JP4991210B2 - Method for producing aqueous dispersion of resin composition and emulsion-type adhesive - Google Patents

Description

  The present invention relates to a method for producing an aqueous dispersion of a resin composition. Specifically, the resin composition is in a state where the polyamide resin and the acrylic copolymer are integrated so as to be a composite resin. More specifically, the present invention relates to a method for producing an aqueous dispersion of a resin composition suitable for an emulsion type adhesive, an emulsion type adhesive and use thereof.

Polyamide resin can improve performance such as oil resistance, solvent resistance, chemical resistance, abrasion resistance, gas barrier property, adhesiveness, water-based ink, fiber treatment agent, fiber sealant, glass fiber It is used for hot melt adhesives such as bundling agents, paper treatment agents, binders, lubricants, steel sheet surface treatment agents, surface modifiers and interlining adhesives, thermal transfer adhesives, laminate adhesives, and the like. Various proposals have been made for basic aqueous dispersions of polyamide resins as those excellent in stability and yellowing resistance (Patent Documents 1 and 2).
On the other hand, a polymer obtained by polymerizing an ethylenically unsaturated monomer, particularly a (meth) acrylic acid derivative-based resin, has characteristics such as excellent weather resistance, hydrolysis resistance, high gloss, and low cost.
However, as the level of physical properties required for various uses in recent years has increased, it has become impossible to satisfy the demands for increasing the use of polyamide resins and (meth) acrylic acid derivative resins alone.

JP 2001-200196 A JP 2005-105192 A

In the present invention, the phase separation between the polyamide resin and the (meth) acrylic acid derivative-based polymer hardly occurs, and the oil resistance, solvent resistance, chemical resistance, wear resistance, gas barrier property, adhesiveness of the polyamide resin In particular, it is to provide a method for producing an aqueous dispersion of a composite resin, which has properties such as weather resistance, hydrolysis resistance, high gloss, and low cost that a (meth) acrylic acid derivative-based polymer has.
Furthermore, the present invention has good adhesion to various substrates such as cloth, paper or plastic film, and is resistant to solvents, oil resistance, heat resistance, alkali resistance, and water resistance to various solvents including chlorinated solvents. An object is to provide an excellent emulsion type adhesive.

  As a result of repeated researches by the present inventors on the above problems, a composite resin emulsion having good polymerization stability and characteristics of each resin can be obtained by using a specific radical polymerization initiator as an essential component. As a result, the present invention has been completed.

That is, in the first invention, a cationic azo radical polymerization initiator (b1) and a zwitterionic azo radical polymerization initiator (b2) in the presence of a basic aqueous dispersion of polyamide resin (C). was used, the radical-polymerizable unsaturated monomer (a) is polymerized in an aqueous medium, and
The radical-polymerizable unsaturated monomer (A) is an acrylic monomer having a vinyl cyanide monomer (a1) and a (meth) acrylic acid-tert-alkyl ester (a2) as essential components and a glass transition temperature of 10 to 80 ° C. The present invention relates to a method for producing an aqueous dispersion of a resin composition, which is a monomer capable of forming a copolymer .

Wherein in good preferable embodiment of the first invention, the ratio of the radical polymerizable unsaturated monomer (A) and polyamide resin (C) [(A) / (C)] is 95 to 5 / 5-95 ( Weight ratio).

In another preferred embodiment of the first invention, the cationic azo radical polymerization initiator (b1) and the zwitterionic azo radical polymerization are carried out with respect to 100 parts by weight of the radical polymerizable unsaturated monomer (A). The total amount of initiator (b2) is 0.01 to 1 part by weight.

  In still another preferred embodiment of the first invention, the ratio of the cationic azo radical polymerization initiator (b1) to the zwitterionic azo radical polymerization initiator (b2) [(b1) / (b2 )] Is 95-5 / 5-95 (weight ratio).

  The second invention relates to an aqueous dispersion of a resin composition obtained by the production method of the first invention.

Moreover, 3rd invention is related with the emulsion type adhesive agent containing the aqueous dispersion of the resin composition of 2nd invention.

The fourth invention relates to an adhesive cloth characterized in that an adhesive layer formed from the emulsion-type adhesive of the third invention is fixed to a base cloth.

Furthermore, the fifth invention is that the base material selected from the group consisting of plastic film (1), paper and base fabric, and the plastic film (2) are formed from the emulsion-type adhesive of the third invention. It is related with the laminated body characterized by being laminated | stacked through the contact bonding layer.

Furthermore, in the sixth invention, the adhesive layer formed from the emulsion-type adhesive of the third invention is laminated on any substrate selected from the group consisting of plastic film (1), paper and base fabric. The present invention relates to an adhesive sheet.

  According to the present invention, the phase separation between the polyamide resin and the (meth) acrylic acid derivative-based polymer hardly occurs, and the oil resistance, solvent resistance, chemical resistance, abrasion resistance, gas barrier property, adhesiveness of the polyamide resin In particular, it has become possible to provide a method for producing an aqueous dispersion of a composite resin, which has properties such as weather resistance, hydrolysis resistance, high glossiness, and low cost that a (meth) acrylic acid derivative-based polymer has.

The present invention is described in detail below.
In the present invention, the polyamide resin (C) used for complexing with the polymer of the radical polymerizable unsaturated monomer (A) is a basic aqueous dispersion state from the viewpoint of polymerization stability and dispersion stability after polymerization. It is important to use in.
First, the polyamide resin (C) produced by a known method is used. For example, polycondensation of diamine and dicarboxylic acid, self-condensation of ω-amino-ω ′ carboxylic acid, polycondensation of ω-amino-ω ′ carboxylic acid with diamine and / or dicarboxylic acid, or ring-opening polymerization of cyclic lactam And polyamide resins produced by such methods. Here, dicarboxylic acid or monocarboxylic acid can be used as a polymerization regulator in the polycondensation or ring-opening polymerization.

  Specific examples of diamines used in the production of the polyamide resin (C) include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, Examples include 1,9-diaminononane, 1,10-diaminodecane, phenylenediamine, and metaxylylenediamine.

  Specific examples of the dicarboxylic acid used in the production of the polyamide resin (C) include glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, tetradecanedicarboxylic acid, and octadecane. And dicarboxylic acid, fumaric acid, phthalic acid, xylylene dicarboxylic acid and dimer acid (unsaturated dicarboxylic acid having 36 carbon atoms synthesized from unsaturated fatty acid mainly composed of linoleic acid and oleic acid).

  Specific examples of the ω-amino-ω ′ carboxylic acid used for the production of the polyamide resin (C) include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid and 12-amino. Examples include dodecanoic acid.

  Specific examples of the cyclic lactam used in the production of the polyamide resin (C) include ε-caprolactam, ω-enantolactam, and ω-lauryl lactam.

