KR102412701B1 - dispersion - Google Patents

Abstract

The present invention is a dispersion comprising water as a dispersion medium and a chlorinated rubber and a compound having a polymerizable group as a dispersoid, wherein the total amount of the chlorinated rubber and the compound having a polymerizable group is a chlorinated rubber, a compound having a polymerizable group, and water It is 1 to 60 wt% in the total, and backscattered light measured 24 hours after starting the measurement with respect to the backscattered light intensity (%) measured 30 minutes after starting the measurement under the measurement conditions described in the specification The requirement that the maximum value α (%) in the absolute value of the change in intensity (%) is (I) α (top) < 20, (II) α (middle part) < 5, (III) α (bottom) < 10 A dispersion solution satisfying [the meaning of α (top), α (middle part), α (bottom), etc. is as described in the specification] is provided.

Description

dispersion

The present invention relates to dispersions.

BACKGROUND ART Dispersions (especially aqueous dispersions) such as emulsions and suspensions are widely 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 an adherend with sufficient strength, or could not adhere adherends to each other with sufficient strength. In addition, Patent Document 2 describes an aqueous emulsion excellent in adhesion comprising a chlorinated rubber having a chlorine atom content of 45 wt% or more, a compound having one or more polymerizable groups, and water. However, when such an aqueous emulsion was used after long-term storage, the adhesiveness was not necessarily sufficient.

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

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

[1] A dispersion comprising water as a dispersion medium and a compound having a chlorinated rubber and a polymerizable group as a dispersoid,

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,

30 ml of the dispersion liquid is poured into a 100 ml container, and using a rotational revolution stirrer, stirring is performed for 1 minute under the conditions of rotation speed of 800 rpm and rotation speed of 2,000 rpm to prepare a measurement sample, and 20 ml of the measurement sample having a diameter of 25 mm Backscattered light intensity by pouring into a cylindrical sample cell, irradiating the measurement sample in the sample cell with incident light having a wavelength of 880 nm, and detecting backscattered light from the measurement sample at a position of 45° to the incident light ( %) is started within 10 minutes from the preparation of the measurement sample, and the backscattered light intensity ( %), the maximum value α (%) in the absolute value of the amount of change in the backscattered light intensity (%) measured 24 hours after starting the measurement is the following formulas (I) to (III):

α (top) < 20 (I)

α (middle) < 5 (II)

α (bottom) < 10 (III)

[wherein, α (upper part) represents the maximum value α (%) in the upper part of the measurement sample, and α (middle part) represents the maximum value α (%) in the middle part of the measurement sample, α (bottom) represents the maximum value α (%) at the bottom of the measurement sample, and the top, middle, and bottom of the measurement sample respectively represent the height of the measurement sample in the sample cell excluding the meniscus portion. The portion of the measurement sample divided by 1/3 from the top is shown.]

A dispersion that meets the requirements of

[2] The dispersion liquid according to the above [1], wherein the total amount of the chlorinated rubber and the compound having a polymerizable group is 3 to 30% by weight in the total of the chlorinated rubber, the compound having a polymerizable group and water.

[3] The dispersion according to the above [1], wherein the total amount of the chlorinated rubber and the compound having a polymerizable group is 5 to 15% by weight in the total of the chlorinated rubber, the compound having a polymerizable group and water.

[4] The dispersion liquid according to any one of [1] to [3], wherein the chlorine atom content in the chlorinated rubber is 45 wt% or more.

[5] The dispersion liquid according to any one of [1] to [3], wherein the chlorine atom content in the chlorinated rubber is 45 to 85 wt%.

[6] The dispersion liquid according to any one of [1] to [3], wherein the chlorine atom content in the chlorinated rubber is 55 to 80 wt%.

[7] The dispersion liquid according to any one of [1] to [6], wherein the chlorinated rubber is a chlorinated rubber having a melting point.

[8] The dispersion according to the above [7], wherein the melting point of the chlorinated rubber is 100°C or higher.

[9] The dispersion according to the above [7], wherein the melting point of the chlorinated rubber is 200°C or higher.

[10] The dispersion according to the above [7], wherein the melting point of the chlorinated rubber is 240°C or higher.

[11] The dispersion liquid according to any one of [7] to [10], wherein the melting point of the chlorinated rubber is 350°C or less.

[12] The dispersion liquid according to any one of [7] to [10], wherein the melting point of the chlorinated rubber is 300°C or less.

[13] The dispersion liquid according to any one of [1] to [12], wherein the chlorinated rubber has a polystyrene equivalent weight average molecular weight of 1,000 or more.

[14] The dispersion liquid according to any one of [1] to [12], wherein the chlorinated rubber has a polystyrene equivalent weight average molecular weight of 3,000 or more.

[15] The dispersion liquid according to any one of [1] to [12], wherein the chlorinated rubber has a polystyrene equivalent weight average molecular weight of 5,000 or more.

[16] The dispersion liquid according to any one of [1] to [12], wherein the chlorinated rubber has a polystyrene equivalent weight average molecular weight of 10,000 or more.

[17] The dispersion liquid according to any one of [1] to [16], wherein the polystyrene equivalent weight average molecular weight of the chlorinated rubber is 400,000 or less.

[18] The dispersion liquid according to any one of [1] to [16], wherein the polystyrene equivalent weight average molecular weight of the chlorinated rubber is 200,000 or less.

[19] The dispersion according to any one of [1] to [18], wherein the amount of the chlorinated rubber is 1 to 30 parts by weight based on 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[20] The dispersion according to any one of [1] to [18], wherein the amount of the chlorinated rubber is 3 to 25 parts by weight based on 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[21] The dispersion according to any one of [1] to [18], wherein the amount of the chlorinated rubber is 5 to 20 parts by weight based on 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[22] The dispersion liquid according to any one of [1] to [21], wherein the amount of the chlorinated rubber is 0.01 to 18 wt% in the total of the chlorinated rubber, the compound having a polymerizable group, and water.

[23] The dispersion liquid according to any one of [1] to [21], wherein the amount of the chlorinated rubber is 0.1 to 10 wt% in the total of the chlorinated rubber, the compound having a polymerizable group, and water.

[24] The dispersion liquid according to any one of [1] to [21], wherein the amount of the chlorinated rubber is 0.2 to 5% by weight of the total of the chlorinated rubber, the compound having a polymerizable group, and water.

[25] The dispersion according to any one of [1] to [24], wherein at least a part of the chlorinated rubber is dissolved in a liquid dispersoid.

[26] The dispersion liquid according to any one of [1] to [25], wherein at least a part of the compound having a polymerizable group is liquid at 23°C and atmospheric pressure.

[27] The dispersion according to the above [26], 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 under atmospheric pressure.

[28] The dispersion according to any one of [1] to [27], wherein the dispersoid is liquid.

[29] The compound according to any one of [1] to [28], wherein 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. dispersion.

[30] The dispersion according to the above [29], wherein the amount of the compound having a polymerizable group and not having a cyclic structure is 40 to 99% by weight in the total of the compounds having a polymerizable group.

[31] The dispersion according to the above [29], wherein the amount of the compound having a polymerizable group and not having a cyclic structure is 60 to 97 wt% in the total of the compound having a polymerizable group.

[32] The dispersion according to the above [29], wherein the amount of the compound having a polymerizable group and not having a cyclic structure is 80 to 95 wt% in the total of the compound having a polymerizable group.

[33] The dispersion according to any one of [29] to [32], wherein the amount of the compound having a polymerizable group and a cyclic structure is 1 to 60% by weight of the total of the compound having a polymerizable group.

[34] The dispersion according to any one of [29] to [32], wherein the amount of the compound having a polymerizable group and a cyclic structure is 3 to 40 wt% in the total of the compound having a polymerizable group.

[35] The dispersion according to any one of [29] to [32], wherein the amount of the compound having a polymerizable group and a cyclic structure is 5 to 20% by weight of the total of the compound having a polymerizable group.

[36] Any one of [29] to [35] above, wherein the amount of the compound having a polymerizable group and not having a cyclic structure is 0.4 to 50 wt% in the total of the chlorinated rubber, the compound having a polymerizable group, and water. The dispersion described in .

[37] any one of [29] to [35] above, wherein the amount of the compound having a polymerizable group and not having a cyclic structure is 1 to 25 wt% in the total of the chlorinated rubber, the compound having a polymerizable group, and water The dispersion described in .

[38] any one of [29] to [35] above, wherein the amount of the compound having a polymerizable group and not having a cyclic structure is 3 to 25 wt% in the total of the chlorinated rubber, the compound having a polymerizable group, and water The dispersion described in .

[39] The dispersion according to any one of [29] to [38], wherein the amount of the compound having a polymerizable group and a cyclic structure is 0.01 to 30% by weight of the total of the chlorinated rubber, the compound having a polymerizable group, and water.

[40] The dispersion according to any one of [29] to [38], wherein the amount of the compound having a polymerizable group and a cyclic structure is 0.1 to 15% by weight of the total of the chlorinated rubber, the compound having a polymerizable group, and water.

[41] The dispersion according to any one of [29] to [38], wherein the amount of the compound having a polymerizable group and a cyclic structure is 0.2 to 5% by weight of the total of the chlorinated rubber, the compound having a polymerizable group, and water.

[42] The compound having a polymerizable group and not having a cyclic structure is 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylic At least one member selected from the group consisting of rate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate The dispersion according to any one of [29] to [41].

[43] the above [43] wherein the compound having a polymerizable group and not having a cyclic structure is at least one selected from the group consisting of dodecyl (meth) acrylate and 1,6-hexanediol di (meth) acrylate. 29] The dispersion liquid according to any one of [41].

[44] The compounds having a polymerizable group and not having a cyclic structure are at least one selected from the group consisting of dodecyl methacrylate and 1,6-hexanediol dimethacrylate, [29] to [ 41], the dispersion according to any one of the above.

[45] The compound having a polymerizable group and a cyclic structure is 2-phenoxyethylene glycol (meth) acrylate, 2-phenoxydiethylene glycol (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate The dispersion according to any one of [29] to [44], wherein the dispersion is at least one selected from the group consisting of.

[46] The above [29] wherein 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 and tricyclodecane dimethanol di (meth) acrylate. ] to the dispersion according to any one of [44].

[47] the above [29] to wherein the compound having a polymerizable group and a cyclic structure is at least one selected from the group consisting of 2-phenoxyethylene glycol methacrylate and tricyclodecane dimethanol di(meth)acrylate The dispersion according to any one of [44].

[48] The dispersion according to any one of [1] to [41], wherein the compound having a polymerizable group is at least one selected from the group consisting of a compound having an ethylenically unsaturated bond, an epoxy compound, and an oxetane compound.

[49] The dispersion according to any one of [1] to [41], wherein the compound having a polymerizable group is a compound having an ethylenically unsaturated bond.

[50] The dispersion according to [48] or [49], wherein the number of ethylenically unsaturated bonds in the compound having an ethylenically unsaturated bond is 1 to 3.

[51] The dispersion according to [48] or [49], wherein the number of ethylenically unsaturated bonds in the compound having an ethylenically unsaturated bond is 1 to 2.

[52] The dispersion according to any one of [1] to [51], further comprising a surfactant.

[53] The dispersion according to [52], wherein the amount of the surfactant is 1 part by weight or more based on 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[54] The dispersion according to the above [52] or [53], wherein the amount of the surfactant is 30 parts by weight or less based on 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[55] The dispersion according to the above [52] or [53], wherein the amount of the surfactant is 15 parts by weight or less based on 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[56] The dispersion according to [52] or [53], wherein the amount of the surfactant is 10 parts by weight or less based on 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[57] The dispersion according to any one of [1] to [56], further comprising a photoinitiator.

[58] The dispersion according to the above [57], wherein the amount of the photoinitiator is 0.01 parts by weight or more with respect to 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[59] The dispersion according to [57] or [58], wherein the amount of the photoinitiator is 40 parts by weight or less based on 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[60] The dispersion according to [57] or [58], wherein the amount of the photopolymerization initiator is 20 parts by weight or less based on 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[61] The dispersion according to [57] or [58], wherein the amount of the photopolymerization initiator is 10 parts by weight or less based on 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[62] The dispersion according to [57] or [58], wherein the amount of the photopolymerization initiator is 5 parts by weight or less based on 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[63] The dispersion according to any one of [1] to [62], further comprising an optical brightener.

[64] The dispersion according to [63], wherein the amount of the optical brightener is 0.01 parts by weight or more with respect to 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[65] The dispersion according to [63] or [64], wherein the amount of the optical brightener is 5 parts by weight or less based on 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[66] The dispersion according to the above [63] or [64], wherein the amount of the optical brightener is 3 parts by weight or less based on 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[67] The dispersion according to the above [63] or [64], wherein the amount of the optical brightener is 1 part by weight or less based on 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[68] The dispersion according to any one of [1] to [67], further comprising a leveling agent.

[69] The dispersion according to the above [68], wherein the amount of the leveling agent is 1 part by weight or more with respect to 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[70] The dispersion according to [68] or [69], wherein the amount of the leveling agent is 20 parts by weight or less based on 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[71] The dispersion according to the above [68] or [69], wherein the amount of the leveling agent is 10 parts by weight or less with respect to 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.

[72] The dispersion according to any one of [1] to [71], wherein the volume-based median diameter of the dispersoid in the dispersion is 10 µm or less.

[73] The dispersion according to any one of [1] to [71], wherein the volume-based median diameter of the dispersoid in the dispersion is 0.01 to 5 µm.

[74] The dispersion according to any one of [1] to [71], wherein the volume-based median diameter of the dispersoid in the dispersion is 0.01 to 2 µm.

[75] The dispersion according to any one of [1] to [71], wherein the volume-based median diameter of the dispersoid in the dispersion is 0.01 to 1 µm.

[76] The dispersion liquid according to any one of [1] to [75], wherein the chlorinated rubber is a chlorinated rubber having no carboxyl group or carboxylic acid anhydride structure.

[77] A coating film formed from the dispersion according to any one of [1] to [76].

[78] A cured product of the coating film according to the above [77].

[79] A laminate in which a first substrate, the cured product according to [78], an adhesive layer, and a second substrate are laminated in this order.

