer are bonded to each other, crimped by hand, and further pressed at 3 MPa at 20. The pressure was applied for seconds to obtain a laminated body 1 which is a laminated body of EVA (first base material), a cured product, an adhesive layer, and cotton canvas (second base material).

<Examples 9 to 14 and Comparative Examples 6 to 10: Production of laminates 2 to 12>
EVA (first base material), cured product, adhesive layer, and cotton canvas (second base material) are the same as in Example 8 except that the water-based adhesive F1 is changed to any of the water-based adhesives F2 to F12. The laminated bodies 2 to 12 which are the laminated bodies with the base material of the above were obtained.

In Examples 8 to 14 and Comparative Examples 6 to 10, in order to evaluate the adhesiveness of the water-based adhesives F1 to F12 obtained in Examples 1 to 7 and Comparative Examples 1 to 5 after long-term storage, As described above, laminates 1 to 12 were produced using the water-based adhesives F1 to F12 stored at 50 ° C. for 7 days. The adhesiveness of the water-based adhesive stored at 50 ° C. for 7 days can be considered to correspond to the adhesiveness of the water-based adhesive stored at room temperature for several months.

<Test Example 1: Evaluation of initial adhesiveness>
The laminate is left at room temperature for 5 minutes after its production, and then the laminate is used under the conditions of a peeling speed of 50 mm / min, a peeling angle of 180 degrees, and room temperature using a tensile tester (manufactured by Shimadzu Corporation, Autograph). The peel strength between EVA (first base material) and cotton canvas (second base material) was measured, and the initial adhesiveness was evaluated according to the following criteria. The results are shown in Table 3.
◯: Peeling strength is 45 N / inch or more ×: Peeling strength is less than 45 N / inch

<Test Example 2: Evaluation of final adhesiveness>
After the laminate is left at room temperature for 24 hours after its production, the laminate is used under the conditions of a peeling speed of 50 mm / min, a peeling angle of 180 degrees, and room temperature using a tensile tester (manufactured by Shimadzu Corporation, Autograph). The peel strength between EVA (first base material) and cotton canvas (second base material) was measured, and the final adhesiveness was evaluated according to the following criteria. The results are shown in Table 3.
◯: Peeling strength is 90 N / inch or more or material destruction ×: Peeling strength is less than 90 N / inch

Types of laminates produced in Examples 8 to 14 and Comparative Examples 6 to 10; Evaluation results of the type of water-based adhesive used and the amount of change in the backward scattered light intensity thereof; Is shown in Table 3 below.

Laminates 1 to 7 produced by using the water-based adhesives F1 to F7 that satisfy the requirement for the amount of change in backscattered light intensity of the present invention are water-based adhesives that do not satisfy the requirement for the amount of change in backscattered light intensity of the present invention. The initial adhesiveness and the final adhesiveness were better than those of the laminated bodies 8 to 12 produced by using F8 to F12.

The dispersion liquid of the present invention is useful as an aqueous adhesive, a primer, a raw material thereof, or the like.

Claims (18)

A dispersion liquid containing water as a dispersion medium and a chlorinated rubber as a dispersoid and a compound having a polymerizable group.
The total amount of the chlorinated rubber and the compound having a polymerizable group is 5 to 60% by weight in the total of the chlorinated rubber, the compound having a polymerizable group and water.
The compound having a polymerizable group is a mixture of a compound having a polymerizable group and not having a cyclic structure and a compound having a polymerizable group and a cyclic structure.
The amount of the compound having a polymerizable group and not having a cyclic structure is 3 to 25% by weight in the total of the chlorinated rubber, the compound having a polymerizable group and water.
The amount of the compound having a polymerizable group and a cyclic structure is 0.2 to 5% by weight in the total of the chlorinated rubber, the compound having a polymerizable group and water .
A 30 mL dispersion is poured into a 100 mL container and stirred for 1 minute under the conditions of a rotation speed of 800 rpm and a rotation speed of 2,000 rpm using a rotation / revolution stirrer to prepare a measurement sample, and 20 mL of the measurement sample is placed in a cylinder having a diameter of 25 mm. Backscattered light by pouring into a sample cell in the shape of a sample, irradiating the measurement sample in the sample cell with incident light having a wavelength of 880 nm, and detecting the backward scattered light from the measured sample at a position of 45 ° with respect to the incident light. Intensity (%) measurement was started within 10 minutes of preparation of the measurement sample, and backscattering measured 30 minutes after the start of measurement at each of the top, middle and bottom of the measurement sample in the sample cell. The maximum value α (%) in the absolute value of the amount of change in the backward scattered light intensity (%) measured 24 hours after the start of the measurement with respect to the light intensity (%) is the following formulas (I) to (III):
α (upper part) <20 (I)
α (middle part) <5 (II)
α (bottom) <10 (III)
[In the formula, α (upper part) indicates the maximum value α (%) in the upper part of the measurement sample, α (intermediate part) indicates the maximum value α (%) in the middle part of the measurement sample, and α ( The bottom) indicates the maximum value α (%) at the bottom of the measurement sample, and the top, middle, and bottom of the measurement sample each indicate the height of the measurement sample in the sample cell excluding the meniscus portion from above. The part of the measurement sample divided by 1/3 is shown. ]
Meet the requirements,
Compounds having a polymerizable group and not having a cyclic structure are 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, and 1,6-hexanediol di. At least one selected from the group consisting of (meth) acrylates, 1,9-nonanediol di (meth) acrylates, and 1,10-decanediol di (meth) acrylates, and
The compound having a polymerizable group and a cyclic structure is at least one selected from the group consisting of 2-phenoxyethylene glycol (meth) acrylate, 2-phenoxydiethylene glycol (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate. A dispersion that is. The dispersion liquid according to claim 1, wherein the chlorine atom content in the chlorinated rubber is 45% by weight or more. The dispersion according to claim 1 or 2, wherein the amount of the chlorinated rubber is 1 to 30 parts by weight with respect to a total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group. The dispersion according to any one of claims 1 to 3, wherein at least a part of the chlorinated rubber is dissolved in a liquid dispersoid. The dispersion according to any one of claims 1 to 4, wherein at least a part of the compound having a polymerizable group is liquid at 23 ° C. and atmospheric pressure. The dispersion according to claim 5, wherein at least a part of the chlorinated rubber is dissolved in a compound having a polymerizable group which is liquid at 23 ° C. and atmospheric pressure. The dispersion liquid according to any one of claims 1 to 3, wherein the dispersoid is a liquid. The dispersion liquid according to any one of claims 1 to 7, wherein the compound having a polymerizable group is a compound having an ethylenically unsaturated bond. The dispersion according to any one of claims 1 to 8 , further comprising a surfactant. The dispersion according to any one of claims 1 to 9 , further comprising a photopolymerization initiator. The dispersion liquid according to any one of claims 1 to 10 , further comprising a fluorescent whitening agent. The dispersion according to any one of claims 1 to 11 , further comprising a leveling agent. The dispersion liquid according to any one of claims 1 to 12 , wherein the volume-based median diameter of the dispersoid in the dispersion liquid is 10 μm or less. The dispersion according to any one of claims 1 to 13 , wherein the chlorinated rubber is a chlorinated rubber having no carboxy group and a carboxylic acid anhydride structure. A coating film formed from the dispersion liquid according to any one of claims 1 to 14. The cured product of the coating film according to claim 17. A laminate in which the first base material, the cured product according to claim 16 , the adhesive layer, and the second base material are laminated in this order. The laminate according to claim 17 , wherein the first base material is an olefin polymer or an ethylene-vinyl acetate copolymer.