  Specific examples of the dicarboxylic acid used as a polymerization regulator in the polycondensation or ring-opening polymerization include glutaric acid, adipic acid, pimelic acid, suberic acid, azelain, as well as the dicarboxylic acid used in the production of the polyamide resin. Examples include acids, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, tetradecanedicarboxylic acid, octadecanedicarboxylic acid, fumaric acid, phthalic acid, xylylene dicarboxylic acid, and dimer acid. Specific examples of the monocarboxylic acid include caproic acid, heptanoic acid, nonanoic acid, undecanoic acid, and dodecanoic acid.

In the present invention, among the polyamide resins obtained by the above method, in particular, — [NH (CH ₂ ) ₅ CO] —, — [NH (CH ₂ ) ₆ NHCO (CH ₂ ) ₄ CO] —, — [NH _{(CH 2) 6 NHCO (CH} 2) 8 CO] -, - [NH (CH 2) 10 CO] -, - [NH (CH 2) 11 CO] - and _{- [NH (CH 2) 2} NHCO-D -CO]-(wherein D represents an unsaturated hydrocarbon group having 34 carbon atoms in the dimer acid molecule)
A polyamide resin having at least one selected from the group consisting of as structural units is preferably used.

  Specific examples thereof include 6-nylon, 66-nylon, 610-nylon, 11-nylon, 12-nylon, 6/66 copolymer nylon, 6/610 copolymer nylon, 6/11 copolymer nylon, 6/12. Copolymer nylon, 6/66/11 copolymer nylon, 6/66/12 copolymer nylon, 6/66/11/12 copolymer nylon, 6/66/610/11/12 copolymer nylon and dimer acid polyamide Examples thereof include resins. These polymers or copolymers may be used alone or in combination of two or more.

The basic aqueous dispersion of the polyamide resin (C) used in the present invention can be obtained by various methods. For example, the following method can be used.
(1) A method in which a polyamide resin is heated and forcibly dispersed by a means such as stirring in an aqueous dispersion medium in which a surfactant and / or a dispersant is dissolved.
By adding a basic compound before or during forced dispersion or after forced dispersion, a basic aqueous dispersion can be obtained.
(2) A method of manufacturing by a so-called post-emulsification method in which a polyamide resin solution dissolved in a water-insoluble organic solvent is stirred and emulsified with a surfactant in an aqueous dispersion medium with high shearing force, and then the organic solvent is removed.
A basic aqueous dispersion can be obtained by adding a basic compound to an aqueous dispersion medium in advance, or by adding a basic compound when emulsifying and emulsifying with high shearing force or after stirring and emulsifying. .
(3) A method in which the terminal carboxylic acid of the polyamide resin is self-emulsified with a basic compound and dispersed in water.
(4) A method in which a polyamide resin and an ammonium compound are melt-mixed to obtain a polyamide resin composition, and the polyamide resin composition is dispersed in an aqueous dispersion medium to obtain an aqueous dispersion.

  Basic compounds used for obtaining the basic aqueous dispersion of polyamide resin (C) include ammonia compounds, hydroxide compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, diethylamine, triethylamine And the like, and ammonia compounds are particularly preferable.

  The ammonium compound used for obtaining the basic aqueous dispersion of the polyamide resin (C) is not particularly limited. For example, ammonium salt of sulfate ester, ammonium salt of carboxylic acid, ammonium salt of sulfonic acid, phosphate ester And ammonium salts and the like.

  Of the ammonium compounds, ammonium salts of sulfate esters are preferably used. As the ammonium salt of the sulfate ester, an alkyl sulfate ammonium salt such as ammonium lauryl sulfate is preferably used, and a polyoxyethylene alkyl ether ammonium sulfate salt such as polyoxyethylene lauryl ether ammonium sulfate is preferably used.

  Furthermore, among ammonium compounds, ammonium salts of carboxylic acids are preferably used. As an ammonium salt of carboxylic acid, ethylene-α, β-unsaturated carboxylic acid copolymer ammonium salt, for example, ethylene-acrylic acid copolymer ammonium salt is preferably used. In addition, you may use an above described ammonium compound individually or in combination of 2 or more types.

  In the basic aqueous dispersion of the polyamide resin (C), the aqueous dispersion medium in which the polyamide resin is dispersed is generally normal tap water or deionized water. For example, the stability of the aqueous dispersion can be further improved. For the purpose, water whose viscosity is adjusted by adding a water-soluble resin such as polyglycerin fatty acid ester, polyvinyl alcohol, sodium polyacrylate, carboxymethylcellulose, and hydroxyethylcellulose may be used. The aqueous dispersion medium may contain an antifoaming agent, a viscosity adjusting agent, an antifungal agent and the like in addition to the above components as long as the object of the present invention is not impaired. If necessary, an antioxidant, a fatty acid amide, a wax, a slipping improver such as silicone oil, a surfactant, and the like may be blended.

  The weight average particle diameter of the polyamide resin particles contained in the basic aqueous dispersion of polyamide resin (C) obtained by various methods is preferably 0.1 to 1000 μm, and preferably 0.1 to 500 μm. More preferred.

  As a commercial product of the basic aqueous dispersion of the polyamide resin (C) used in the present invention, there is Sephojon PA-150, 200 manufactured by Sumitomo Seika Co., Ltd. Further, these basic aqueous dispersions of polyamide resin (C) can maintain dispersion stability at pH 8.0 or more, and dispersion stability becomes poor at pH less than 8.0, and precipitation and aggregation of polyamide occur. Accordingly, the pH of the basic aqueous dispersion of the polyamide resin (C) used in the present invention is preferably 8.0 or more, and more preferably 8.5 to 12.0.

Next, the polymer of the radical polymerizable unsaturated monomer (A) and the polyamide resin (C) are complexed, that is, the radical polymerizable unsaturated monomer (A) is present in the basic aqueous dispersion of the polyamide resin (C). Below, the polymerization initiator used when superposing | polymerizing in an aqueous medium is demonstrated.
Examples of the polymerization initiator include water-soluble polymerization initiators, and those having the ability to initiate radical polymerization generally include azo-based initiators and peroxide-based initiators.
Peroxide-based polymerization initiators such as ammonium persulfate and potassium persulfate are generally used in emulsion polymerization. However, when these peroxide-based polymerization initiators are used, the pH during emulsion polymerization becomes 2.0 to 3.0, so that the dispersion stability of the polyamide resin (C) is impaired during the polymerization. Aggregates and a stable aqueous dispersion cannot be obtained.
Therefore, in the present invention, it is necessary to use an azo initiator, and among the azo initiators, the cationic azo radical polymerization initiator (b1) and the zwitterionic azo radical polymerization start. In combination with the agent (b2), it is further necessary from the viewpoint of polymerization stability.

Here, “cationic” refers to the property that only a cationic moiety can be formed in the molecular structure in water (for example, having an amino group in the molecule).
In addition, “zwitterionic” refers to a property in which both a cation moiety and an anion moiety can be formed in the molecular structure in water (for example, both carboxylic acid groups and amino groups are represented by amino acids. Etc.).