[80] The laminate according to the above [79], wherein the first substrate is made of an olefin-based polymer or an ethylene-vinyl acetate copolymer.

Even if the dispersion liquid of the present invention is used after long-term storage, it can adhere to an adherend with sufficient strength.

<dispersion liquid>

The dispersion liquid of this invention contains water as a dispersion medium, and contains the compound which has a chlorinated rubber and a polymeric group as a dispersoid. The dispersion liquid of the present invention is useful as a water-based adhesive, a primer, or a raw material thereof.

The dispersion (dispersion) of the present invention may be a suspension (suspension) in which the dispersoid is in a solid phase, or an emulsion (emulsion) in which the dispersoid is liquid, a part of the dispersoid is in a solid phase, and the rest of the dispersoid is in a liquid phase. A dispersion may be sufficient. The dispersion of the present invention is preferably an emulsion in which the dispersoid is liquid, or a dispersion in which a part of the dispersoid is in a solid phase and the remaining dispersoid is in a liquid phase, and 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, that at least a part of the chlorinated rubber is dissolved in the liquid dispersion means that when the dispersion is filtered through a filter having a pore diameter of about 0.50 µm, at least a part of the chlorinated rubber is contained in the filtrate. 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, it is 70 parts by weight or more. It is particularly preferable that all of the chlorinated rubber is dissolved in a liquid dispersoid (that is, 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 atmospheric pressure, and more preferably all of the compound having a polymerizable group is in a liquid state at 23°C and atmospheric pressure. In this aspect, it is preferable that at least a part of the chlorinated rubber is dissolved in a compound having a liquid polymerizable group at 23° C. and atmospheric pressure (hereinafter sometimes abbreviated as “a compound having a liquid polymerizable group”), It is more preferable that all of the chlorinated rubber is dissolved in a compound having a liquid polymerizable group.

The fact that at least a part of the chlorinated rubber is dissolved in a compound having a liquid polymerizable group means that when the mixture of the chlorinated rubber and the compound having a liquid polymerizable group is filtered through a filter having a pore diameter of about 0.50 μm, at least a part of the chlorinated rubber is It means that it is contained in the filtrate. 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, it is 70 parts by weight or more. It is particularly preferable that all of the chlorinated rubber is dissolved in a liquid dispersoid (that is, all of the chlorinated rubber is contained in the filtrate).

The mixing temperature at the time of preparing the mixture of a chlorinated rubber and the compound which has a polymeric group is 25-100 degreeC normally, and the mixing time is preferably as short as possible. For this reason, as a mixer used for this, a Banbury mixer, a Henschel mixer, a homo mixer, etc. are mentioned, for example.

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, and more preferably 5 to 15% by weight in the total of the chlorinated rubber, the compound having a polymerizable group and water. . By carrying out the total amount of a chlorinated rubber and the compound which has a polymeric group in the said range, adhesiveness becomes favorable.

The dispersion liquid of the present invention is prepared by pouring 30 ml of the dispersion into a 100 ml container, and stirring for 1 minute under the conditions of a rotation speed of 800 rpm and a rotation speed of 2,000 rpm using a rotation or revolution stirrer to prepare a measurement sample, and measure 20 ml The sample is poured into a cylindrical sample cell with 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 backscattered light from the measurement sample is detected at a position of 45° with respect to the incident light. The measurement of the backscattered light intensity (%) by the The maximum value α (%) in the absolute value of the amount of change in the backscattered light intensity (%) measured 24 hours after the start of the measurement for one backscattered light intensity (%) is expressed by the following formulas (I) to (III) ) :

α (top) < 20 (I)

α (middle) < 5 (II)

α (bottom) < 10 (III)

[wherein, α (upper part) represents the maximum value α (%) in the upper part of the measurement sample, and α (middle part) represents the maximum value α (%) in the middle part of the measurement sample, α (bottom) represents the maximum value α (%) at the bottom of the measurement sample, and the top, middle, and bottom of the measurement sample respectively represent the height of the measurement sample in the sample cell excluding the meniscus portion. The portion of the measurement sample divided by 1/3 from the top is shown.]

One of the features is to satisfy the requirements of Further, in the present invention, the boundary between the upper portion and the middle portion of the measurement sample and the boundary between the middle portion and the bottom portion of the measurement sample are all included in the intermediate portion of the measurement sample. The dispersion liquid of the present invention satisfying these requirements can adhere to an adherend with sufficient strength even when used after long-term storage.

A series of operations consisting of the preparation of the measurement sample and the measurement of the backscattered light intensity (%) are performed in a 24-26°C environment using an apparatus placed in a 24-26°C environment. In addition, the dispersion liquid left still for 1 hour or more in the environment of 24-26 degreeC is used for preparation of a measurement sample (that is, stirring of the dispersion liquid by an autorotation revolution stirrer).

As an autorotation/revolution stirrer for preparing the said measurement sample, the "rotation/revolution mixer Awatori Rentaro ARE-310" made by a Thinky company is mentioned, for example. As an apparatus which measures the amount of change of the backscattered light intensity (%) of the said measurement sample, the "tabiscan TOWER" by a Formulation company is mentioned, for example.

Said "backscattered light intensity (%)" means "intensity of detected backscattered light with respect to the intensity of irradiated incident light (%)". The "change in backscattered light intensity (%) measured 24 hours after the start of the measurement with respect to the backscattered light intensity (%) measured 30 minutes after starting the measurement" means "after the measurement is started" It means the difference between the backscattered light intensity (%) measured after 30 minutes and the backscattered light intensity (%) measured 24 hours after starting the measurement." The "maximum value in the absolute value" means "the maximum value in the plurality of absolute values calculated in 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, and still more preferably 0.01 to 1 µm. When the median diameter is within the above range, the dispersion liquid has good stationary stability.

The volume-based median diameter of the dispersoid means the particle diameter at which the value of the integrated particle size distribution becomes 50% by volume. This median diameter can be measured by the HORIBA Corporation make, laser diffraction particle diameter measuring apparatus LA-950V2.

<Chlorinated rubber>

A chlorinated rubber means what chlorinated natural rubber or synthetic rubber. The number of chlorinated rubbers may be one, and 2 or more types may be sufficient as them. In the present specification, "rubber" means "uncrosslinked rubber" unless otherwise specified.

Chlorinated rubber with low crystallinity does 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 a 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 the chlorinated rubber can be measured by differential scanning calorimetry (DSC). As an apparatus of DSC, the Shimadzu Corporation DSC-60Plus is mentioned, for example.

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

It is preferable to use the thing which does not have a carboxy group and a carboxylic acid anhydride structure as a chlorinated rubber. When the dispersion liquid of the present invention containing such a chlorinated rubber is used as a water-based adhesive, a primer, or a raw material thereof, the concern about a decrease in the water resistance of the coating film is extremely small and effective.

The chlorinated rubber is not particularly limited as long as natural rubber or synthetic rubber is chlorinated, for example, chlorinated natural rubber, chlorinated butadiene rubber, chlorinated butyl rubber, chlorinated isoprene rubber, butadiene/chlorinated cyclic conjugated diene adduct, chlorinated butadiene styrene copolymer, brominated poly(2,3-dichloro-1,3-butadiene) and ?-haloacrylonitrile-co-2,3-dichloro-1,3-butadiene copolymer; and the like. A 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 rubber.

As a method for chlorinating natural rubber or synthetic rubber, a conventionally known method can be employed. For example, a method of dissolving natural rubber or synthetic rubber in chlorinated organic solvents, such as carbon tetrachloride and monochlorobenzene, or organic solvents, such as toluene, and injecting chlorine gas; A method of spraying chlorine gas in a state in which natural rubber or synthetic rubber is suspended or emulsified in water; A method of introducing chlorine gas while irradiating with ultraviolet rays in a state in which natural rubber or synthetic rubber is suspended or emulsified in water; A method of directly chlorination by bringing natural rubber or synthetic rubber into contact with liquid chlorine under low-temperature and pressurization, and the like. In addition, the agglomerated and solidified natural rubber or synthetic rubber may be dissolved in an organic solvent and then chlorinated, or the agglomerated and solidified natural rubber or synthetic rubber may be dissolved in an organic solvent and then emulsified and dispersed, followed by chlorination while the solvent is volatilized. have. In the case of chlorination of natural rubber, it may be chlorinated by spraying chlorine gas on the natural rubber on latex. For example, polyisoprene, a surfactant, and an acid such as hydrochloric acid, sulfuric acid or nitric acid are added to water, emulsified, and then uniformly chlorinated polyisoprene can be obtained by spraying chlorine gas.

The chlorinated rubber has a polystyrene conversion weight average molecular weight (Mw) of preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, particularly preferably 10,000 or more, preferably 400,000 or less, more preferably Usually less than 200,000. This Mw can be measured by gel permeation chromatography (GPC). When the dispersion of the present invention containing the chlorinated rubber having such Mw is used as a water-based adhesive, a primer, or a raw material thereof, sufficient adhesive strength can be secured and excessive increase in viscosity is suppressed, and Adhesiveness can be sufficiently ensured.

As the chlorinated rubber, for example, a commercially available product, a known method, or one manufactured according thereto can be used. As a commercial item, For example, Superclone (trademark) CR-10, CR-20 (Nippon Paper Co., Ltd.), Fergut S-5, Fergut S-10, Fergut S-20, Fergut S -40, Fergut S-90, Fergut S-130, Fergut S-170 (Covestro), Alloprene (registered trademark) R10, R20, R40 (manufactured by ICI UK), and the like. As a well-known method, the method of Unexamined-Japanese-Patent No. 2660478 is mentioned, for example.

The amount of the 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 with respect to 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group. .

The amount of the chlorinated rubber is preferably 0.01 to 18% by weight, more preferably 0.1 to 10% by weight, and still more preferably 0.2 to 5% by weight in the total of the chlorinated rubber, the compound having a polymerizable group and water.

<Compound having a polymerizable group>

Only 1 type may be used for the compound which has a polymeric group, and may use 2 or more types together. In addition, the number of the polymeric group which this compound has may be one, and two or more may be sufficient as it. In addition, the compound may have only 1 type of polymeric group, and may have 2 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)acryl group, a (meth)acryloyl group, a vinyl ether group, a vinylbenzyl ether group, (meth) Acryloxy 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 and ring-opening polymerizable groups such as oxetane group). In addition, in this specification, "(meth)acryl" means "acryl and methacryl", and "(meth)acryloyl" means "acryloyl and methacryloyl." Other expressions of "(meth)" have the same meaning.

The compound which has a polymeric group, Preferably it is at least 1 selected from the group which consists of a compound which has an ethylenically unsaturated bond, an epoxy compound, and an oxetane compound, More preferably, it is a compound which has an ethylenically unsaturated bond. The number of ethylenically unsaturated bonds in the compound which has an ethylenically unsaturated bond becomes like this. Preferably it is 1-3, More preferably, it is 1-2.

As a compound which has one ethylenically unsaturated bond, For example, heterocyclic ethylenically unsaturated compound (For example, N-vinyl, such as N-vinylpyrrolidone, N-vinylpyridine, and N-vinylcaprolactam, - Heterocyclic (meth)acrylates such as nitrogen-containing heterocyclic compounds, morpholine (meth)acrylate, tetrahydrofurfuryl (meth)acrylate and glycidyl (meth)acrylate), N-vinylformamide , N-vinylacetamide, dialkylaminoethyl (meth)acrylate (eg, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, etc.), N,N'-dimethylacrylamide , Alkoxy (poly) alkylene glycol (meth) acrylate (eg, methoxyethylene (meth) acrylate, ethoxy-diethylene glycol (meth) acrylate, methoxy polyethylene (meth) acrylate, butoxy polyethylene (meth) acrylate, etc.), alkyl (meth) acrylates (eg, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylic rate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate ) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, stearyl (meth) acrylate ) acrylate, cetyl (meth) acrylate, behenyl (meth) acrylate, etc.), hydroxyl group-containing (meth) acrylate (eg, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalic acid, glycerin mono (meth) acrylate, 2- Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, neopentyl glycol mono (meth) acrylic LATE, polypropylene glycol mono(meth) ) acrylate, polyethylene glycol mono(meth)acrylate, polyethylene glycol-propylene glycol mono(meth)acrylate, etc.), polyε-caprolactone mono(meth)acrylate, mono[2-(meth)acryloyloxy ethyl] acid phosphate, halogen-containing (meth)acrylate (eg, trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, N,N,N-trimethyl-N-(2-hydroxy-3 methacryloyloxypropyl)-ammonium chloride, etc.), silicone-containing (meth)acrylate (e.g., (meth)acrylate ) Acrylic modified organopolysiloxane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth) ) acryloxypropylmethyldiethoxysilane, etc.), unsaturated carboxylic acid glycidyl ester-containing (meth)acrylate (eg, glycidyl (meth)acrylate, glycidyl methacrylate, 3,4- Epoxybutyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, etc.), aliphatic vinyl compounds (eg, acetic acid) Vinyl, vinyl propionate, vinyl butyrate, vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, etc.), unsaturated amides or unsaturated imides (eg, acrylamide, methacrylamide, diacetone (meth) acrylamide; α-Chloroacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, N-(meth)acryloylphthalimide, N-(2-hydroxyethyl)acrylamide, N-(2-hydroxyl ethyl)methacrylamide and maleimide, etc.), acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and polymers (eg, polystyrene, polymethylacrylate, polymethylmethacrylate, polyn -Butyl acrylate, polyn-butyl methacrylate, polysilicon, etc.) the macromonomer etc. which have a monoacryloyl group or a monomethacryloyl group at the terminal.

