JPH09111218A - Emulsion composition for adhesive and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject composition having well-balanced adhesive strength and cohesive force, heat-resistance, water-resistance and bonding strength to polyolefin by emulsion polymerizing a specific monomer (mixture) dissolving a tackifier resin in the presence of a specific emulsion. SOLUTION: This adhesive is produced by carrying out the emulsion polymerization of the mixture of monomer (mixture) (B) selected from (A1 ) a (meth) acrylate, (A2 ) a vinyl aromatic compound and (A3 ) a carboxylic acid containing vinyl group and 10-300 pts. of a tackifying resin dissolved per 100 pts.wt. of (B), in the presence of a polymer emulsion which is produced by the polymerization of the monomer (mixture) selected from A1 , A2 and A3 , in an amount of 45-250 pts. of this mixture per 100 pts. of solid in (A).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an emulsion modified with a tackifying resin suitable for adhesives and a method for producing the same. More specifically, the present invention relates to an emulsion having an excellent balance between adhesive strength and cohesive strength, good heat resistance and water resistance, and good adhesion to polyolefin, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, the use of solvents has been regulated from the viewpoint of environmental protection, and emulsion type adhesives, which are water-dispersed systems, have been in the spotlight. Emulsion type adhesives are usually produced by blending a polymer emulsion with a filler, a thickener, a crosslinking agent, and other additives as required. Although the emulsion type has the advantage of not containing a solvent, on the other hand, it has drawbacks such as a slow drying speed, poor wettability to low surface energy substances, and weak adhesive strength compared to solvent systems. There is.

As one of the methods for overcoming such drawbacks,
Blending a tackifying resin when manufacturing an adhesive,
Several methods are known for modifying with a tackifying resin in the production of the polymer emulsion itself. For example, Japanese Patent Application Laid-Open No. 54-23641 and Japanese Patent Publication No. 2-30351 disclose a method in which a polymer compound or a tackifying resin is dissolved in a polymerizable monomer and subjected to emulsion polymerization. There is no disclosure of using the prepared polymer. The latter discloses a method of polymerizing by continuous addition. Adhesives produced by these methods are said to exhibit superior performance to adhesives produced by the method of mixing a pre-emulsified tackifying resin with a polymer emulsion. Japanese Patent Publication No. 7-57864 discloses a method of emulsion-polymerizing a polymerizable monomer in which a tackifying resin is dissolved in the presence of a seed polymer having a limited particle size. Since the amount is too large, no one having a good balance between adhesive strength and cohesive strength has been obtained.

[0004]

The problem to be solved by the present invention is that the prior art methods are still sufficiently satisfactory in the balance between the adhesive force and the cohesive force, and also in the balance between heat resistance, water resistance and polyolefin adhesiveness. The object of the present invention is to provide a polymer emulsion having an excellent balance of physical properties.

[0005]

Means for Solving the Problems As a result of intensive investigations by the present inventors regarding such a problem, as a result, a specific amount of a monomer containing a specific amount of a tackifying resin was polymerized in the presence of a specific polymer. By doing so, they have found that the above problems can be solved, and completed the present invention. That is, the present invention is a polymer emulsion obtained by emulsion polymerization of one monomer or a mixture of two or more monomers selected from (meth) acrylic acid esters, aromatic vinyl compounds or vinyl group-containing carboxylic acids. In the presence of, one monomer or a mixture of two or more monomers selected from (meth) acrylic acid esters, aromatic vinyl compounds, vinyl group-containing carboxylic acids 10
An emulsion composition obtained by emulsion-polymerizing a mixture obtained by dissolving 10 to 300 parts by weight of a tackifying resin in 0 part by weight with respect to 100 parts by weight of a solid content of the polymer emulsion. is there. Alternatively, in the presence of a polymer emulsion obtained by emulsion-polymerizing one monomer or a mixture of two or more monomers selected from (meth) acrylic acid esters, aromatic vinyl compounds or vinyl group-containing carboxylic acids. , A (meth) acrylic acid ester, an aromatic vinyl compound, a vinyl group-containing carboxylic acid, or a mixture of two or more monomers 10
This is a method for producing an emulsion composition, wherein a mixture of 10 parts by weight to 300 parts by weight of a tackifying resin is dissolved in 0 parts by weight, and 45 parts by weight to 250 parts by weight is emulsion polymerized with respect to 100 parts by weight of the solid content of the polymer emulsion. .