  In the present invention, examples of the cationic azo radical polymerization initiator (b1) include 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries), 2,2 ′. -Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (VA-044, manufactured by Wako Pure Chemical Industries), 2,2'-azobis [2- (2-imidazolin-2-yl) propane] disulfate Dihydrate (VA-046B, manufactured by Wako Pure Chemical Industries), 2,2′-azobis [2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane] dihydrochloride (VA-060, Wako Pure) 2,2′-azobis [2- (2-imidazolin-2-yl) propane] (VA-061, Wako Pure Chemical Industries), 2,2′-azobis (1-imino-1) Pirorojirino-2-ethyl propane) dihydrochloride (VA-067, can be preferably used a water-soluble polymerization initiator such as manufactured by Wako Pure Chemical).

  In the present invention, examples of the zwitterionic azo radical polymerization initiator (b2) include 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (VA-057). , Manufactured by Wako Pure Chemical Industries, Ltd.) can be suitably used.

The ratio [(b1) / (b2)] between the cationic azo radical polymerization initiator (b1) and the zwitterionic azo radical polymerization initiator (b2) is preferably 95-5 / 5-95 ( (Weight ratio), more preferably 80 to 20/20 to 80, still more preferably 75 to 40/25 to 60.
The total amount of the cationic azo radical polymerization initiator (b1) and the zwitterionic azo radical polymerization initiator (b2) is 100 parts by weight based on the total amount of the radical polymerizable unsaturated monomer (A). 1 part by weight or less is preferable, and an amount of about 0.01 to 1 part by weight is more preferable. When the total amount of both initiators is more than 1 part by weight, the hot water resistance of the film formed from the aqueous dispersion of the resulting resin composition tends to decrease, and the film tends to whiten, which is not preferable. On the other hand, when the total amount of both initiators is less than 0.01 part by weight, the polymerization reaction may not be completed and unreacted monomers may remain.

  In the present invention, when emulsion polymerization is performed, it is possible to use redox polymerization by using the azo-based polymerization initiator as an oxidizing agent and a reducing agent in combination with them. Thereby, it becomes easy to accelerate the emulsion polymerization rate or to carry out emulsion polymerization at a low temperature.

  Examples of the reducing agent used in the redox polymerization include reducing organic compounds such as metal salts such as ascorbic acid, tartaric acid, citric acid, glucose, formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, and bisulfite. Examples include reducing inorganic compounds such as sodium, sodium metabisulfite, hydrosulfite, ferrous chloride, Rongalite, thiourea dioxide, and the like.

The oxidizing agent and reducing agent may be used in amounts of about 0.01 to 1 part by weight and about 0.01 to 2 parts by weight, respectively, with respect to a total of 100 parts by weight of the radical polymerizable unsaturated monomer (A). preferable.
In the case of redox polymerization, since a higher molecular weight composite resin is formed as compared with the case where only the azo initiator is used, it is preferable in terms of heat resistance and water resistance.

  The radically polymerizable unsaturated monomer (A) used in the present invention is selected from one or more of acrylic acid, methacrylic acid and their alkyl esters or derivatives, and vinyl monomers known in the art. can do. More specifically, it can be exemplified as follows.

  Examples of the ethylenically unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid and the like.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene and the like.

Examples of the ethylenically unsaturated carboxylic acid alkylamide include aminoethylacrylamide, dimethylaminomethylmethacrylamide, methylaminopropylmethacrylamide, (meth) acrylamide, N-methylolacrylamide and the like.
Examples of the ethylenically unsaturated carboxylic acid aminoalkyl ester include aminoethyl acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, butylaminoethyl acrylate, and the like.

  As unsaturated aliphatic glycidyl ester or ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl vinyl ether, 3,4-epoxycyclohexyl vinyl ether, glycidyl (meth) allyl ether, 3,4 -Epoxy cyclohexyl (meth) allyl ether etc. can be mentioned as an example.

  Examples of the hydroxyl group-containing carboxylic acid ester include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like.

  (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth ) Tert-butyl acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isodecyl (meth) acrylate Examples thereof include tridecyl (meth) acrylate, alkylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, and isobonyl (meth) acrylate.

In the present invention, a radically polymerizable unsaturated monomer having an alkoxysilyl group can also be used in the polymerization in order to improve the solvent resistance by introducing a crosslinked structure into the dispersion particles.
Specific examples of the radical polymerizable monomer having an alkoxysilyl group include vinyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, allyltriethoxysilane, trimethoxysilylpropylallylamine, vinyltriethoxysilane, vinyltris ( β-methoxyethoxy) silane, γ- (meth) acryloxypropyltriethoxysilane, and the like. These may use only 1 type and may use 2 or more types together suitably.

  The content of the radically polymerizable monomer having an alkoxysilyl group is 0.05 to 5% by weight, preferably 100% by weight of the total of monomers used for polymerization, that is, 100% by weight of the radically polymerizable unsaturated monomer (A), preferably It is good to be 0.1 to 3% by weight. When the content of the radically polymerizable monomer having an alkoxysilyl group is less than 0.05% by weight, the effect of crosslinking hardly appears. On the other hand, when the content exceeds 5% by weight, the coating tends to become brittle and during storage. This is not preferable because the physical properties easily change.

  As in the case of the radically polymerizable monomer having an alkoxysilyl group, divinylbenzene, diallyl phthalate, ethylene dimethacrylate, neopentyl glycol dithiophene is introduced in order to improve the solvent resistance by introducing a crosslinked structure into the dispersion particles. Polyfunctional vinyl monomers such as methacrylate and triallyl isocyanurate and polyfunctional allyl monomers can be used.

  The content of the polyfunctional vinyl monomer and the polyfunctional allyl monomer is 0.05 to 5% by weight, preferably 100% by weight of the total of the monomers to be subjected to polymerization, that is, 100% by weight of the radical polymerizable unsaturated monomer (A), It is good that it is 0.1 to 3% by weight. When the content of the polyfunctional vinyl monomer and the polyfunctional allyl monomer is less than 0.05% by weight, the effect of crosslinking hardly appears, while when the content exceeds 5% by weight, the coating film tends to become brittle and during storage. This is not preferable because the physical properties easily change.

  In particular, when an emulsion-type adhesive is obtained using the aqueous dispersion obtained according to the present invention, the following vinyl cyanide monomer (a1) and (meth) acrylic acid are used as the radical polymerizable unsaturated monomer (A). It is preferable to use -tert-alkyl ester (a2) as an essential component. In particular, when the polyamide resin (C) is less than 50 wt% in the total 100 wt% of the polyamide resin (C) and the radical polymerizable unsaturated monomer (A), vinyl cyanide is used to improve the solvent resistance. It is preferable to use a radically polymerizable unsaturated monomer (A) containing (meth) acrylic acid-tert-alkyl ester (a2) in order to improve the adhesiveness of the system monomer (a1).