As a compound having one ethylenically unsaturated bond and having a cyclic structure, for example, (meth)acrylate having an alicyclic skeleton (eg, 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, phenyl norbornyl (meth) acrylate, cyano norbornyl (meth) acrylate, menthyl (meth) acrylate, pentyl (meth) acrylate, adamantyl (meth) acrylate, dimethyl Adamantyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] deca-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] deca-4-methyl (meth) acrylate , cyclodecyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, isobornyl (meth) acrylate, bornyl (meth) acrylate, dicyclopentadiene (meth) acrylate, Dicyclopentenyloxyalkyl (meth) acrylate, tricyclodecanyloxyethyl (meth) acrylate, isoboryloxyethyl (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 (for example , 2-phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, etc.), alkylphenoxymethyl (meth) acrylate (eg, nonylphenoxyethyl (meth) acrylate, etc.), phenoxy Cy (poly) alkylene glycol (meth) acrylate (eg, phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, etc.), alkylphenoxy Cy (poly) alkylene glycol (meth) acrylate (for example, nonylphenoxy polyethylene glycol (meth) acrylate, paracumyl phenoxy ethylene glycol (meth) acrylate, etc.), a hydroxyl group and an alicyclic skeleton or Aromatic skeleton-containing (meth)acrylates (eg, 2-hydroxy-3-phenyloxypro Phil (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-chlorostyrene, p-chlorostyrene, p- methoxystyrene, vinyl benzoate, etc.).

Examples of the compound having two ethylenically unsaturated bonds include di(meth)acrylate of 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, poly Oxyalkylene glycol di (meth) 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) acrylic rate, polyethylene glycol-propylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 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-nonanediol 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 (meth) acrylate, 3-methyl-pentanediol Di(meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, etc.), silicone-containing (meth)acrylate (for example, ( meth)acryl-modified organopolysiloxane), and diacetone acrylamide.

As a compound having two ethylenically unsaturated bonds and having a cyclic structure, for example, di(meth)acrylate ( For example, di(meth)acrylate of 2,2-bis(2-hydroxyethoxyphenyl)propane), di(meth)acrylate having a crosslinked cyclic hydrocarbon group (eg, cyclohexanedimethanol di(meth)acrylate, di(meth)acrylate of tricyclodecanedimethylol (eg, tricyclodecanedimethanoldi(meth)acrylate), dicyclopentadienedi(meth)acrylate, etc.); (meth)acrylic acid adduct of bifunctional epoxy resin (eg, (meth)acrylic acid adduct of 2,2-bis(glycidyloxyphenyl)propane, bisphenol A diglycidyl ether methacrylic acid adduct etc.) can be mentioned.

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 dipentaeryth. Ritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylol propane tetraacrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, tris (acryloyloxy) isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (hydroxy Tri (meth) acrylate of propyl) isocyanurate, triallyl trimellitic acid, triallyl isocyanurate, and silicone-containing (meth) acrylate (eg, (meth) acrylic modified organopolysiloxane, etc.) and the like.

Carbon number of the compound which has an ethylenically unsaturated bond becomes like this. Preferably it is 5-25, More preferably, it is 6-23, More preferably, it is 8-20.

Examples of the epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2 -Butylene oxide, 1,3-butadiene monoxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene Oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, bisphenol A diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl Diyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F di Glycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, bis(3,4-epoxy-6-methylcyclohexyl) Methyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopenta Diene diepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl)ether, ethylenebis(3,4-epoxycyclohexanecarboxylate), epoxyhexahydrophthalate dioctyl, epoxyhexahydrophthalate di-2 -Ethylhexyl, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, poly Propylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, etc. can

As an epoxy compound, an aromatic epoxide and an alicyclic epoxide are preferable from a viewpoint of being excellent in a curing rate, and an alicyclic epoxide is more preferable.

Examples of the oxetane compound include 2-hydroxymethyl-2-methyloxetane, 2-hydroxymethyl-2-ethyloxetane, 2-hydroxymethyl-2-propyloxetane, and 2-hydroxy Methyl-2-butyloxetane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, etc. are 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 of the present invention is preferably 70 to 99 parts by weight, more preferably 75 to 97 parts by weight, still more preferably based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. It is 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.

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

The compound having a polymerizable group and a cyclic structure is preferably 2-phenoxyethylene glycol (meth) acrylate, 2-phenoxy diethylene glycol (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate. At least one selected from the group consisting of, more preferably at least one selected from the group consisting of 2-phenoxyethylene glycol (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate, more preferably Preferably, it is at least one selected from the group consisting of 2-phenoxyethylene glycol methacrylate and tricyclodecane dimethanol 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, the compound having a polymerizable group and not having a cyclic structure The amount is preferably 0.4 to 50% by weight, more preferably 1 to 25% by weight, still more preferably 3 to 25% by weight, in the total of the chlorinated rubber, the compound having a polymerizable group and water, and the polymerizable group and the cyclic The amount of the compound having a structure is preferably 0.01 to 30% by weight, more preferably 0.1 to 15% by weight, and still more preferably 0.2 to 5% by weight in the total of the chlorinated rubber, the compound having a polymerizable group, and water.

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, the compound having a polymerizable group and not having a cyclic structure The amount is preferably 40 to 99% by weight, more preferably 60 to 97% by weight, still more preferably 80 to 95% by weight, in the total of the compounds having a polymerizable group, the polymerizable group and the cyclic structure The amount of the compound to have is in the total of the compounds having a polymerizable group, preferably 1 to 60% by weight, more preferably 3 to 40% by weight, still more preferably 5 to 20% by weight.

<Water>

There is no limitation in particular as water contained in the dispersion liquid of this invention, 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 another component, only 1 type may be used and may use 2 or more types together. Other components include, for example, polymerization inhibitors, surfactants, photoinitiators, light stabilizers, ultraviolet curable oligomers, optical brighteners, leveling agents, basic compounds, organic solvents, crosslinking agents, photosensitizers, and chlorinated rubbers. different resins or rubbers, phenolic stabilizers, phosphite-based stabilizers, amine-based stabilizers, amide-based stabilizers, anti-aging agents, weathering stabilizers, preservatives, anti-settling agents, antioxidants, heat stabilizers, thixotropic agents, thickeners, defoamers, viscosity modifiers, a weathering agent, a pigment dispersant, an antistatic agent, a lubricant, a nucleating agent, a flame retardant, an oil agent, dye, a hardening|curing agent; transition metal compounds such as titanium oxide (rutile type) and zinc oxide; Pigments, such as carbon black; Glass fiber, carbon fiber, potassium titanate fiber, wollastonite, calcium carbonate, calcium sulfate, talc, glass flake, barium sulfate, clay, kaolin, fine powder silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, inorganic or organic fillers such as magnesium oxide and celite; and the like. All of these may use only 1 type, and may use 2 or more types together.

<Polymerization inhibitor>

There is no limitation in particular in a polymerization inhibitor, A well-known polymerization inhibitor can be used. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, monoesterified 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-benzoquinone, 4-methoxyphenol, chloranyl, pyrogallol, 2-oxydiphenylamine, phenothiazine, etc. are mentioned.

Commercially available polymerization inhibitors include, for example, quinopower QS-10, quinopower QS-20, quinopower QS-30, quinopower QS-40, quinopower QS-W10 (manufactured by Kawasaki Chemical Industry Co., Ltd.), metoquinone flakes. , Nonflex Alba, MH, TBH, PBQ, toluquinone, TBQ (manufactured by Seiko Chemical), and the like.

A polymerization inhibitor has the effect|action which improves the storage stability of a dispersion liquid and ensures sclerosis|hardenability. In consideration of such an action and the like, the amount of the polymerization inhibitor in the dispersion is preferably 0.005 to 0.4 parts by weight, more preferably 0.01 to 0.4 parts by weight, based on 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group. , Even more preferably 0.01 to 0.3 parts by weight, still more preferably 0.02 to 0.3 parts by weight, still more preferably 0.02 to 0.2 parts by weight, particularly preferably 0.035 to 0.2 parts by weight. As a polymerization inhibitor, the polymerization inhibitor made to melt|dissolve in the compound which has a liquid polymeric group is preferable.

<Surfactant>

It is preferable that surfactant acts as an emulsifier. As surfactant, cationic, anionic, amphoteric, or nonionic surfactant is mentioned, for example, Preferably, it is anionic or nonionic surfactant. Surfactant may be used independently and may be used in combination of 2 or more type.

As anionic surfactant, For example, fatty acid sodium, such as sodium palmitate, sodium ether carboxylate, such as polyoxyethylene lauryl ether carboxylate sodium, lauroyl sarcosine sodium, N-lauroyl Amino acid condensates of higher fatty acids such as sodium glutamate, higher fatty acid ester sulfonates such as higher alkyl sulfonates and lauric acid ester sulfonates, dialkyl sulfosuccinates such as dioctyl sulfosuccinate, and higher fatty acids such as oleic acid amide sulfonic acid Alkylarylsulfonates such as amidesulfonate, sodium dodecylbenzenesulfonate and diisopropylnaphthalenesulfonate, formalin condensates of alkylarylsulfonates, higher alcohol sulfate esters such as pentadecane-2-sulfate, dipolyoxyethylenedode Polyoxyethylene alkyl phosphate ester, such as silether phosphate ester, lignin sulfonate, polyoxyethylene-1-(allyloxymethyl) ammonium ammonium sulfate, polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate, bis(polyoxyethylene ester) Cyclic phenyl ether) bismethacrylate sulfate ester salt, alkylallyl succinate sulfonate sodium salt, polyoxyalkylene alkenyl ether ammonium sulfate, 2-sodium sulfoethyl methacrylate, alkoxy polyethylene glycol maleate, sulfuric acid ester of higher alcohol Salts, higher carboxylates, alkylbenzenesulfonates, polyoxyethylenealkylsulfate salts, polyoxyethylenealkylphenylethersulfate salts and vinylsulfosuccinates, sodium poly(meth)acrylate, poly(meth)ammonium acrylate, (meth) ) acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, styrene-maleic acid copolymer ammonium salt, styrene-maleic acid half ester copolymer ammonium salt, sodium carboxymethylcellulose and sodium naphthalenesulfonate formalin condensate, etc. can

Examples of the cationic surfactant include alkylamine hydrochloride such as dodecylamine hydrochloride, alkyldimethylbenzylammonium salt, alkylisoquinolinium salt, and alkyl quaternary ammonium salt such as dialkylmorpholinium salt, benzethonium chloride, and poly Alkyl ammonium salts such as alkylvinylpyridinium salt, dodecyltrimethylammonium salt and cetyltrimethylammonium salt, alkylpyridium salt such as cetylpyridium salt and decylpyridium salt, oxyalkylenetrialkylammonium salt, dioxyalkylenedialkylammonium salt, allyl Trialkylammonium salts, diallyldialkylammonium salts, polydiallyldimethylammonium chloride, etc. are mentioned.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene lanolin alcohol, polyoxyethylene alkylphenol formalin condensate, polyoxyethylene sorbitan fatty acid ester, polyoxy Ethylene glyceryl monofatty acid ester, 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, poly Oxyethylene polyoxypropylene block polymer, polyoxyethylene fatty acid amide, alkylolamide, polyoxyethylene alkylamine, polyoxyethylene alkanediol, alkoxy polyethylene glycol methacrylate, polyoxyethylene alkylphenyl ether, polyethylene glycol fatty acid ester, poly Oxyethylene fatty acid amide, polyalkylene polyamine alkylene oxide adduct, polyalkylene polyimine alkylene oxide adduct, polyvinyl pyrrolidone, dicyandiamide polyalkylene polyamine condensate, polyethylene glycol, polyvinyl alcohol, etc. can be heard

Examples of the amphoteric surfactant include N-lauryalanine, N,N,N-trimethylaminopropionic acid, N,N,N-trihydroxyethylaminopropionic acid, N-hexyl-N,N-dimethylamino Acetic acid, 1-(2-carboxyethyl) pyrimidinium betaine, lecithin, lauryl betaine, lauryl dimethylamine oxide, etc. are mentioned.

Commercially available surfactants include, for example, Emal 0, Emal 10G, Emal 2F paste, Emal 20C, Emal E-27C, Emal 270J, Emal E-27C, Neopelex GS, Neopelex G-15, Neo Pelex G-25, Neopelex G-65, Latemul PD-104, Pelex OT-P, Pelex TR, Pelex SS-L, Pelex SS-H, Demol N, Demol EP, Emalgen 102KG , Emalgen 104P, Emalgen 105, Emalgen 106, Emalgen 108, Emalgen 404, Emalgen 130K, Emalgen 147, Emalgen LS-106, Emalgen LS-110, Emalgen A-60, Emalgen 109P , Emalgen 350, Lattemul PD-420, Leodol 430V, Emanon 1112, Emanon CH-25, Amit 102, Acetamine 86, Cortamine 24P, Amphitol 24B, Neopelex No.6 powder, Latte Water E-1000A, Pelex OT-P, Emalgen LS-114, Emalgen 210P, Emalgen 220, Emalgen 306P, Emalgen 320P, Emalgen 408, Emalgen 409PV, Emalgen 420, Amphitol 86B and Cancer Phytol 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, Hythenol NF-08, Hi Tenol 227L, Flysurf A212C, Flysurf A210D, Neocol P, Monogen Y-100, Catiogen TML, Aquaron KH-10, Aquaron KH-1025, Aquaron HS-10, Aquaron RN-20, Aquaron RN-30, Fitzcall K-17L and Fitzcall V-7154 (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), Adeka Pluronic F108, Adeka Pluronic L-61, Adeka Pluronic 17R-2 ( Manufactured by ADEKA) Eleminol JS-20, Eleminol RS-3000, Sanmorin OT-70 and Carribon EN-200 (manufactured by Sanyo Chemical Industry Co., Ltd.), Kurare Poval PVA-103, Kurare Poval PVA-105, Kurare Poval PVA-117, Kurare Poval PVA-217, Kurare Poval PVA-205, Kurare Poval PVA-205 PVA-203, Kurare Poval PVA-210, Kurare Poval PVA-235, Kurare Poval PVA-403, Kurare Poval PVA-405, Kurare Poval PVA-417, Kurare Poval M-205, Kurare Poval MP -203, Kurare Poval KL-506 and Kuraray Poval KL-318 (manufactured by Kurare), Akumarim AKM-1511-60, Akumarim AKM-0531, Polystar OM and Pronon #102 (manufactured by Nichiyu Corporation), etc. can be heard

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

<Photoinitiator>

A photoinitiator is a compound which generate|occur|produces an active species by the action of light. As the photopolymerization initiator, for example, a photo-radical generator that generates an active radical by the action of light, a photo-acid generator that generates an acid by the action of light, and a photobase generator that generates a base by the action of light can be heard

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.), carboxylate esters Ryu, etc. are mentioned.