As the vinyl cyanide monomer (a1), (meth) acrylonitrile is preferable.
The vinyl cyanide monomer (a1) is an important component in terms of resistance to chlorinated organic solvents. The chlorine cyanide-based organic solvent is such that the vinyl cyanide monomer (a1) is 0.5 to 20% by weight in 100% by weight of the total of monomers used for polymerization, that is, the total of the radically polymerizable unsaturated monomer (A). From the viewpoint of the properties, it is preferably 1 to 10% by weight.

  As (meth) acrylic acid-tert-alkyl ester (a2), in addition to tert-butyl (meth) acrylate, tert-amyl (meth) acrylate, tert-butylaminoethyl (meth) acrylate, (meth ) Tert-butylethyl acrylate, tert-butylacetyl (meth) acrylate, tert-butyldimethylsilyl (meth) acrylate, tert-amylcyclohexyl (meth) acrylate, tert-butylphenyl (meth) acrylate, (meth ) Tert-butyl benzyl acrylate can be mentioned as an example, but tert-butyl (meth) acrylate is preferred.

  The (meth) acrylic acid-tert-alkyl ester (a2) is important from the viewpoint of securing adhesiveness when the aqueous dispersion of the resin composition of the present invention is used as the main component of the adhesive or coating agent. The adhesiveness of the (meth) acrylic acid-tert-alkyl ester (a2) is 1 to 60% by weight in the total of monomers used for polymerization, that is, 100% by weight of the radical polymerizable unsaturated monomer (A). It is preferable at this point, and it is more preferable that it is 5 to 40 weight%.

The radical polymerizable monomer (A) is preferably a monomer capable of forming an acrylic copolymer having a glass transition temperature (Tg) of 10 to 80 ° C., and a copolymer having a Tg of 20 to 60 ° C. More preferred are monomers that can be formed.
When Tg is lower than 10 ° C., the heat resistance of the obtained adhesive tends to be lowered. Moreover, when Tg exceeds 80 degreeC, the adhesiveness of the adhesive agent obtained tends to fall. When Tg is in the range of 10 to 80 ° C., heat resistance and adhesiveness are excellent.
In the present invention, when a radical polymerizable unsaturated monomer having an alkoxysilyl group, or a polyfunctional vinyl monomer or a polyfunctional allyl monomer is used for copolymerization, these monomers are used in the calculation of Tg described below. Shall be excluded.

In the present invention, the Tg of an acrylic copolymer formed from n types of monomers is theoretically derived from the following formula [I].
1 / Tg = [(W1 / Tg1) + (W2 / Tg2) +... (Wn / Tgn)] / 100 [I]
Where W1:% by weight of monomer 1, Tg1: glass transition temperature (° K) of homopolymer that can be formed from monomer 1 alone,
W2:% by weight of monomer 2, Tg2: Glass transition temperature (° K) of homopolymer that can be formed from monomer 2 alone,
Wn:% by weight of monomer n, Tgn: glass transition temperature (° K) of a homopolymer that can be formed only from monomer n,
It is assumed that W1 + W2 +... + Wn = 100.
In the case of using a reactive emulsifier having a radical polymerizable unsaturated group as an emulsifier when the radical polymerizable unsaturated monomer (A) is polymerized in an aqueous medium, the radical polymerizable unsaturated monomer (A) is used. The reactive emulsifier having a radically polymerizable unsaturated group is not included in the monomer in the specification of the structure and the calculation of Tg of the copolymer.

In the present invention, a chain transfer agent can be used in the polymerization reaction for molecular weight adjustment for the purpose of improving adhesion.
As the chain transfer agent, stearyl mercaptan, t-dodecyl mercaptan, mercaptopropionic acid derivative, thioglycolic acid derivative and the like can be used.
These chain transfer agents are preferably about 0.01 to 1 part by weight, preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the total amount of the radical polymerizable unsaturated monomer (A). More preferred.

  As an emulsifier used when polymerizing the radically polymerizable unsaturated monomer (A) in the aqueous medium in the presence of the basic aqueous dispersion of the polyamide resin (C), a radically polymerizable group is incorporated in the structure. Conventionally known ones such as one or more reactive emulsifiers and / or non-reactive emulsifiers can be arbitrarily used.

  Reactive emulsifiers having one or more radically polymerizable groups in the structure can be further roughly classified into anionic and nonionic ones. The anionic reactive emulsifier having one or more radically polymerizable unsaturated groups may be used alone or in combination of two or more.

  Specific examples of the anionic reactive emulsifier are shown below, but the emulsifiers that can be used in the present invention are not limited to those described below.

  Alkyl ether type (as commercial products, for example, Aqualon KH-05, KH-10, KH-20 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adeka Soap SR-10N, SR-20N manufactured by Asahi Denka Kogyo Co., Ltd., Kao Corporation Latemul PD-104, etc.) or sulfosuccinic acid ester-based (commercially available products include Latemul S-120, S-120A, S-180P, S-180A manufactured by Kao Corporation, Elemiol JS-2 manufactured by Sanyo Chemical Co., Ltd., etc.) )

  Furthermore, alkylphenyl ether type or alkylphenyl ester type (commercially available products include, for example, Aqualon H-2855A, H-3855B, H-3855C, H-3856, HS-05, HS-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. HS-20, HS-30, Adeka Soap SDX-222, SDX-223, SDX-232, SDX-233, SDX-259, SE-10N, SE-20N, etc. manufactured by Asahi Denka Kogyo Co., Ltd.).

  Furthermore, (meth) acrylate sulfate ester type (commercially available products such as Antox MS-60, MS-2N manufactured by Nippon Emulsifier Co., Ltd., Eleminol RS-30 manufactured by Sanyo Chemical Industries Ltd.) and phosphate ester type ( Examples of commercially available products include H-3330PL manufactured by Daiichi Kogyo Seiyaku Co., Ltd. and Adeka Soap PP-70 manufactured by Asahi Denka Kogyo Co., Ltd.).

In the present invention, if necessary, a nonionic reactive emulsifier can be used together with the above-mentioned anionic reactive emulsifier or alone.
Examples of nonionic reactive emulsifiers that can be used in the present invention include alkyl ethers, alkylphenyl ethers or alkylphenyl esters, (meth) acrylate sulfates, and the like.
As the alkyl ether-based commercial products, Adeka Soap ER-10, ER-20, ER-30, ER-40 manufactured by Asahi Denka Kogyo Co., Ltd., Latemul PD-420, PD-430, PD-450 manufactured by Kao Corporation Etc.
Examples of commercially available alkyl phenyl ether or alkyl phenyl ester products include, for example, Aqualon RN-10, RN-20, RN-30, RN-50, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adeka Soap NE manufactured by Asahi Denka Kogyo Co., Ltd. -10, NE-20, NE-30, NE-40 and the like.
Examples of commercially available (meth) acrylate sulfate esters include RMA-564, RMA-568, and RMA-1114 manufactured by Nippon Emulsifier Co., Ltd.