As a benzoin compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

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, 2,4,6-trimethylbenzophenone, etc. are mentioned.

Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)butan-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-methylpropy and an oligomer of ofenone and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one.

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, 2,4-bis(trichloromethyl) -6-(4-Methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl )-6-[2-(furan-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)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3; 5-triazine etc. are mentioned.

As a photo-radical generator, a commercially available thing can be used. Commercially available photo-radical generators include, for example, Irgacure (registered trademark) 1173, 907, 184, 651, 819, 250, 2959, 127, 754 and 369 (BASF Japan Co., Ltd.), Sei Quol (registered trademark) BZ, Z and BEE (Seiko Chemical Co., Ltd.), kayacure (registered trademark) BP100 (Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow Corporation), Adeka Opto Mercury SP-152 and SP-170 (ADEKA Co., Ltd.), TAZ-A and TAZ-PP (Nippon Syiber Heigner Co., Ltd.), TAZ-104 (Sanwa Chemical Co., Ltd.) and MBF (BASF Japan Co., Ltd.) )) and the like. These photo-radical generators may be used independently and may be used in combination. Specific examples of the combination include Irgacure (registered trademark) 500 (1-hydroxy-cyclohexyl-phenyl-ketone/benzophenone: 50/50%), Irgacure (registered trademark) 1700 (bis(2, 6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide/2-hydroxy-2-methylphenylpropan-1-one: 25/75%) and Irgacure (registered trademark) 1800 (bis( 2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide/1-hydroxycyclohexyl-phenyl ketone: 25/75%) (BASF Japan Co., Ltd.) etc. are mentioned.

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

Examples of the sulfonic acid derivative include disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, trifluoromethylsulfonates, benzoinsulfonates, 1-oxy-2- Sulfonates of hydroxy-3-propyl alcohol, pyrogallol trisulfonates, and benzyl sulfonates are mentioned. Specifically, diphenyldisulfone, ditosyldisulfone, bis(phenylsulfonyl)diazomethane, bis(chlorphenylsulfonyl)diazomethane, bis(xylylsulfonyl)diazomethane, phenylsulfonylbenzoyldiazo Methane, bis(cyclohexylsulfonyl)methane, benzointosylate, 1,2-diphenyl-2-hydroxypropyltosylate, 1,2-di(4-methylmercaptophenyl)-2-hydroxypropyl tosylate, pyrogallolmethylsulfonate, pyrogallolethylsulfonate, 2,6-dinitrophenylmethyltosylate, ortho-nitrophenylmethyltosylate, para-nitrophenyltosylate, and the like.

Examples of onium salts include tetrafluoroborate (BF ^4- ), hexafluorophosphate (PF ^6- ), hexafluoroantimonate (SbF ^6- ), hexafluoroalsenate (AsF ^6- ) ), hexachlorantimonate (SbCl ^6- ), tetraphenylborate, tetrakis(trifluoromethylphenyl)borate, tetrakis(pentafluoromethylphenyl)borate, perchlorate ion ( ^ClO4- ), trifluoromethanesulfonic acid sulfonium salts and iodonium salts having anions such as ions (CF ₃ SO ^3- ), fluorosulfonic acid ions (FSO ^3- ), toluenesulfonic acid ions, trinitrobenzenesulfonic acid anions, and trinitrotoluenesulfonic acid anions; and the like. .

Examples of the sulfonium salt include triphenylsulfonium hexafluoroacylate, triphenylsulfonium hexafluoroborate, triphenylsulfonium tetrafluoroborate, and triphenylsulfonium tetrakis(pentafluorobenzyl)borate. , methyldiphenylsulfoniumtetrafluoroborate, methyldiphenylsulfoniumtetrakis(pentafluorobenzyl)borate, dimethylphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoro Roantimonate, diphenylnaphthylsulfonium hexafluoroalsenate, tritoylsulfonium hexafluorophosphate, anisyldiphenylsulfonium hexahexafluoroantimonate, 4-butoxyphenyldiphenylsulfoniumtetrafluoroborate , 4-butoxyphenyldiphenylsulfoniumtetrakis(pentafluorobenzyl)borate, 4-chlorophenyldiphenylsulfoniumhexafluoroantimonate, tris(4-phenoxyphenyl)sulfoniumhexafluorophosphate, Di(4-ethoxyphenyl)methylsulfonium hexafluoroalsenate, 4-acetylphenyldiphenylsulfoniumtetrafluoroborate, 4-acetylphenyldiphenylsulfoniumtetrakis(pentafluorobenzyl)borate, tris( 4-thiomethoxyphenyl) sulfonium hexafluorophosphate, di (methoxysulfonylphenyl) methylsulfonium hexafluoroantimonate, di (methoxynaphthyl) methylsulfonium tetrafluoroborate, di (methoxy Naphthyl) methylsulfonium tetrakis (pentafluorobenzyl) borate, di (carbomethoxyphenyl) methylsulfonium hexafluorophosphate, (4-octyloxyphenyl) diphenylsulfonium tetrakis (3,5-bis -Trifluoromethylphenyl)borate, tris(dodecylphenyl)sulfoniumtetrakis(3,5-bis-trifluoromethylphenyl)borate, 4-acetamidephenyldiphenylsulfoniumtetrafluoroborate, 4-acetamide Phenyldiphenylsulfoniumtetrakis(pentafluorobenzyl)borate, dimethylnaphthylsulfoniumhexafluorophosphate, trifluoromethyldiphenylsulfoniumtetrafluoroborate, trifluoromethyldiphenylsulfoniumtetrakis(pentafluoro Lobenzyl) borate, phenylmethylbenzylsulfonium hexafluorophosphate, 10-methylphenoxatiinium hexafluorophosphate, 5-methylthianthrenium hexafluorophosphate, 10-phenyl-9,9-dimethylthioxante Nium hexafluorophosphate, 10-phenyl-9-oxothioxanthenium xanthenium tetraflu Oroborate, 10-phenyl-9-oxothioxanthenium tetrakis (pentafluorobenzyl) borate, 5-methyl-10-oxothiathenium tetrafluoroborate, 5-methyl-10-oxothiathenium tetra kiss(pentafluorobenzyl) borate, and 5-methyl-10,10-dioxothiathenium hexafluorophosphate.

Examples of the iodonium salt include (4-n-decyloxyphenyl)phenyliodonium hexafluoroantimonate, [4-(2-hydroxy-n-tetradecyloxy)phenyl]phenyliodonium Hexafluoroantimonate, [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) Idonium 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 triflate, diphenyliodonium bisulfate, 4,4' -dichlorodiphenyl iodonium bisulfate, 4,4'-dibromodiphenyl iodonium bisulfate, 3,3'-dinitrodiphenyl iodonium bisulfate, 4,4'-dimethyldiphenyl iodonium bisulfate, 4,4' -bissuccinimide diphenyl iodonium bisulfate, 3-nitrodiphenyl iodonium bisulfate, 4,4'-dimethoxydiphenyl iodonium bisulfate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate and (4-octyloxyphenyl)phenyliodoniumtetrakis(3,5-bis-trifluoromethylphenyl)borate.

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

Commercially available onium salts include, for example, Sanade 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 Optomer SP-150 , SP-151, SP-170, SP-171, SP-172 (above, manufactured by ADEKA), Irgacure261, Irgacure250 (manufactured by BASF), CI-2481, CI-2624, CI-2639, CI-2064 (above) , manufactured by Nippon Soda), CD-1010, CD-1011, CD-1012 (above, manufactured by Sartomer), 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 (above, manufactured by Midori Chemicals), PCI- 061T, PCI-062T, PCI-020T, PCI-022T (above, manufactured by Nippon Kayaku Co., Ltd.), IBPF, IBCF (manufactured by Sanwa Chemical) CD1012 (manufactured by Sartomer), IBPF, IBCF (above, manufactured by Sanwa Chemical), BBI-101, BBI-102, BBI-103, BBI-109 (above, manufactured by Midori Chemical), UVE1014 (manufactured by General Electronics), RHODORSIL-PI2074 (manufactured by Rhodia), WPI-113, WPI-116 (Wako Pure) Pharmaceutical company manufacture), etc. are mentioned.

In addition, J. Polymer Science: Part A: Polymer Chemistry, Vol. 31, 1473-1482 (1993), J. Polymer Science: Part A: Polymer Chemistry, Vol. 31, 1483-1491 (1993) described in The diaryliodonium salt which can be manufactured by this method can also be used. These may be used independently and may use 2 or more types together.

Examples of the dicarboxylic acid imides include N-(methylsulfonyloxy)naphthalene-1,8-dicarboxyimide, N-(tosyloxy)naphthalene-1,8-dicarboxyimide, N-[ (trifluoromethyl)sulfonyloxy]naphthalene-1,8-dicarboxyimide, N-(camphorsulfonyloxy)naphthalene-1,8-dicarboxyimide, N-(phenylsulfonyloxy)succinimide; N-(tosyloxy)succinimide, N-[(trifluoromethyl)sulfonyloxy]succinimide, N-(camphorsulfonyloxy)succinimide, N-[(trifluoromethyl)sulfonyl oxy]phthalimide, N-[(trifluoromethyl)sulfonyloxy]-cis-5-norbornene-end-2,3-dicarboxyimide, and the like.

Examples of the photobase generator include an acyclic acyloxyimino compound, an acyclic carbamoyloxime compound, a carbamoylhydroxylamine compound, a carbamic acid compound, a formamide compound, an acetamide compound, and a carbamate. compound, benzyl carbamate compound, nitrobenzyl carbamate compound, sulfonamide compound, imidazole derivative compound, amineimide compound, pyridine derivative compound, α-aminoacetophenone derivative compound, quaternary ammonium salt derivative compound, α-lactone ring derivative compound, an amineimide compound, a phthalimide derivative compound, etc. are mentioned. These may be used independently and may use 2 or more types together.

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

<Light Stabilizer>

As a light stabilizer, a ultraviolet absorber and a hindered amine type light stabilizer are mentioned, for example. An optical stabilizer may be used independently and may be used in combination of 2 or more type.

As the ultraviolet absorber, for example, salicylic acids (eg, phenyl salicylate, p-t-butylphenyl salicylate, p-octylphenyl salicylate, etc.), benzophenones (eg, 2,4 -dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-di Hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 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'-ditert-butylphenyl)benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2- (2'-hydroxyl-3',5'-ditert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxyl-3',5'-ditert-amylphenyl)benzotria Sol, 2-{(2'-hydroxyl-3',3",4",5",6"-tetrahydrophthalimidemethyl)-5'-methylphenyl}benzotriazole, etc.), triazines ( For example, 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-hydride Roxy-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)-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 anilides oxalate (eg For example, N-(2-ethylphenyl)-N'-(2-ethoxy-5-t-butylphenyl)oxalic acid diamide, N-(2-ethylphenyl)-N'-(2-ethoxy-phenyl ) oxalic acid diamide, 2-ethoxy-2'-ethyl-oxalic acid bisanilide, oxalic acid diamides having an aryl group which may be substituted on a nitrogen atom, etc.);

As the hindered amine light stabilizer, for example, 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, dimethyl succinate-1-(2-) Hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate with 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-penta Condensate of methyl-4-piperidinol and tridecyl alcohol, etc.) etc. are mentioned.

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

<UV-curable oligomer>

As an ultraviolet curable oligomer, a urethane acrylate oligomer, an epoxy acrylate oligomer, a polyester acrylate oligomer, etc. are mentioned, for example. An ultraviolet curable oligomer may be used independently and may be used in combination.

A commercially available urethane acrylate oligomer can be used. Commercially available urethane acrylate oligomers include, for example, CN929, CN965, CN968, CN981A75, CN985B88, CN991, CN970AH75, CN975, CN992, CN994 and CN9165 (manufactured by Sartomer Corporation), U-4HA and U-6HA (Sin-Nakamura). Chemical Industries, Ltd.), AH-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, and DAUA-167 (made by Kyoeisha Chemical Company), etc. are mentioned.

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

A commercially available polyester acrylate oligomer can be used. Commercially available polyester acrylate oligomers include, for example, CN292, CN2259, CN2262, CN2270, CN2271E, CN2272, CN2273, CN2276, CN2279, CN2285, CN2298, CN2300, CN2301, CN2302, CN2303 and CN2304 manufactured by Satomer. ) and the like. These polyester acrylate oligomers may be used independently and may be used in combination.

When the dispersion of the present invention contains an ultraviolet curable oligomer, the amount is preferably 0.01 parts 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. Preferably it is 15 weight part or less, More preferably, it is 10 weight part or less, More preferably, it is 5 weight part or less.

<Fluorescent brightener>

As the optical brightener, for example, dialkylaminocoumarin, bisdimethylaminostilbene, bismethylaminostilbene, 4-alkoxy-1,8-naphthalenedicarboxylic acid-N-alkylimide, bisbenzoxazolyl Ethylene, 1, 4-bis (2-benzooxazolyl) naphthalene, dialkyl stilbene, etc. are mentioned. Commercially available optical brighteners include, for example, Kayahor 3BS Liq., Kayahor TAC Liq., Kayaphor HBC Liq., Kayalight B, Kayaphor AS 150, Kayaphor CR 200, Kayaphor JB Liq., Mikawhite ATN conc. (manufactured by Nippon Kayaku Co., Ltd.), TINOPAL OB, TINOPAL NFW Liqid (manufactured by BASF), Hakkol P, Hakkol PHD, Hakkol RF, Hakkol PSR, Hakkol PSR-B, Hakkol CHP-B, Hakkol PY-2000, Hakkol PYB-D , Hakkol BE conc, Hakkol SG conc 150, Hakkol TH-100, Hakkol S-100, Hakkol RX-1, Hakkol OW-11, Hakkol OW-10 extra, Hakkol KIP H/C, Hakkol SF, Hakkol JC, and Hakkol PMS H/C (made by Showa Chemical Industries, Ltd.), Nikkafluor SB conc, Nikkafluor KB, Nikkafluor OB, Nikkabright CX H/C (made by Nippon Chemical Industries, Ltd.), etc. are mentioned. An optical brightener may be used independently and may be used in combination of 2 or more type.