  When obtaining the aqueous dispersion of the present invention, a non-reactive emulsifier, if necessary, together with a reactive emulsifier having one or more radically polymerizable groups, as long as the performance as an adhesive is not adversely affected. Can be used in combination.

Non-reactive emulsifiers can be broadly classified into nonionic and anionic types.
Examples of non-reactive nonionic emulsifiers include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether,
Polyoxyethylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether;
Sorbitan higher fatty acid esters such as sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate,
Polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate,
Polyoxyethylene higher fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monostearate,
Glycerol higher fatty acid esters such as oleic acid monoglyceride, stearic acid monoglyceride,
Examples thereof include polyoxyethylene / polyoxypropylene / block copolymers. Or polyoxyethylene distyrenated phenyl ether etc. are mentioned.

  Examples of non-reactive anionic emulsifiers include higher fatty acid salts such as sodium oleate, alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate, alkyl sulfate esters such as sodium lauryl sulfate, and polyoxyethylene lauryl ether sulfate. Polyoxyethylene alkyl ether sulfates such as sodium, polyoxyethylene alkylaryl ether sulfates such as sodium polyoxyethylene nonylphenyl ether sulfate, sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate And alkylsulfosuccinic acid ester salts and derivatives thereof. Alternatively, polyoxyethylene distyrenated phenyl ether sulfate ester salts may be mentioned.

  The usage-amount of the emulsifier used in this invention is not necessarily limited, According to the physical property calculated | required when the aqueous dispersion obtained is finally used, it can select suitably. For example, the emulsifier is preferably 0.1 to 30 parts by weight, more preferably 0.3 to 20 parts by weight, based on 100 parts by weight of the total amount of the monomers (A) to be subjected to polymerization. More preferably, it is in the range of 5 to 10 parts by weight.

  In obtaining an aqueous dispersion in the present invention, a water-soluble protective colloid is added in order to increase the affinity for an aqueous medium within a range that does not adversely affect the performance of the coating film or adhesive composed of the aqueous dispersion. It can also be used together.

Examples of the water-soluble protective colloid include polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and modified polyvinyl alcohol; for example, cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose salt, and guar gum Natural polysaccharides such as these can be used, and these can be used singly or in combination.
The amount of the water-soluble protective colloid used is about 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight per 100 parts by weight of the radical polymerizable unsaturated monomer (A).

The polymerization temperature varies depending on the polymerization initiator to be used. For example, in 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries), it may be usually about 60 ° C.
The polymerization time is not particularly limited, but is usually 2 to 24 hours.
Further, from the viewpoint of the stability during polymerization and the dispersion stability of the resulting dispersion, the pH is preferably 8.0 or more, more preferably 8.5 to 12.0 during and after the polymerization. .

  The ratio [(A) / (C)] of the radically polymerizable unsaturated monomer (A) and the polyamide resin (C) used in the present invention is preferably 95 to 5/5 to 95 (weight ratio), More preferably, it is 90-10 / 10-90, More preferably, it is 80-20 / 20-80. When the ratio of the radically polymerizable unsaturated monomer (A) or the polyamide resin (C) is less than 5%, characteristics as a composite resin utilizing each of them cannot be obtained.

  The aqueous dispersion of the resin composition obtained by the above-described production method of the present invention includes water-based inks, fiber treatment agents, fiber sealants, glass fiber sizing agents, paper treatment agents, various paints, lubricants, steel sheet surface treatment agents. It can be suitably used for hot-melt adhesives such as surface modifiers and interlining adhesives, thermal transfer adhesives, laminate adhesives, and the like.

When obtaining various adhesives, various crosslinking agents can be added for the purpose of improving the cohesive strength of the resulting adhesive layer.
Examples of the crosslinking agent include an epoxy compound, an isocyanate compound, an oxazoline compound, a hydrazide compound, a titanium compound, a zirconium compound, a carbodiimide compound, an aziridine compound, an aluminum compound, and the silane compound, and at least one of these can be used.

  Examples of the epoxy compound used in the present invention include glycerol diglycidyl ether, (poly) glycerol diglycidyl ether, (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, glycidol, epichlorohydrin, Examples include epibromohydrin and α-methylepichlorohydrin. In the present invention, “poly” represents a polymer including oligomers such as dimers and trimers.

  Examples of the isocyanate compound used in the present invention include aromatic, aliphatic and alicyclic organic polyisocyanates such as 2,4-tolylene diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate, or a mixture thereof and these organic polyisocyanates. Examples include blocked isocyanate obtained by blocking an isocyanate compound with a blocking agent.

  Examples of the oxazoline compound used in the present invention include 1,2-ethylenebisoxazoline, 2-cyclohexyl-2-oxazoline, 2- (2′-cyclohexenyl) -2-oxazoline, 2-oxazoline, 2-methyl- 2-oxazoline, 2-ethyl-2-oxazoline, 2-isopropyl-2-oxazoline, 2-n-propyl-2-oxazoline, etc., or a mixture thereof and a polymer thereof can be mentioned.

  Examples of the hydrazide compound used in the present invention include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 7,11-octadecadien-1,18-dicarbohydrazide, adipic acid dihydrazide, and the like. Can be mentioned.

  Examples of the titanium compound used in the present invention include dihydroxytitanium bislactate, diisopropoxytitanium bis (triethanolaminate), tetramethoxytitanate, polyhydroxytitanium stearate, titanium acetylacetonate, titanium tetraacetylacetonate, and tetraisopropyl. Examples include titanate.

  Examples of the zirconium compound used in the present invention include zirconium acetate, zirconium tributoxy monostearate, zirconium tetraacetyl acetonate, zirconium monoacetyl acetonate, tetra n-propoxy zirconium, tetra n-butoxy zirconium, ammonium zirconium carbonate, Examples thereof include zirconium oxychloride and zirconium sulfate.

  Examples of the carbodiimide compound used in the present invention include p-phenylene (poly) carbodiimide, dicyclohexyl (poly) carbodiimide, diisopropyl (poly) carbodiimide, dimethyl (poly) carbodiimide and diisobutyl (poly) carbodiimide.

  Examples of the aziridine compound used in the present invention include diphenylmethane-bis-4,4′-N, N′-diethyleneurea and 2,2-bishydroxymethyl-butanol-tris [3- (1-aziridinyl) propionate. ] Etc. are mentioned.

  Examples of the aluminum compound used in the present invention include aluminum chloride and aluminum nitrate.

  In the present invention, the epoxy compounds, isocyanate compounds, oxazoline compounds, hydrazide compounds, titanium compounds, zirconium compounds, silane compounds, aziridine compounds, aluminum compounds and carbodiimide compounds may be used alone or in combination of two or more. It may be used.