When the dispersion of the present invention contains an optical brightener, the amount is preferably 0.01 parts by weight or more, preferably 5 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. Preferably it is 3 weight part or less, More preferably, it is 1 weight part or less.

<Leveling agent>

As a leveling agent, For example, Polyflow No.45, Polyflow KL-245, Polyflow No.75, Polyflow No.90, Polyflow No.95 (made 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 Shin-Etsu Chemical Co., Ltd.), Sufflon SC-101, Sufflon KH-40 (manufactured by AGC Semi-Chemical Co., Ltd.), Ptergent 222F, Ptergent 251, FTX-218 ( Neos Corporation), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (Mitsubishi Materials Corporation), Megapac F-171, Megapac F-177, Mega Pak F-475, Mega Pak F-556, Mega Pak R-30 (manufactured by DIC), Adeca Col W-193, Adeca Col W-287, Ade Ca Col W-288, Ade Ca Col W-304 ( ADEKA), SN Wet 366, Nobco 38-C, SN Disper Sand 5468, SN Disper Sand 5034, SN Disper Sand 5027, SN Disper Sand 5040, SN Disper Sand 5020 (Sannovco), Fluoro Alkylbenzenesulfonate, fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether, fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylsulfonate, diglycerin tetrakis(fluoroalkylpolyoxyethylene ether ), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, poly Oxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurate Lylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate rate, polyoxyethylene sorbitanoleate, polyoxyethylene naphthyl ether, alkylbenzenesulfonate, alkyldiphenyletherdisulfonate, and the like.

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

<Basic compound>

As a basic compound, ammonia, an organic amine compound, a metal hydroxide, etc. are mentioned, for example. The basic compound is preferably ammonia or an 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, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorph Poline, N-ethylmorpholine, etc. are mentioned. Among these, N,N-dimethylethanolamine is preferable.

As a metal hydroxide, lithium hydroxide, potassium hydroxide, sodium hydroxide, etc. are mentioned, for example.

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

<Organic solvent>

As an organic solvent, For example, 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; alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, and n-butanol; Glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether and 3-methoxy-3-methyl-1-butanol ; cellosolves such as methyl cellosolve, cellosolve, butyl cellosolve, dioxane, MTBE (methyl tertiary butyl ether) and butyl carbitol; Glycol esters, such as ethylene glycol monomethyl ether acetate, PMA (propylene glycol monomethyl ether acetate), diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl ether acetate, etc. are mentioned. These may be used independently and may be used in combination of 2 or more type.

The amount of the organic solvent in the dispersion of the present invention is preferably 0 to 100 parts by weight, more preferably 0 to 50 parts by weight, from the viewpoint of odor, etc., with respect to 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group. , More preferably, it is 0-30 weight part, More preferably, it is 0-10 weight part. It is particularly preferred that the dispersion of the present invention contains no organic solvent.

<crosslinking agent>

By including a crosslinking agent, there exists a tendency for adhesiveness, the water resistance of an adhesive layer, and solvent resistance of an adhesive layer to improve more. Examples of the crosslinking agent include an epoxy compound, a polyisocyanate compound (particularly an aliphatic polyisocyanate compound), an oxazoline compound, an aziridine compound, a carbodiimide compound, an active methylol compound, an active alkoxymethyl compound, a metal chelate, hydra A zide compound, a hydrazine compound, etc. are mentioned. Among these, an aliphatic polyisocyanate compound, a carbodiimide compound, an oxazoline compound, a hydrazide compound, and a hydrazine compound are preferable. Among them, an aqueous (water-soluble or water-dispersible) one is more preferable. These crosslinking agents may be used independently and may be used 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 Sumi Jour (registered trademark) N3200, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547, and 44V10 manufactured by Sumika Covestro Urethane. , 44V20 and E 21-1, Desmojour (registered trademark) N3100, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP manufactured by Sumitomo Covestro Urethane -2547 and DA-L, E14 and E 22, Baihi Jour (registered trademark) 304 and XP2655 by Sumitomo Kovestro Urethane, BASONAT (BASONAT (registered trademark)) PLR8878 and HW-100 by BASF, Takenate (trademark) WD720, WD725, and WD730 by Takeda Chemical Industries, Ltd., Duranate (trademark) WB40-100, WB40-80D, and WX-1741 by Asahi Chemical Industries, Ltd. are mentioned.

As a specific example of a carbodiimide compound, Nisshinbo Chemical Co., Ltd.: Carbodilite (SV-02, V-02, V-02-L, V-04, E-01, E-02) etc. are mentioned can

As a specific example of a hydrazide compound, Otsuka Chemical Co., Ltd.: ADH (dipic acid dihydrazide), SDH (sebacic acid dihydrazide), DDH (dodecanediohydrazide), IDH (isophthalic acid dihydrazide) , SAH (salicylic acid hydrazide), etc. are mentioned.

As a specific example of a hydrazine compound, Otsuka Chemical Co., Ltd.: monohydrochloric acid hydrazine, dihydrochloric acid hydrazine, monohydrobromic acid hydrazine, hydrazine carbonate, etc. are mentioned.

When the dispersion of the present invention contains a crosslinking agent, the amount is preferably 0.01 parts by weight or more, preferably 30 parts by weight or less, more preferably based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. is 15 parts by weight or less, more preferably 10 parts by weight or less, and 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 a photosensitizer is 450 nm or less normally, Preferably it is 250-380 nm. Examples of the photosensitizer include triethanolamine, triisopropanolamine, 4,4-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminoethylbenzoate and 4-dimethylaminobenzoic acid isoacyl. can be heard

When the dispersion liquid of the present invention contains a photosensitizer, the amount is preferably 0.01 parts by weight or more, preferably 15 parts by weight or less, with respect to 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group. Preferably it is 10 weight part or less, More preferably, it is 5 weight part or less.

＜Other resins or rubbers＞

The dispersion liquid of the present invention may contain other resin or rubber different from the chlorinated rubber as long as the effect of the present invention is not impaired. All other resin or rubber may use only 1 type, and may use 2 or more types together. In addition, in this specification, rubber means the elastomer which has elasticity, and resin means a thermoplastic resin or thermosetting resin which does not have 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, (meth)acrylic resins, 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 copolymer, vinyl chloride Leadene-(meth)acrylic acid ester copolymer, vinylidene chloride-acrylonitrile copolymer, chlorinated resin having a structural unit derived from α-olefin having 2 to 20 carbon atoms, polyurea, acrylonitrile-butadiene-styrene copolymer , chloroprene-based resin, acid-modified chloroprene-based resin, butyl rubber, brominated butyl rubber, modified rubber, styrene-(meth)acrylic acid copolymer, synthetic rubber, natural rubber, styrene-butadiene copolymer, polybutadiene, poly(meth)acrylic Ronitrile, poly(meth)acrylamide, polyester, modified polyamide, an epoxy resin, a styrenic block copolymer, these oligomers, etc. are mentioned. The other resin or rubber may be in the form of a solid (eg, powder of resin or rubber) or may be in the form of an emulsion.

An ethylene-vinyl ester copolymer is a copolymer containing an ethylene unit and a vinyl ester unit. As the vinyl ester unit, for example, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl ester of a tertiary carboxylic acid having 8 to 10 carbon atoms, and so-called vinyl versatate (for example, manufactured by Shell Chemicals, trade name: Veova) (trademark) 10) and the like unit derived from alkyl acid vinyl ester, etc. are mentioned.

The ethylene-vinyl ester copolymer may contain the unit derived from the monomer copolymerizable with ethylene and vinyl ester other than an ethylene unit and a vinyl ester unit. Examples of the monomer include a vinyl halide such as vinyl chloride, a monomer having a small amount of a functional group such as an amide group, (meth)acrylic acid ester, and the like.

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

The ethylene-vinyl acetate copolymer has different properties depending on the content of vinyl acetate and the like, and various vinyl acetate content and shapes (film, block, fiber, foam) can be used. The ethylene-vinyl acetate copolymer may contain other olefin units other than the ethylene unit. Examples of the ethylene-vinyl acetate copolymer containing another olefin unit include an ethylene-octene-vinyl acetate copolymer, an ethylene-butene-vinyl acetate copolymer, and an ethylene-propylene-vinyl acetate copolymer.

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

The ethylene-vinyl ester copolymer may be in the form of an emulsion. Such an emulsion may be manufactured by emulsion-polymerizing the monomer which comprises the said ethylene unit and a vinyl ester unit, and a commercially available thing may be used for it. Ethylene-vinyl ester copolymer emulsions include, for example, Sumika Flex (registered trademark) 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 (or higher, manufactured by Sumitomo Chemical Co., Ltd.), Vanflex OM-4000 and OM-4200 (or higher) , manufactured by Kuraray Co., Ltd.), Polysol (registered trademark) EVA AD-2, AD-3, AD-4, AD-5, AD-51, AD-56, AD-59 and P-900 (above, Showa Polymer Co., Ltd. product), Denka EVA tex (trademark) #20, #30, #40M, #60, #81, and #82 (above, Denka Co., Ltd. product) etc. are mentioned.

As the styrene-maleic acid copolymer, for example, Arasta 700, 703S (manufactured by Arakawa Chemical Industry Co., Ltd.), SMA (registered trademark) 1000, SMA (registered trademark) 2000, SMA (registered trademark) 3000 (Cray Valley's) company) and the like. As an emulsion of a styrene- maleic acid copolymer, VE-1122 (made by Seiko PMC Co., Ltd.) etc. is mentioned, for example.

Any of a homopolymer, a random copolymer, a block copolymer, and a graft copolymer may be sufficient as the resin which has a structural unit derived from the C2-C20 alpha-olefin. Moreover, what was made into low molecular weight and high molecular weight with a peroxide etc. may be sufficient.

Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-unde. cene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene and vinylcyclohexane and the like. Among 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 low-density. α-olefin homopolymers such as polyethylene, ultra-high molecular weight polyethylene and polypropylene (PP), isotactic (isotactic) polypropylene, syndiotactic polypropylene, and atactic polypropylene; α-olefin copolymers such as an ethylene-propylene copolymer, a propylene-1-butene copolymer, an ethylene-1-butene copolymer, an ethylene-1-octene copolymer, and an ethylene-1-hexene copolymer; and a copolymer of an α-olefin having 2 to 20 carbon atoms and a monomer copolymerizable with the α-olefin. In addition, the copolymer of an α-olefin having 2 to 20 carbon atoms and a monomer copolymerizable with the α-olefin may contain one type of unit derived from each, or two or more types of units derived from each. it may be

Examples of the monomer copolymerizable with α-olefin having 2 to 20 carbon atoms include α,β-unsaturated carboxylic acid and anhydrides thereof, metal salts of α,β-unsaturated carboxylic acid, α,β-unsaturated carboxylic acid and esters, vinyl esters, saponified vinyl esters, cyclic olefins, vinyl aromatic compounds, polyene compounds (such as dienes), (meth)acrylonitrile, vinyl halides, amides, and vinylidene halides. These may be used independently and may be used in combination.

α,β-unsaturated carboxylic acids and their anhydrides include, for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, monomethyl maleic acid, maleic acid monoethyl, half ester of maleic acid, half amide of maleic acid, half ester of itaconic acid, half amide of itaconic acid, and the like. Among them, 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. Specifically, the sodium salt and magnesium salt of (meth)acrylic acid are mentioned.

As α,β-unsaturated carboxylic acid ester, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) and esters of acrylate, 2-hydroxyethyl acrylate, dimethyl maleate and methacrylic acid and alcohol. Especially, methyl (meth)acrylate and ethyl (meth)acrylate are preferable.

Examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, and vinyl versatate. Especially, vinyl acetate is preferable.

As a saponified vinyl ester, vinyl alcohol etc. which are obtained by saponifying a vinyl ester with a basic compound etc. are mentioned, for example.

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 and vinylcyclohexane; and the like.

Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert. -Butyl styrene, ethyl styrene, vinyl naphthalene, etc. are mentioned.

Examples of the polyene compound include a linear or branched aliphatic conjugated polyene compound, an alicyclic conjugated polyene compound, an aliphatic non-conjugated polyene compound, an alicyclic non-conjugated polyene compound, and an aromatic non-conjugated polyene. compounds, and the like. 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, and 2-isopropyl-1,3-butadiene. , 2-methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-octadiene and 2,3-dimethyl-1,3-decadiene and the like.

Examples of the alicyclic conjugated polyene compound include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, and 2,3-dimethyl-1,3-cyclohexadiene. , 2-chloro-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-decadiene, 3,3-dimethyl-1,4 -hexadiene, 5-ethyl-1,4-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 4- methyl-1,4-nonadiene, 5-methyl-1,4-decadiene, 6-methyl-1,6-undecadiene and 4-ethylidene-12-methyl-1,11-pentadecadiene; can be heard

Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexane, vinylcyclohexene, 5-vinyl-2-norbornene, 1,4-divinylcyclohexane, and 1-isopropenyl-3-vinyl. Cyclopentane, methyltetrahydroindene, etc. are mentioned.

As an aromatic non-conjugated polyene compound, divinylbenzene, vinyl isopropenylbenzene, etc. are mentioned, for example.

Examples of the copolymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms include an ethylenically unsaturated carboxylic acid copolymer such as an ethylene-acrylic acid copolymer and an ethylene-methacrylic acid copolymer, and the ethylenically unsaturated carboxylic acid copolymer. Ionomer in which part or all of the carboxyl groups of the acid copolymer are neutralized with metal, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-isobutyl acrylate copolymer, ethylene -Ethylene-unsaturated carboxylic acid esters such as ethylene-unsaturated carboxylic acid ester copolymers such as n-butyl acrylic acid copolymer, ethylene-isobutyl acrylate-methacrylic acid copolymers, and ethylene-acrylic acid n-butyl-methacrylic acid copolymers - An unsaturated carboxylic acid copolymer and an ionomer in which part or all of its carboxyl groups are neutralized with a metal, etc. are mentioned.

As a modified product of a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, for example, a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms is mixed with α,β-unsaturated carboxylic acids or the like. The modified product obtained by modifying|denaturing by this is mentioned.

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

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

A modified product of a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms is a method in which the resin is melted and then α,β-unsaturated carboxylic acids or the like are added to the melt to modify the resin, toluene , can be produced by dissolving the resin in an organic solvent such as xylene, and then adding α,β-unsaturated carboxylic acids 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 wt%, more preferably 40 to 75 wt%, based on 100 wt% of the copolymer before modification. It is weight %, More preferably, it is 55 to 70 weight%.

For chlorination of a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms is dissolved or dispersed in an organic solvent, and chlorine gas is sprayed into the resulting mixture. It can be carried out by a method or the like.

As a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms and a modified product thereof, for example, Melten (registered trademark) H-6410M, H-6051, H-6960, H-6820 and H-6822X (Toso Corporation), Eval (registered trademark) L171B, F171B, H171B, E105B and G156B (Kurare, Inc.), Soanol (registered trademark) D2908, DT2904, DC3212, DC3203, E3808, ET3803, A4412, AT4403 , BX, 16DX, D2908H4 and A4412H4 (Nippon Synthetic Chemical Industry Co., Ltd.), Soa Resin (registered trademark) PG505 (Nippon Synthetic Chemical Industry Co., Ltd.), NISSO (registered trademark) PB (Nippon Soda Co., Ltd.), Poly Tail (registered trademark) H (Mitsubishi Chemical Co., Ltd.), EPOL (registered trademark) (Idemitsu Kogsan Co., Ltd.), OREVAC (registered trademark) G 18211, OE808 and OE825 (Arkema Co., Ltd.), LOTADAR MAH2210, 3200 , P3 3200, 3210, 4210, 6200, 3410, 3430 and 4720 (Arkema Corporation), BONDINE (registered trademark) LX4110, HX8210, TX8030, HX8290, HX8410 and AX8390 (Arkema Corporation), OREVAC (registered) Trademarks) T9314, T9318 and G18211 (Arkema Co., Ltd.), Umex (registered trademark) 2000 (Sanyo Chemical Industries, Ltd.), and Auroren (registered trademark) 100S and 200T (Nippon Paper Chemicals Co., Ltd.), etc. can be heard

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 prepared 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 emulsion may be used. As an emulsion of a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms and a modified product thereof, for example, Arobase (registered trademark) SA-1200, SB-1200, SE-1200, SB-1010 (Uni Tika Co., Ltd.), Aptorok (registered trademark) BW-5550 (Mitsubishi Chemical Co., Ltd.), Aurora (registered trademark) AE-202, AE-301 (Nippon Paper Co., Ltd.), Aquatex (registered trademark) EC-1200, EC-1700, AC-3100, MC-4400, HA-1100, 909 (Chuo Ewha Industrial Co., Ltd.) etc. are mentioned.

Examples of the chlorinated resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms include Elaslen (registered trademark) 401A, 303B (Showa Denko Co., Ltd.), Hadlene (registered trademark) CY- 9122P, 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 Superclone (registered trademark) 803L, 803MW, 814HS, 390S, HE-305, HE-505, HE -510, HE-515, HE-910, HE-915, HE-1070, HE-1200, HP-205, HP-215 and HP-620 (Nippon Paper Chemicals Co., Ltd.) etc. are mentioned.

The form of an emulsion may be sufficient as resin which has the structural unit derived from the chlorinated C2-C20 alpha-olefin. Such an emulsion may be prepared by emulsifying a chlorinated resin having a structural unit derived from α-olefin having 2 to 20 carbon atoms, or a commercially available emulsion may be used. As an emulsion of a resin having a structural unit derived from a chlorinated α-olefin having 2 to 20 carbon atoms, for example, Hadlene (registered trademark) EW-5303, EH-801, EW-5504, EZ-1000 and EZ- 2000 (Toyobo Co., Ltd.), Superclone (trademark) E-604, E-480T, and E-415 (Nippon Paper Chemicals Co., Ltd.), etc. are mentioned.

The polyurethane may be either expanded polyurethane or non-foamed polyurethane, but is preferably non-foamed polyurethane. Among non-foamed polyurethanes, water-soluble or water-dispersible polyurethanes are preferable. A commercially available polyurethane can be used. As a commercially available polyurethane, nipporan (trademark) 3110, 3116, 3016, 3113, 3124, 3126, 3230 (Nippon Polyurethane Kogyo Co., Ltd.) etc. are mentioned, for example. Commercially available water-soluble or water-dispersible polyurethanes include, for example, Dispercoll (registered trademark) U-42, U-53, U-54, U-56, KA-8481, KA-8584, KA-8755, KA -8756 and KA-8766 (Sumitomo Kovestro 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 Corporation), Youprene (registered trademark) UXA-306, UXA-307, Permarine UA-150, Permarine UA-200, Permarine UA-300, Permarine UA -310 and UWS-145 (Sanyo Chemical Industry Co., Ltd.), Superflex (registered trademark) 107M, 110, 126, 130, 150, 160, 210, 300, 361, 370, 410, 420, 460, 500M , 700, 750, 820 and 860 (Daichi Kogyo Pharmaceutical Co., Ltd.), and Adeca Bontiter (registered trademark) HUX-401, HUX-420A, HUX-380, HUX-561, HUX-210, HUX- 822, HUX-895, and HUX-830 (ADEKA, Ltd.) etc. are mentioned.

Polyvinyl chloride is obtained by a method of suspension polymerization or bulk polymerization of vinyl chloride, or the like. As polyvinyl chloride, hard polyvinyl chloride, semi-rigid polyvinyl chloride, soft polyvinyl chloride, etc. are mentioned, for example. Preferably, it is flexible polyvinyl chloride. As for polyvinyl chloride, Kanevinyl S-400, PSH-180, PSL-180 (Kaneka Corporation) etc. are mentioned, for example. As an emulsion of polyvinyl chloride, Viniblan 701, 700, 711 (Nissin Chemical Industry Co., Ltd.) etc. are mentioned, for example.

Chlorinated polyvinyl chloride is a thing obtained by chlorinating polyvinyl chloride by a chlorination method such as gaseous or liquid phase. As polyvinyl chloride, the homopolymer of vinyl chloride, and the copolymer of vinyl chloride and another monomer are mentioned, for example. Examples of the other monomer include ethylene, propylene, alkyl vinyl ether, vinylidene chloride, vinyl acetate, acrylic acid ester, and maleic acid ester. As for chlorinated polyvinyl chloride, Sekisui PVC-HA (Sekisui Chemical Industry Co., Ltd.) etc. are mentioned, for example.

As polyvinylidene chloride, Saran (SARAN) X05253-16 (made by Dow Chemical Corporation), resin for Saran Lab (trademark) (made by Asahi Chemical Corporation), etc. are mentioned, for example. As an emulsion of polyvinylidene chloride, Diofan 193D, A736, A036, A050, A063, B204, A115 (made by Solvay) etc. are mentioned, for example.

As a vinyl chloride-vinylidene chloride copolymer, IXAN SGA-1 (made by Solvay) etc. are mentioned, for example.

As a vinylidene chloride (meth)acrylic acid ester copolymer, IXAN PVS-109, 801, 815, Diofan A586, A602, A610 (made by Solvay) etc. are mentioned, for example.

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

The acid-modified chloroprene-based resin is obtained by graft copolymerizing the chloroprene-based resin with at least one selected from α,β-unsaturated carboxylic acids and anhydrides thereof. Examples of the α,β-unsaturated carboxylic acid and its acid anhydride include those exemplified as modified products of resins having structural units derived from α-olefins having 2 to 20 carbon atoms.

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

Examples of the brominated butyl rubber include JSR BROMOBUTYL 2255 and 2244 (manufactured by JSR), and Exxon bromobutyl 2255 (manufactured by Exxon Mobil Chemicals).

As a modified rubber, the chlorinated or bromination modified copolymer of the copolymer of isomonoolefin and paramethylstyrene is mentioned, for example, As a commercial item, Expro50 (Exxon Corporation) is mentioned, for example.

As a styrenic block copolymer, the block copolymer which consists of a diene block and a styrene block is mentioned, for example. Specifically, styrene-butadiene block copolymer (SB), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-butylene-styrene copolymer (SBBS) ) or a hydrogenated substance of those block copolymers, a styrene-isobutylene-styrene triblock copolymer (SIBS), and a styrene-isobutylene diblock copolymer (SIB) are mentioned. Such a hydrogenated substance may be a block copolymer in which both a styrene block and a diene block are hydrogenated, partial hydrogen such as a block copolymer in which only a diene block is hydrogenated, or a block copolymer in which a styrene block and a part of a diene block are hydrogenated. An additive may be sufficient.

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

The dispersion liquid of this invention may contain tackifying resin as another resin. As such resin, for example, rosin, a terpene-based resin, a petroleum-based resin obtained by polymerizing a petroleum fraction having 5 carbon atoms, and this hydrogenated resin, a petroleum resin obtained by polymerizing a petroleum fraction having 9 carbon atoms, and this hydrogenated resin , and other petroleum-based resins, coumarone resins, and indene resins. Specifically, for example, rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumarated rosin and their glycerin esters, pentaerythritol esters, methyl esters, triethylene glycol esters, phenol-modified products and rosins such as esters thereof; terpene-based resins such as terpene polymers, terpene phenols, β-pinene polymers, aromatic modified terpene polymers, α-pinene polymers, and terpene-based hydrogenated resins; Petroleum-type resin which superposed|polymerized the C5 petroleum fraction, the petroleum-type resin which superposed|polymerized the C9 petroleum fraction, and these hydrogenated resins; and petroleum-based resins such as maleic acid-modified products and fumaric acid-modified products, and chlorinated paraffins.

Examples of the terpene-based resin 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.) And Tertac 80 (Nippon Terpene Chemical Co., Ltd.) etc. are mentioned. As an emulsion of a terpene type resin, Tamanol E-200NT, E100 (Arakawa Chemical Industry Co., Ltd.) etc. are mentioned, for example.

As chlorinated paraffin, for example, Enpara (registered trademark) 70, 50, AR-500 (Ajinomoto Fine Techno Co., Ltd.), Toyoparax (registered trademark) 250, 265, 270, 150, A50 (Toso ( Note)) and the like.

When the dispersion of the present invention contains other resins or rubbers, the amount is preferably 0.01 parts by weight or more, preferably 100 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, it is 50 weight part or less, More preferably, it is 30 weight part or less, More preferably, it is 20 weight part or less.

<Thickener>

A thickener can be used for viscosity adjustment of a dispersion liquid. Thickeners include, for example, adecanol (registered trademark) UH-140 S, 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 Thickener 920, 922, 924, 926, 929-S, A-801, A-806, A- 812, A-813, A-818, 621N, 636, 601, 603, 612, 613, 615, 618, 621N, 630, 634, 636 and 4050 (Sannobco Co., Ltd.) and the like.

<Method for producing dispersion>

The dispersion liquid of the present invention can be prepared by a method similar to that described in Examples to be described later. Hereinafter, the manufacturing method of the dispersion liquid of this invention is demonstrated in detail.

Water, a chlorinated rubber, a compound having a polymerizable group, and, if necessary, other components (especially surfactants, etc.) are mixed and stirred to prepare a preliminary dispersion liquid. There is no limitation in particular in the method of this preliminary dispersion, It can implement using well-known means and apparatus. A known apparatus is, for example, a homomixer. When using a homomixer, 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 to 10 minutes. to be. It is preferred to start stirring with a mixture at room temperature.

Next, using a high-pressure homogenizer, the obtained preliminary dispersion liquid is homogenized. 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, fine dispersion of the dispersoid becomes insufficient, and conversely, even if the pressure exceeds 1,000 bar, fine dispersion of the dispersoid is not improved. The number of times of the homogenization treatment by a high pressure homogenizer becomes like this. Preferably it is 2-10 times, More preferably, it is 3-8 times. If the number of times of the treatment is less than 2, fine dispersion of the dispersoid becomes insufficient, and conversely, even if the number of times of the treatment exceeds 10 times, the fine dispersion of the dispersoid is not improved. It is preferable to cool the preliminary dispersion obtained by the homomixer to room temperature, and then start the homogenization treatment by the high-pressure homogenizer.

As a high-pressure homogenizer, "LAB1000", "LAB2000", "15MR", "G-MODEL", "R-MODEL" by SMT Co., Ltd. product, etc. are mentioned, for example.

To the dispersion of the present invention prepared as described above, water may be further added and stirred to prepare a diluted dispersion. Moreover, you may manufacture the dispersion liquid containing another component by adding and stirring another component (for example, a leveling agent) further to the dispersion liquid of this invention manufactured as mentioned above.

<Use of dispersion>

As mentioned above, the dispersion liquid of this invention is useful as a water-based adhesive agent, a primer, or those raw materials. Further, the present invention provides a coating film formed from the dispersion, and a cured product of the coating film. Moreover, this invention provides the laminated body in which the 1st base material, the said hardened|cured material, the adhesive bond layer, and the 2nd base material are laminated|stacked in this order. It is preferable that the 1st base material consists of an olefin polymer or an ethylene-vinyl acetate copolymer. The laminate of this invention WHEREIN: The said hardened|cured material may further exist between an adhesive bond layer and a 2nd base material.

As a material for an adherend to which the dispersion of the present invention is applied, or an adherend to which the coating film and cured product of the present invention are laminated (including the first and second substrates), for example, wood, plywood, medium density Wood-based materials, such as a fiberboard (MDF), a particle board, and a fiber board; Cellulose materials, such as cotton cloth, cotton-containing fiber, abrasion cloth, and rayon; (1) homopolymers and copolymers of ethylene, olefinic polymers such as homopolymers and copolymers of propylene, (2) homopolymers and copolymers of styrene, (3) polycarbonate, (4) acrylonitrile-butadiene- Styrene copolymer (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 copolymer (EVA), (11) Plastic materials such as polyamide-based resins, such as polyamide 6 and polyamide 66; 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. An adherend may consist of 1 type of material, and may consist of 2 or more types of materials. In addition, the to-be-adhered body may be a kneaded-molded article of the said plastic material and fillers, such as talc, silica, activated carbon, and carbon fiber.