  In the emulsion-type adhesive of the present invention, the content of the crosslinking agent is the total of the resin composition obtained by polymerization, that is, the composite resin of the acrylic copolymer and the polyamide resin, from the viewpoint of film hardness and adhesiveness. It is preferable that it is 0.005-20 weight part with respect to 100 weight part, More preferably, it is 0.05-10 weight part.

  In the emulsion type adhesive of the present invention, various adhesion aids can be used in combination in order to increase the adhesiveness within a range that does not adversely affect the performance as an adhesive.

Examples of the above-mentioned adhesion assistant include tackifier, vinyl chloride vinyl acetate resin, SBR, NBR, and the like, and these can be used alone or in a combination of a plurality of types.
The amount of the adhesion aid used is preferably about 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the radical polymerizable unsaturated monomer (A).

The emulsion adhesive of the present invention may contain organic particles and / or inorganic particles.
Organic particles and inorganic particles contribute to improving adhesion to adherends and improve heat resistance.
Organic particles include epoxy resin, melamine resin, urea resin, acrylic resin, polyimide resin, Teflon (registered trademark) resin, polyethylene resin, polyester resin, polyurethane resin, polyamide resin, etc. Can be mentioned.
Examples of the inorganic particles include silica, talc, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, precipitated barium sulfate, precipitated barium carbonate, barium titanate, and barium sulfate.
The particles may be used alone or in combination of two or more. The particles preferably have an average particle size of 10 μm or less, and more preferably 5 μm or less.

When an aqueous dispersion of a composite resin of the present invention comprising a polyamide resin and an acrylic copolymer is used as an emulsion type adhesive, the minimum film forming temperature (hereinafter referred to as “MFT”) is 10 to 80 ° C. It is preferable that it is 20-60 degreeC.
When MFT is higher than 80 ° C., the adhesiveness tends to decrease.

A base fabric (natural fiber such as cotton, hemp, silk, wool, etc., regenerated fiber such as rayon, cupra, semi-synthetic fiber such as acetate, triacetate, polyester, etc. Nylon, urethane, polypropylene, polyethylene, polyvinyl chloride and other synthetic fibers, glass fibers, etc.) with a gravure (micro gravure) roll method, double dot method, paste dot method, powder dot method, spray method, etc. It is possible to obtain an adhesive cloth having good washing resistance (water resistance and solvent resistance) by using, coating, drying and curing, and fixing the adhesive layer.
Alternatively, the adhesive cloth can also be obtained by immersing the base cloth in the adhesive, impregnating the base cloth with the adhesive, and drying and curing it without using the coating as described above.
The obtained adhesive cloth is particularly useful for applications such as an adhesive label for identifying a washing object in dry cleaning.
In addition, after the coating, a part or all of the coated adhesive may be impregnated in the base fabric.

  In addition, the emulsion type adhesive of the present invention is a plastic film (1) (as a kind of plastic film, for example, poval film, PET film, polyolefin film, unsaponified triacetate film, polyester film, polyvinyl chloride film, polyurethane film, Cycloolefin film etc.), processed or unprocessed paper, or base fabric (cotton, synthetic fiber, glass fiber, etc.) processed to a certain thickness, dried and cured After forming the adhesive layer, another laminate of the plastic film (2) is bonded to the adhesive layer, whereby a laminate having good solvent resistance, adhesiveness, and heat resistance can be obtained.

Examples of the coating method that can be used when the adhesive is applied to the plastic film (1) or paper include the curtain roll method, the comma roll method, the kiss roll method, the slit die, as well as the methods exemplified in the method for producing the adhesive cloth. A method such as a method or a lip method can be used. In these coating methods, the reverse method can also be applied.
The plastic film (1) and the plastic film (2) may be of the same type or different.

  Moreover, in the said laminated body, when using the peeling film by which the surface is peel-processed as a plastic film (2), peeling off this peeling film and sticking it on arbitrary adherends, and using it. Therefore, it is useful as an adhesive sheet.

  Examples of the use of the aqueous dispersion of the resin composition of the present invention include water-based inks, fiber treatment agents, fiber sealants, glass fiber sizing agents, paper treatment agents, binders, lubricants, steel sheet surface treatment agents, surface modification agents. When used as an adhesive, there are hot melt adhesives such as interlining adhesives, heat-sensitive transfer adhesives, and laminating adhesives.

  Hereinafter, although the effect of the present invention is explained still in detail by an example, the present invention is not limited to these. In addition, in an example, a part shows a weight part and% shows weight%, respectively.

Example 1
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a refluxer, 94.5 parts of ion-exchanged water and 1.9 parts by weight of Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.) as an anionic reactive emulsifier Sephajon PA-200 (manufactured by Sumitomo Seika Co., Ltd., nonvolatile content: 40%), 622.6 parts by weight, and 2.5% by weight of 25% aqueous ammonia as an aqueous dispersion of polyamide resin, and an aqueous dispersion having a pH of 9.5 A liquid was obtained.

  Next, 7.8 parts by weight of acrylonitrile as the monomer (a1), 33.1 parts by weight of tert-butyl methacrylate as the monomer (a2), 0.5 parts by weight of glycidyl methacrylate, 5.7 parts by weight of styrene, Methyl methacrylate 26.9 parts, acrylic acid 0.5 parts, acrylic acid-2-ethylhexyl 30.5 parts, divinylbenzene 0.5 parts and 2-hydroxyethyl methacrylate 1.0 parts, ion exchange 62.9 parts by weight of water and 3.3 parts by weight of Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.) as an anionic reactive emulsifier were mixed to obtain a pre-emulsion.

  After raising the internal temperature of the reaction vessel to 60 ° C. and sufficiently purging with nitrogen, 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50) was used as a cationic azo radical polymerization initiator (b1). 3.7% by weight of a 5% aqueous solution of Wako Pure Chemical Industries, Ltd.) and 2,2′-azobis [N- (2-carboxyethyl) -2-methyl as an amphoteric azo radical polymerization initiator (b2) Propionamidine] hydrate (VA-057, manufactured by Wako Pure Chemical Industries, Ltd.) 5% aqueous solution 1.9 parts by weight was added.

After completion of the initiator addition, the inside of the reaction system was maintained at 60 ° C. for 5 minutes, and then the pre-emulsion was dropped into the reaction vessel over 3 hours while maintaining the internal temperature at 60 ° C. One hour after the completion of the dropwise addition, 0.3 parts by weight of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50) is added 4 times every 30 minutes, and the mixture is further stirred for 1 hour. Continued. During the emulsion polymerization, the pH of the polymerization reaction solution was 9.0. After completion of the reaction, the temperature was cooled to 30 ° C. to obtain an aqueous emulsion of a composite resin having a nonvolatile content concentration of 40.0%.
In addition, the glass transition temperature (calculated value) of the acrylic copolymer part in the aqueous emulsion of the obtained composite resin was 41 ° C., and the MFT of the aqueous emulsion of the composite resin was 30 ° C.
The obtained aqueous emulsion was subjected to the evaluation described below as an emulsion type adhesive.