The dispersion of the present invention is, among the above-mentioned adherends, adhesion between a cellulosic material and a plastic material, polyvinyl chloride, ethylene-vinyl acetate copolymer, cotton-containing fiber, polyamide-based resin, olefinic polymer, polyurethane, rubber or crosslinking. It can be used suitably for adhesion|attachment of rubber, synthetic leather, etc. Examples of the shape of these adherends include films, sheets, and blocks, but preferably, the adherends in the form of films or sheets are preferred.

Examples of the olefin-based polymer include resins and modified products having structural units derived from α-olefins having 2 to 20 carbon atoms described in <Other resin or rubber>. Moreover, as a plastic material, what was demonstrated in <Other resin or rubber> is mentioned, for example.

The cotton-containing fiber may be a fiber of 100% cotton, or a blend fiber of cotton and other natural fibers and/or chemical fibers. Other natural fibers include, for example, wool, silk and hemp. Examples of chemical fibers include synthetic fibers (eg, polyester fibers, polyamide fibers), semi-synthetic fibers (eg, cellulose fibers such as acetate, protein fibers such as promix); Regenerated fibers (for example, cellulosic fibers such as rayon, cupra, and polynosic) and inorganic fibers (for example, carbon fibers, glass fibers) and the like are mentioned. As a shape of a cotton-containing fiber, a woven fabric, a knitted fabric, a nonwoven fabric, meriyasu, a felt, a film, or a block form etc. are mentioned, for example.

As polyamide-type resin, polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, polyamide 12, etc. are mentioned, for example. The shape of the polyamide-based resin may be any of a film, a block, a fiber, or a foam shape.

As rubber or crosslinked rubber, it is a thermoplastic rubber, for example; diene rubbers such as natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, and chloroprene rubber; non-diene rubbers such as butyl rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, silicone rubber, and fluororubber; and cross-linked products thereof. Rubber or crosslinked rubber may be used individually, respectively, and may use 2 or more types together. If necessary, a reinforcing agent such as clay, carbon black or silica, a silane coupling agent, an antioxidant, a softening agent, zinc oxide, stearic acid, a vulcanization accelerator, a vulcanizing agent, sulfur, or the like may be used in combination.

Synthetic leather includes both synthetic leather and artificial leather in a narrow sense. In short, synthetic leather may be synthetic leather obtained by applying a synthetic resin to natural or synthetic fabric, etc. An artificial leather obtained by impregnating cloth (usually, a nonwoven fabric) with a synthetic resin and further applying the synthetic resin may be used. As these synthetic resins, a polyurethane-type resin, polyamide-type resin, polyamino acid-type resin, etc. are mentioned, for example, Preferably, it is a polyurethane-type resin.

The dispersion liquid of the present invention can be effectively used for adhesion to adherends such as films, sheets, structural materials, building materials, automobile parts, electrical/electronic products, packaging materials, clothing and footwear. In particular, the dispersion of the present invention is suitable for bonding constituent materials (subjects) such as upper, middle, and outer soles in footwear such as men's shoes, women's shoes, and industrial work shoes, such as sports shoes, town shoes, and business shoes. It is preferable as an adhesive, a primer or a raw material for them. The surfaces of these adherends may be smooth or may have irregularities. Moreover, in order to improve adhesiveness, you may surface-treat a to-be-adhered body. Examples of surface treatment include primer treatment, blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, and formation of an anchor layer. can

Next, the manufacturing method of the laminated body of this invention mentioned above is demonstrated.

First, the dispersion is applied to the surface of a first substrate, optionally a second substrate. What is necessary is just to implement application|coating by a well-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, brushing, and spatula coating. have.

Application|coating and drying of a dispersion liquid may be performed only once, respectively, and may be performed 2 times or more. The method of application|coating and drying may combine the same method, respectively, and may combine different methods.

After apply|coating a dispersion liquid to a 1st base material, you may dry or heat-process a coating film, and you may irradiate an electromagnetic wave after that. Heating temperature is about 30-150 degreeC, for example, Preferably it is about 40-80 degreeC. 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 drying or heat processing of a coating film, you may perform leaving-to-stand (natural drying) of a coating film further. It is preferable to irradiate the coating film formed from the dispersion liquid with an electron beam (in particular, ultraviolet rays) to form a cured product of the coating film.

When irradiating an electromagnetic wave to a coating film, as a light source for it, a metal halide lamp, a high-pressure mercury-vapor lamp, an ultra-high pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, an arc lamp, a laser etc. are mentioned, for example. Among these, a metal halide lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, and a low pressure mercury lamp are preferable. The peak illuminance of electron beam irradiation is preferably from 5 to 2000 mW/cm 2 , more preferably from 10 to 2000 mW/cm 2 . The cumulative dose is preferably 20 to 3000 mJ/cm 2 , and more preferably 100 to 2500 mJ/cm 2 .

Before apply|coating a dispersion liquid to a to-be-adhered body, you may surface-treat to a 1st base material. As the surface treatment, for example, primer treatment, blast treatment, chemical treatment, degreasing treatment, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, formation of an anchor layer, etc. can be heard

It is preferable that 95 weight% or more of the water contained in the dispersion liquid is removed from the coating film after drying. Thus, by reducing the water|moisture content in a coating film, the adhesiveness of a coating film and the hardened|cured material obtained from it can be ensured.

The thickness of the coating film after drying becomes like this. Preferably it is about 0.01-300 micrometers, More preferably, it is about 0.01-200 micrometers, More preferably, it is about 0.01-50 micrometers.

Next, a liquid adhesive is applied to at least one of the first substrate and the second substrate to which the dispersion is applied, followed by drying or heat treatment. Although these application|coating and drying or heat processing may only be performed once to at least one of a 1st base material and a 2nd base material, you may apply|coat an adhesive agent and heat-dry both once or more once. Conditions, such as the application|coating method of an adhesive agent, the thickness of the coating film after drying, the method of drying or heat processing, temperature, and time, etc. can be changed suitably. The same conditions as application|coating of the above-mentioned dispersion liquid etc. may be selected, and different conditions may be selected.

When apply|coating an adhesive agent to both of a 1st base material and a 2nd base material, the same adhesive agent may be apply|coated with respect to a 1st base material and a 2nd base material, and different adhesive agents may be apply|coated. For good adhesion of the first substrate and the second substrate, it is preferable to use the same adhesive. The dispersion liquid used above may be sufficient as an adhesive agent, and a commercially available adhesive agent may be sufficient as it.

The thickness of the adhesive layer can be appropriately adjusted according to the composition of the adhesive to be used, the material and shape of the substrate, and the like. The thickness of an adhesive bond layer becomes like this. Preferably it is about 0.01-300 micrometers, More preferably, it is about 0.01-200 micrometers.

Before applying the liquid adhesive to the adherend (the first substrate and/or the second substrate), the adherend may be subjected to the surface treatment described above.

There is no limitation in particular as a method of bonding together the 1st base material and 2nd base material to which the dispersion liquid and/or adhesive agent were apply|coated, What is necessary is just to bond these together mechanically or manually. At the time of bonding, you may apply a heat|fever, a pressure, or both. In the case of heating, it is necessary to heat within a temperature range in which the first and second substrates and the adhesive layer do not deteriorate, and the heating temperature is preferably about 120° C. or less, more preferably about 100° C. or less. . Heating can be performed using a normal hot-air circulation type oven, an infrared heater, a microwave oven, etc. In the case of pressurization, the pressure is, for example, about 100 g/cm 2 or more and less than the pressure at which the shapes of the first and second substrates are deformed. When heating and/or pressurizing, the time is, for example, about 1 second to 10 days.

As a 1st base material and a 2nd base material, the thing similar to the to-be-adhered body mentioned above is mentioned, for example. The first substrate is preferably a substrate made of an olefin-based polymer or an ethylene-vinyl acetate copolymer. The second substrate is preferably a substrate selected from the group consisting of polyvinyl chloride, synthetic leather, rubber, cotton-containing fibers and polyolefin-based polymers.

The adhesive layer is obtained by, for example, applying a liquid polyurethane adhesive, a liquid rubber-based adhesive, a liquid acrylic adhesive, or a liquid epoxy adhesive, and removing water, an organic solvent, and the like.

As a liquid polyurethane adhesive agent, the above-mentioned water-soluble or water-dispersible polyurethane etc. are mentioned, for example.

Examples of the liquid rubber adhesive include natural rubber, chloroprene rubber, styrene-butadiene copolymer rubber (SBR), isobutylene rubber, butyl rubber, styrene-isoprene-styrene block copolymer rubber (SIS), styrene-butadiene- and liquid adhesives containing rubber components such as styrene block copolymer rubber (SBS), butadiene-acrylonitrile copolymer rubber (NBR), and butadiene rubber (BR). A rubber component may use only 1 type and may use 2 or more types together. Moreover, in addition to these rubber components, you may add adhesion-imparting resin, such as a rosin resin, a terpene resin, and a petroleum resin, to a rubber-type adhesive agent.

Examples of the liquid acrylic adhesive include a liquid adhesive containing a copolymer of an acrylic acid ester and/or methacrylic acid ester as an adhesive component, a functional group-containing monomer, and a monomer for the purpose of improving cohesion. can An isocyanate crosslinking agent, a chelate crosslinking agent, an epoxy crosslinking agent, etc. may be added to the liquid acrylic adhesive.

Examples of acrylic acid esters include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, Acrylic acid n-lauryl etc. can be illustrated preferably. Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, methacrylate. Preferred examples include n-hexyl acrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, and n-lauryl methacrylate.

Examples of the functional group-containing monomer 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; hydroxyalkyl esters of acrylic acid or methacrylic acid such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; N-substituted such as acrylamide, methacrylamide, diacetone (meth)acrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-butoxymethylacrylamide, N-butoxymethacrylamide or unsubstituted acrylamide; glycidyl esters of acrylic acid or methacrylic acid such as glycidyl methacrylate and glycidyl methacrylate; Acrylonitrile etc. can be illustrated preferably.

Examples of the liquid epoxy adhesive include liquid adhesives containing an epoxy resin having one or more epoxy groups per molecule on average. As an epoxy resin, the epoxy resin obtained from bisphenol A and epichlorhydrin, the polyglycidyl ether obtained from bisphenol F and epichlorhydrin, or hydrogenated bisphenol A and epichlorhydrin, etc. are illustrated. In addition, oxazolidone-modified epoxy resins, novolac-type epoxy resins, polyfunctional phenol-type epoxy resins, various halogenated epoxy resins, glycidyl ester-type epoxy resins, polyglycol-type epoxy resins, cyclic aliphatic epoxy resins, etc. can also be used. have. These epoxy resins may be used independently and may use 2 or more types together.

Liquid polyurethane adhesive, liquid rubber adhesive, liquid acrylic adhesive, and liquid epoxy adhesive may be adhesives in the form of solutions, dispersions, or emulsions, or hot melt adhesives used in a molten state.

The adhesive agent which comprises an adhesive bond layer may contain the other component (for example, resin) different from the above-mentioned component. Examples of the resin that the adhesive may contain include olefin resin, polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), polytetrafluoroethylene (PTFE) , an acrylonitrile-butadiene-styrene copolymer (ABS resin), an AS resin, and a modified product of the resin. These may be used independently and may use 2 or more types together.

Moreover, as resin which an adhesive agent may contain, tackifying resin is mentioned, for example. As tackifying resin, for example, rosin, a terpene-type resin, the petroleum resin which superposed|polymerized the C5 petroleum fraction, this hydrogenated resin, the petroleum resin which superposed|polymerized the C9 petroleum fraction, and this hydrogenated resin. , and other petroleum-based resins, coumarone resins, indene resins, polyurethane resins, and the like.

In addition, as other components which the adhesive agent may contain, for example, surfactant, photoinitiator, light stabilizer, ultraviolet curable oligomer, optical brightener, leveling agent, basic compound, organic solvent, crosslinking agent, photosensitizer, Phenolic stabilizer, phosphite stabilizer, amine stabilizer, amide stabilizer, antioxidant, weathering stabilizer, antisettling agent, antioxidant, heat stabilizer, thixotropic agent, thickener, defoaming agent, viscosity modifier, weathering agent, pigment dispersant, antistatic agent , lubricants, nucleating agents, flame retardants, oil agents, dyes, curing agents; transition metal compounds such as titanium oxide (rutile type) and zinc oxide; Pigments, such as carbon black; Glass fiber, carbon fiber, potassium titanate fiber, wollastonite, calcium carbonate, calcium sulfate, talc, glass flake, barium sulfate, clay, kaolin, fine powder silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, inorganic or organic fillers such as magnesium oxide and celite; and the like.

Example

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 and the like, and is implemented with appropriate changes within the range that can be suitable for the above and below gist. It is of course possible, and all of them are included in the technical scope of the present invention.

In addition, "part", "%" and "ppm" described below mean "part 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 the flask combustion-ion chromatography method.

The median diameter (volume basis) of the dispersoid described in the table below is a value measured with a laser diffraction particle diameter measuring apparatus LA-950V2 manufactured by HORIBA Corporation.

As a rotation and revolution stirrer for preparing the measurement sample of backscattered light intensity, "rotation/revolution mixer Awatori Rentaro ARE-310" manufactured by Thinky was used.

As an apparatus for measuring the backscattered light intensity of the measurement sample, "Taviscan TOWER" manufactured by Formulation was used.

A measurement sample is prepared from the dispersion prepared in Examples and Comparative Examples to be described later by using the rotational revolution stirrer, measurement is started within 10 minutes from sample preparation, and the upper, middle and bottom portions of the measurement sample in the sample cell are The maximum value in the absolute value of the amount of change in the backscattered light intensity (%) measured 24 hours after starting the measurement with respect to the backscattered light intensity (%) measured 30 minutes after starting the measurement in each α was calculated and evaluated according to the following criteria. The results are shown in the table below.

(circle): All the requirements of said Formula (I) - (III) are satisfied.

x: Any or all of the requirements of the above formulas (I) to (III) are not satisfied.

The chlorinated rubber used in the Example and the comparative example, the compound which has a polymeric group, a photoinitiator, surfactant, and a leveling agent are as follows.

Chlorinated rubber 1: Pergut S20 (Covestro, chlorine atom content: 64.5% or more, melting point: 250°C, polystyrene conversion weight average molecular weight (Mw): 75,000, chlorinated rubber having no carboxyl group or carboxylic acid anhydride structure)

Compound 1 having a polymerizable group: dodecyl methacrylate (containing 970 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)

Compound 2 having a polymerizable group: 1,6-hexanediol dimethacrylate (contains 60 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)

Compound 3 having a polymerizable group: 2-phenoxyethylene glycol methacrylate (containing 100 ppm of 4-methoxyphenol, Shin-Nakamura Chemical Co., Ltd.)

Compound 4: having a polymerizable group: tricyclodecanedimethanol diacrylate (contains 800 ppm of 4-methoxyphenol, Shin-Nakamura Chemical Co., Ltd.)

Compound having a polymerizable group 5: tricyclodecanedimethanol dimethacrylate (containing 300 ppm of 4-methoxyphenol, Shin-Nakamura Chemical Co., Ltd.)

Photoinitiator 1: 2-hydroxy-2-methylpropiophenone (Tokyo Chemical Industry Co., Ltd.)

Surfactant 1: Aqualon KH-10 (Daichi Kogyo Pharmaceutical Co., Ltd.)

Surfactant 2: Emalgen 109P (Kao Co., Ltd.)

Basic compound 1: 2-(dimethylamino)ethanol (Tokyo Chemical Industry Co., Ltd.)

Fluorescent brightener 1: Nikkafluor OB (Nippon Chemical Industry Co., Ltd.)

Leveling agent 1: BYK-349 (Big Chemie Japan)

<Production Example 1: Preparation of dispersion 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), compound 2 having a polymerizable group (45 parts), and polymerization Compound 3 (10 parts) having an open group and photoinitiator 1 (1 part) were injected and stirred at 60°C to prepare a solution (hereinafter referred to as “solution 1”), and the solution 1 was cooled to room temperature .

Surfactant 1 (5 parts) was put into ion-exchange water (300 parts), it stirred at 60 degreeC, and the aqueous solution (henceforth "solution 2") of surfactant 1 was prepared.

At room temperature, solution 2 was added to solution 1 and stirred to prepare a mixture. Then, at room temperature, using TK Robomix (manufactured by PRIMIX, Ltd.) equipped with a homomixer MARKII, the obtained mixture was stirred at 16,000 rpm for 5 minutes 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 resulting emulsion was filtered through a 200 mesh nylon net to give an emulsion A liquid dispersion E1 was obtained. The nonvolatile matter concentration of the obtained dispersion liquid E1 was 25%.

<Production Examples 2 to 7: Preparation of dispersions E2 to E7>

Emulsions E2 to E7 were obtained in the same manner as in Production Example 1 except that the amounts of chlorinated rubber shown in Table 1, a compound having a polymerizable group, a photopolymerization initiator, a surfactant, and ion-exchanged water were used. In addition, in manufacture example 6, dispersion liquid E6 was manufactured using the solution which added the optical brightening agent of the quantity shown in Table 1. In Production Example 7, a dispersion liquid E7 was prepared without using a photoinitiator.

<Production Examples 8 to 12: Preparation of dispersion liquids E8 to E12>

The same as in Production Example 1 except for the amounts of the chlorinated rubber shown in Table 1, the compound having a polymerizable group, the photopolymerization initiator, the surfactant, and the ion-exchanged water, the stirring time by a homomixer, and the number of homogenization treatments by the high-pressure homogenizer. and dispersions E8 to E12 which are emulsions were obtained. In Production Example 12, a dispersion liquid E12 was prepared using a solution to which a basic compound in the amount shown in Table 1 was added.

Types of dispersions prepared in Production Examples 1 to 12; type and amount (parts) of ingredients used; The total amount (%) of the chlorinated rubber and the compound having a polymerizable group in the obtained dispersion, the amount (%) of the chlorinated rubber, the amount (%) of the compound having a polymerizable group and not having a cyclic structure, and a polymerizable group and a cyclic structure Amount (%) of the compound which has a structure (all are a value with respect to the sum total of a chlorinated rubber, the compound which has a polymeric group, and water); Stirring time by homomixer (min); the number of treatments by a high-pressure homogenizer; And the evaluation result of the median diameter (micrometer) of a dispersoid is shown in Table 1 below.

<Examples 1-7 and Comparative Examples 1-5: Preparation of water-based adhesives F1-F12>

Any of dispersion liquids E1-E12, leveling agent 1 (BYK (registered trademark)-349, Big Chemie Japan), and ion-exchanged water in an amount shown in Table 2 were mixed, stirred with a three-one motor, and emulsified Liquid water-based adhesives F1 to F12 were obtained.

In addition, after Examples 1-7 and Comparative Examples 1-5, a leveling agent is further contained, and the dispersion liquid preferable as an adhesive agent is described as "aqueous adhesive agent".

Types of the water-based adhesives manufactured in Examples 1-7 and Comparative Examples 1-5; the type and amount (parts) of the dispersion used; amount (parts) of leveling agent 1 and ion-exchange water used; The total amount (%) of the compound having a chlorinated rubber and a polymerizable group in the obtained aqueous adhesive, the amount (%) of the chlorinated rubber, the amount (%) of a compound having a polymerizable group and not having a cyclic structure, and a polymerizable group and a ring Amount (%) of the compound which has a type|mold structure (all are a value with respect to the sum total of a chlorinated rubber, the compound which has a polymeric group, and water); median diameter (μm) of the dispersoid; And the evaluation result of the change amount of backscattered light intensity is shown in following Table 2.

<Production Example 13: Preparation of Liquid Adhesive 1>

Polyurethane emulsion (Dispercoll (registered trademark) U-54, Sumica Covestro Urethane Co., Ltd.), isocyanate (Desmojour (registered trademark) N3300, Sumika Covestro Urethane Co., Ltd.), and Leveling Agent 1 , polyurethane emulsion: isocyanate: the nonvolatile matter ratio of the leveling agent 1 was mixed so that the ratio of 100 parts: 5 parts: 1 part was obtained, and the adhesive 1 which is an emulsion liquid was obtained.

<Example 8: Preparation of laminate 1>

After leaving the water-based adhesive F1 at 50° C. for 7 days with a constant-temperature air blower, it is applied to the foam of ethylene-vinyl acetate copolymer (EVA), which is the first substrate, using a brush (weight per unit area of the coating film after drying: about 3 g/m 2 ), dried at 70° C. for 5 minutes, and irradiated with ultraviolet rays with a conveyor-type UV irradiation device (manufactured by Eye Graphics Co., Ltd., Eye Grand Daisy ECS-4011GX) to obtain a laminate of EVA and a cured product (lamp : High-pressure mercury lamp, lamp output: 3 kW, lamp height: 110 mm, conveyor speed: 276 m/min, peak illuminance: 250 mW/cm2, integrated dose: 700 mJ/cm2 (UVICURE PLUS II, UV -A measurements, FusionUV Systems Japan K.K.).

Next, 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 ), and oven dried at 70° C. for 5 minutes. , a laminate of a cotton cloth and an adhesive layer was obtained.

Adhesive 1 was applied using a brush to the surface on the side of the cured product of the laminate of the EVA and the cured product obtained as described above, and on the surface on the side of the adhesive layer of the laminate of the cotton canvas and the adhesive layer, respectively ( Weight per unit area: about 50 g/m 2 ), and oven-dried at 70° C. for 5 minutes. After that, the adhesive layers of the obtained EVA, the cured product, and the adhesive layer, and the cotton canvas and the adhesive layer, were bonded together, pressed by hand, and further pressed with a press at 3 MPa for 20 seconds, and EVA A laminate 1 was obtained as a laminate of (the first substrate), the cured product, the adhesive layer, and the cotton canvas (the second substrate).

<Examples 9-14 and Comparative Examples 6-10: Preparation of laminates 2-12>

In the same manner as in Example 8 except that the water-based adhesive F1 was changed to any of the water-based adhesives F2 to F12, a laminate consisting of EVA (first substrate), a cured product, an adhesive layer, and a cotton canvas (second substrate). 2 to 12 were obtained.

Further, in Examples 8 to 14 and Comparative Examples 6 to 10, in order to evaluate the adhesiveness after long-term storage of the water-based adhesives F1 to F12 obtained in Examples 1 to 7 and Comparative Examples 1 to 5, as described above, , laminates 1 to 12 were produced using water-based adhesives F1 to F12 stored at 50°C for 7 days. In addition, it is considered that the adhesiveness of the water-based adhesive stored at 50 degreeC for 7 days corresponds to the adhesiveness of the water-based adhesive stored at room temperature for several months.

<Test Example 1: Evaluation of Initial Adhesiveness>

After the laminate was left at room temperature for 5 minutes after its production, a tensile tester (manufactured by Shimadzu Corporation, Autograph) was used under the conditions of a peeling rate of 50 mm/min, a peeling angle of 180 degrees and room temperature, in the laminate, The peel strength of the EVA (first base material) and the cotton canvas (second base material) was measured, and initial adhesiveness was evaluated based on the following criteria. A result is shown in Table 3.

○: peel strength of 45 N/inch or more

×: Peel strength is less than 45 N/inch

<Test Example 2: Evaluation of final adhesiveness>

After the laminate was left to stand at room temperature for 24 hours after its production, a tensile tester (manufactured by Shimadzu Corporation, Autograph) was used under the conditions of a peeling rate of 50 mm/min, a peeling angle of 180 degrees and room temperature, in the laminate The peel strength of the EVA (first substrate) and the cotton canvas (second substrate) was measured, and the final adhesiveness was evaluated based on the following criteria. A result is shown in Table 3.

○: Peel strength of 90 N/inch or more or material destruction

×: Peel strength less than 90 N/inch

The kind of the laminated body manufactured in Examples 8-14 and Comparative Examples 6-10; Evaluation result of the type of water-based adhesive used and the amount of change of the backscattered light intensity; And the evaluation result of initial stage adhesiveness and final adhesiveness is shown in following Table 3.

The laminates 1 to 7 produced by using the water-based adhesives F1 to F7 satisfying the requirement for the amount of change in the backscattered light intensity of the present invention are water-based adhesives F8 to which do not satisfy the requirement for the amount of change in the backscattered light intensity of the present invention. Compared to the laminates 8 to 12 produced using F12, the initial adhesion and final adhesion were good.

The dispersion liquid of the present invention is useful as a water-based adhesive, a primer, or a raw material thereof.

This application is based on Japanese Patent Application No. 2016-212088 for which it applied in Japan, The content is all taken in in this specification.

Claims (18)

A dispersion comprising water as a dispersion medium and a compound having a chlorinated rubber and a polymerizable group as a dispersoid, comprising:
The total amount of the chlorinated rubber and the compound having a polymerizable group is 5 to 60 wt% 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 wt% 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,
30 ml of the dispersion liquid was poured into a 100 ml container, and using a rotational revolution stirrer, stirred for 1 minute under the conditions of rotation speed of 800 rpm and rotation speed of 2,000 rpm to prepare a measurement sample, and 20 ml of the measurement sample with a diameter of 25 mm Backscattered light intensity by pouring into a cylindrical sample cell, irradiating the measurement sample in the sample cell with incident light having a wavelength of 880 nm, and detecting backscattered light from the measurement sample at a position of 45° to the incident light ( %) is started within 10 minutes from the preparation of the measurement sample, and the backscattered light intensity ( %), the maximum value α (%) in the absolute value of the amount of change in the backscattered light intensity (%) measured 24 hours after starting the measurement is the following formulas (I) to (III):
α (top) < 20 (I)
α (middle) < 5 (II)
α (bottom) < 10 (III)
[wherein, α (upper part) represents the maximum value α (%) in the upper part of the measurement sample, and α (middle part) represents the maximum value α (%) in the middle part of the measurement sample, α (bottom) represents the maximum value α (%) at the bottom of the measurement sample, and the top, middle, and bottom of the measurement sample respectively represent the height of the measurement sample in the sample cell excluding the meniscus portion. The portion of the measurement sample divided by 1/3 from the top is shown.]
satisfy the requirements of
A compound having a polymerizable group and not having a cyclic structure is 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, 1 , at least one selected from the group consisting of 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10-decanediol di (meth) acrylate, and ,
The compound having a polymerizable group and a cyclic structure is a group consisting of 2-phenoxyethylene glycol (meth) acrylate, 2-phenoxydiethylene glycol (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate At least one individual dispersion selected from. The method of claim 1,
A dispersion liquid having a chlorine atom content in the chlorinated rubber of 45 wt% or more. The method of claim 1,
A dispersion liquid in which the amount of the chlorinated rubber is 1 to 30 parts by weight based on 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group. The method of claim 1,
A dispersion liquid in which at least a part of chlorinated rubber is dissolved in a liquid dispersoid. The method of claim 1,
A dispersion liquid in which at least a part of the compound having a polymerizable group is liquid at 23°C and atmospheric pressure. 6. The method of claim 5,
A dispersion liquid in which at least a part of chlorinated rubber is dissolved in a compound having a polymerizable group which is liquid at 23°C and under atmospheric pressure. The method of claim 1,
A dispersion liquid in which the dispersoid is a liquid. The method of claim 1,
A dispersion liquid wherein the compound having a polymerizable group is a compound having an ethylenically unsaturated bond. The method of claim 1,
A dispersion further comprising a surfactant. The method of claim 1,
A dispersion liquid further comprising a photoinitiator. The method of claim 1,
A dispersion further comprising an optical brightener. The method of claim 1,
A dispersion further comprising a leveling agent. The method of claim 1,
A dispersion liquid having a median diameter based on volume of the dispersoid in the dispersion liquid of 10 µm or less. The method of claim 1,
A dispersion liquid wherein the chlorinated rubber is a chlorinated rubber having no carboxyl group and no 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 15. A laminate in which the first substrate, the cured product according to claim 16, the adhesive layer, and the second substrate are laminated in this order. 18. The method of claim 17,
A laminate in which the first substrate is made of an olefin-based polymer or an ethylene-vinyl acetate copolymer.