Example 2
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, and reflux, 576.8 parts of ion exchange water, 7.1 parts by weight of Aqualon KH-10 as an anionic reactive emulsifier, and an aqueous dispersion of polyamide resin 30.5 parts by weight of Sephojon PA-200 and 2.5 parts by weight of 25% aqueous ammonia were charged to obtain an aqueous dispersion having a pH of 9.5.

  Next, 28.8 parts by weight of acrylonitrile as the monomer (a1), 122.4 parts by weight of tert-butyl methacrylate as the monomer (a2), 1.8 parts by weight of glycidyl methacrylate, 21.1 parts by weight of styrene, 99.5 parts by weight of methyl methacrylate, 1.9 parts by weight of acrylic acid, 112.8 parts by weight of 2-ethylhexyl acrylate, 1.8 parts by weight of divinylbenzene and 3.7 parts by weight of 2-hydroxyethyl methacrylate, ion exchange 371.3 parts by weight of water and 12.1 parts by weight of Aqualon KH-10 as an anionic reactive emulsifier were mixed to obtain a pre-emulsion.

After raising the internal temperature of the reaction vessel to 60 ° C. and sufficiently purging with nitrogen, 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50) was used as a cationic azo radical polymerization initiator (b1). 16.9 parts by weight of a 2% aqueous solution of 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (zwitterionic azo radical polymerization initiator (b2)) The same procedure as in Example 1 was performed except that 7.1 parts by weight of a 5% aqueous solution of VA-057) was added to the reaction vessel to start the polymerization reaction, and the pH was 9.0 and the nonvolatile content concentration was 40.2. % Aqueous emulsion of composite resin was obtained.
The glass transition temperature (calculated value) of the acrylic copolymer part in the aqueous emulsion of the obtained composite resin was 41 ° C., and the MFT of the aqueous emulsion of the composite resin was 45 ° C.
The obtained aqueous emulsion was subjected to the evaluation described below as an emulsion type adhesive.

Example 3
As a cationic azo radical polymerization initiator (b1), 3.7 parts by weight of a 50% aqueous dispersion of 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50) and a zwitterionic azo series 1.9 parts by weight of 50% aqueous dispersion of 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (VA-057) as the radical polymerization initiator (b2) An aqueous emulsion of a composite resin having a pH of 9.0 and a nonvolatile content concentration of 40.2% was obtained except that the polymerization reaction was started by adding to the reaction vessel.
The glass transition temperature (calculated value) of the acrylic copolymer part in the obtained composite resin aqueous emulsion was 41 ° C., and the MFT of the aqueous composite resin emulsion was 28 ° C.
The obtained aqueous emulsion was subjected to the evaluation described below as an emulsion type adhesive.

Example 4
5.4 parts by weight of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50) as a cationic azo radical polymerization initiator (b1) and zwitterionic azo radical polymerization As initiator (b2), 0.2 part by weight of 5% aqueous solution of 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (VA-057) was added to the reaction vessel. Then, the same operation as in Example 1 was carried out except that the polymerization reaction was started to obtain an aqueous emulsion of a composite resin having a pH of 9.0 and a nonvolatile content concentration of 40.0%.
The glass transition temperature (calculated value) of the acrylic copolymer part in the obtained composite resin aqueous emulsion was 41 ° C., and the MFT of the composite resin aqueous emulsion was 30 ° C.
The obtained aqueous emulsion was subjected to the evaluation described below as an emulsion type adhesive.

Example 5
Example 1 except that 5 parts by weight of carbodilite E-02 (Nisshinbo Co., Ltd., nonvolatile content: 40%) was added as a carbodiimide-based crosslinking agent to 100 parts by weight of the aqueous emulsion of the composite resin obtained in Example 1. The same operation was performed to obtain an emulsion type adhesive.
In addition, the minimum film-forming temperature of the obtained emulsion type adhesive was 30 degreeC.

Example 6
The same operation as in Example 1 was performed except that 5 parts by weight of silica fine particles having an average particle size of 5.0 μm were added to 100 parts by weight of the emulsion to the aqueous emulsion of the composite resin obtained in Example 1, An emulsion type adhesive was obtained. The minimum film forming temperature of the obtained emulsion type adhesive was 35 ° C.

<< Comparative Example 1 >>
As a cationic azo radical polymerization initiator (b1), 5.6 parts by weight of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50) was added to the reaction vessel to conduct a polymerization reaction. And the same operation as in Example 1 was performed except that the zwitterionic azo radical polymerization initiator was not used, but the entire reaction system was thickened and the composite aqueous resin emulsion was stable. Could not get.

<< Comparative Example 2 >>
A 5% aqueous solution of 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (VA-057) as a zwitterionic azo radical polymerization initiator (b2) 5.6 The polymerization reaction was started by adding parts by weight to the reaction vessel, and the same operation as in Example 1 was carried out except that the cationic azo radical polymerization initiator was not used. As a result, a stable aqueous emulsion of the composite resin could not be obtained.

<< Comparative Example 3 >>
The same operation as in Example 1 was performed except that 5.6 parts by weight of a 5% aqueous solution of potassium persulfate as a radical polymerization initiator was added to the reaction vessel to start the polymerization reaction. As a result, a stable aqueous emulsion of the composite resin could not be obtained.

Using the adhesives obtained in each of Examples and Comparative Examples, adhesive cloths and laminates were produced by the methods described below, and each physical property was evaluated.
[Evaluation of polymerization stability]
The amount of resin adhering to the reaction vessel after completion of the reaction and the amount of aggregate after filtration with a filter cloth were visually evaluated. The evaluation criteria are as follows.
A: Good.
○: A level with no practical problem.
Δ: Slightly problematic level.
X: It is bad.

1. Production of Adhesive Fabric The adhesive obtained in each Example and each Comparative Example was screened on a nylon nonwoven fabric with a basis weight of 25 g / m ² using a screen having a pore diameter of 80 μm, and the number of dots was 300 / cm ² and the coating amount was 5 g. / M ² and applied in the form of dots. Subsequently, it dried at 150 degreeC for 1 minute, and obtained the adhesive cloth.
[Adhesion evaluation method]
The adhesive surface of the obtained adhesive cloth and the cotton outer surface were bonded using a hot press under the conditions of 130 ° C., 200 KPa, 15 seconds to obtain a test cloth. The obtained test cloth was cut into a width of 25 mm in accordance with an adhesion strength test method (JIS L 1086), and then the peel strength was determined with a tensile tester under the conditions of a tensile speed and 100 mm / min. The obtained peel strength was determined according to the following criteria.
○: 500 g (4.9 N) / 25 mm or more Δ: 100 g (0.98 N) / 25 mm or more and less than 500 g (4.9 N) / 25 mm X: less than 100 g (0.98 N) / 25 mm

[Dry cleaning resistance evaluation method]
In accordance with the dry cleaning resistance test method wash cylinder method (JIS L 1086), 5 g of an anionic surfactant and 5 g of a nonionic surfactant are dissolved in 10 L of tetrachloroethylene in a wash cylinder, and 0.2 L of water is added thereto. In addition, the test cloth obtained in the same manner as in the method for evaluating the adhesive strength was placed in the treatment liquid prepared, stirred for 15 minutes, and after drying, the dried test cloth was dried in an oven at 60 ° C. The peel strength was determined by the same method as for the property. The obtained peel strength was determined according to the following criteria.
○: 500 g (4.9 N) / 25 mm or more Δ: 100 g (0.98 N) / 25 mm or more and less than 500 g (4.9 N) / 25 mm X: less than 100 g (0.98 N) / 25 mm

2. Manufacture of a laminated body The adhesive agent obtained by each Example and each comparative example was apply | coated to PET film (thickness: 100 micrometers), water was removed by the heating for 100 degreeC-30 seconds, and the thickness of 1.0 g / m < ² > was obtained. An adhesive layer was provided.
While the corona-treated triacetate film (thickness: 100 μm) is in contact with the surface of the adhesive layer, it is heated and pressurized with a nip roll (nip temperature 75 ° C., nip pressure 150 N / cm) to obtain a laminate, which will be described later. The adhesive strength was determined.

[Adhesiveness]
The laminate produced by the above method was cut into a size of 15 mm × 10 mm to obtain a test piece. Using an Inslon-type tensile tester, T-type peel strength (g / 15 mm, average of 5 points) between films was measured for each test piece under the condition of a peel rate of 300 mm / min.
A: Excellent. Peel strength 800 g / 15 mm or more ○: Good. Peel strength 600 g / 15 mm or more and less than 800 g / 15 mm Δ: Somewhat poor. Peel strength 400 g / 15 mm or more and less than 600 g / 15 mm x: Defect. Peel strength less than 400g / 15mm

[Heat-resistant]
The test piece produced by the above method is placed in an 80 ° C. oven for 100 hours, and the appearance change is confirmed.
A: Excellent. No change in appearance.
○: Good. There is some coloring.
Δ: Slightly poor It turns yellow and is not practical.
X: Defect. At the same time as turning yellow, dust is generated, impractical.

[Tetrachloroethylene resistance]
After the absorbent cotton impregnated with tetrachloroethylene was squeezed, the surface of the adhesive layer formed on the PET film was rubbed 100 times, and the following five-stage evaluation was performed on the remaining state of the rubbed adhesive layer.
5: No change in the adhesive layer.
4: The adhesive layer is less than 20%.
3: The adhesive layer is 20% or more and less than 50%.
2: The adhesive layer is 50% or more and less than 80%.
1: More than 80% of the adhesive layer is lost.

[Acetone resistance]
After the absorbent cotton impregnated with acetone was squeezed, the surface of the adhesive layer formed on the PET film was rubbed 100 times, and the following five-stage evaluation was performed on the remaining state of the adhesive layer in the rubbed part.
5: No change in the adhesive layer.
4: The adhesive layer is less than 20%.
3: The adhesive layer is 20% or more and less than 50%.
2: The adhesive layer is 50% or more and less than 80%.
1: More than 80% of the adhesive layer is lost.
The results of the evaluation are shown in Tables 1 and 2.

As shown in Examples, a radical polymerizable monomer is used in the presence of a basic aqueous dispersion of polyamide resin (C) by using a cationic azo initiator and a zwitterionic azo initiator in combination. (A) can be stably emulsion-polymerized in an aqueous medium to obtain an aqueous dispersion of a resin composition in which a copolymer formed from a radical polymerizable monomer (A) and a polyamide resin (C) are combined. it can.
And the adhesive cloth and laminated body produced from the emulsion type adhesive agent containing the aqueous dispersion of the resin composition have high solvent resistance and heat resistance.
On the other hand, as shown in the comparative example, when a cationic azo initiator, a zwitterionic azo initiator, and a peroxide initiator are used alone, the polymerization itself is unstable, It is not possible to obtain an aqueous dispersion of the resin composition.

  The aqueous dispersion of the resin composition of the present invention includes, for example, water-based inks, fiber treatment agents, fiber sealants, glass fiber sizing agents, paper treatment agents, binders, lubricants, steel sheet surface treatment agents, surface modifiers, and the like. As the adhesive, it can be used for hot melt adhesives such as interlining adhesives, heat-sensitive transfer adhesives, laminate adhesives, and the like.

Claims (9)

Using a cationic azo radical polymerization initiator (b1) and a zwitterionic azo radical polymerization initiator (b2) in the presence of a basic aqueous dispersion of polyamide resin (C), radical polymerizable unsaturated Polymerizing monomer (A) in an aqueous medium ; and
The radical-polymerizable unsaturated monomer (A) is an acrylic monomer having a vinyl cyanide monomer (a1) and a (meth) acrylic acid-tert-alkyl ester (a2) as essential components and a glass transition temperature of 10 to 80 ° C. A method for producing an aqueous dispersion of a resin composition, which is a monomer capable of forming a copolymer . The ratio [(A) / (C)] of the radically polymerizable unsaturated monomer (A) and the polyamide resin (C) is 95 to 5/5 to 95 (weight ratio). The manufacturing method of the aqueous dispersion of the resin composition of description. The total amount of the cationic azo radical polymerization initiator (b1) and the zwitterionic azo radical polymerization initiator (b2) is 0.01 to 100 parts by weight of the radical polymerizable unsaturated monomer (A). The method for producing an aqueous dispersion of a resin composition according to claim 1 or 2, wherein the content is 1 part by weight . The ratio [(b1) / (b2)] of the cationic azo radical polymerization initiator (b1) to the zwitterionic azo radical polymerization initiator (b2) is 95 to 5/5 to 95 (weight ratio). The method for producing an aqueous dispersion of a resin composition according to any one of claims 1 to 3, wherein The aqueous dispersion of the resin composition obtained by the manufacturing method in any one of Claims 1 thru | or 4 . An emulsion-type adhesive comprising an aqueous dispersion of the resin composition according to claim 5 . An adhesive fabric, wherein an adhesive layer formed from the emulsion adhesive according to claim 6 is fixed to a base fabric . The base material selected from the group consisting of a plastic film (1), paper and a base fabric, and another plastic film (2) are interposed via an adhesive layer formed from the emulsion-type adhesive according to claim 6. A laminated body characterized by being laminated . An adhesive sheet formed by laminating an adhesive layer formed from the emulsion adhesive according to claim 6 on any substrate selected from the group consisting of a plastic film (1), paper, and a base fabric. .