The present invention will be described in detail below. In the emulsion composition of the present invention, first, a polymer emulsion is obtained by emulsion polymerization of a monomer mixture containing a monomer selected from (meth) acrylic acid esters and aromatic vinyl compounds and vinyl group-containing carboxylic acids. Manufacturing (hereinafter, this step is sometimes referred to as pre-stage polymerization).

The term "(meth) acrylic acid ester" as used herein means methacrylic acid ester and acrylic acid ester. Preferred examples include methyl-, ethyl-, propyl-, n-butyl-, isobutyl-, tert-butyl-, n-amyl-, isoamylhexyl-, octyl-, nonyl-, decyl-, dodecyl-. , Octadecyl-, cyclohexyl-, phenyl-, benzyl-alkyl or allyl (meth) acrylates, glycidyl compounds such as glycidyl (meth) acrylate and methylglycidyl (meth) acrylate,
A hydroxyl group-containing compound such as β-hydroxy (meth) acrylate can be used. Among these, methyl,
Ethyl, butyl, 2-ethylhexyl acrylate, methyl methacrylate and the like are mentioned as preferred examples.

Specific examples of preferred aromatic vinyl compounds are styrene and o-methylstyrene, m
-Methylstyrene, p-methylstyrene, ethylstyrene, ar-vinylxylene, ar-chlorostyrene,
ar-bromostyrene, vinylbenzyl chloride, p-
Examples include tertiary butyl styrene. Of these, styrene is the most preferable.

Preferred specific examples of vinyl group-containing carboxylic acids (hereinafter sometimes abbreviated as carboxylic acid monomers) include acrylic acid, methacrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and vinyl benzoate. Examples include acids. The amount of the carboxylic acid monomer in the first-stage polymerization is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the total monomers.

In the method of the present invention, the presence of a polymer emulsion obtained by emulsion-polymerizing a monomer selected from the above-mentioned (meth) acrylic acid esters and aromatic vinyl compounds and a monomer containing a carboxylic acid monomer. Although emulsion polymerization is carried out below, the polymer emulsion may be copolymerized with other polymerizable monomers in addition to the above monomers. To mention these examples at the monomer level, vinyl acetates such as vinyl acetate, vinyl butyrate, vinyl stearate, vinyl laurate, vinyl myristate, vinyl propionate, vinyl versatate, etc. As vinyl ethers, for example, vinyl ethers having an alkyl group such as methyl, ethyl, propyl, butyl, amyl and hexyl, vinyl cyanides such as acrylonitrile and methacrylonitrile, vinyl chloride, vinyl bromide, vinyl fluoride and vinylidene fluoride. Vinylidene chloride and other vinyl halides, maleic acid, fumaric acid, unsaturated dibasic acid alkyl esters such as mono- or dialkyl esters such as itaconic acid, olefins such as ethylene, acrylamide, methacrylamide, etc. Amides and their N
-Methylol compounds and alkoxy compounds, silicon-containing α, β-ethylenically unsaturated monomers such as vinyltrichlorosilane and vinyltriethoxysilane, unsaturated acids such as cinnamic acid vinylsulfonic acid and styrenesulfonic acid, vinylpyridine, Examples thereof include basic monomers such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, and diethylaminoethyl methacrylate.

In addition, a compound obtained by polymerizing a compound having at least two polymerizable unsaturated bonds in the molecule can also be mentioned. As such examples, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, divinylbenzene, diallyl phthalate, ethylene glycol diacrylate, 1,3- Butylene glycol diacrylate, bis (4-acryloxypolyethoxyphenyl) propane, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, 1,6-
Hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, other polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, allyl methacrylate and so on. In addition, as a diene monomer, for example, butadiene, chloroprene, isoprene, a polyethylene monomer having three or more double bonds such as trivinylbenzene and triallyl isocyanurate, and a reaction having a double bond Specific emulsifiers are also included.

Since the composition of the monomers in the first-stage polymerization has a great influence on the performance as an adhesive, it is necessary to appropriately design Tg, molecular weight and the like according to the application. The emulsion polymerization method is not particularly limited, and a conventionally known method can be adopted. That is, it is a method of polymerizing a monomer using a polymerization initiator in the presence of an emulsifier and, if necessary, a chain transfer agent or seed particles. As the emulsifier, anionic, nonionic or cationic surfactants can be used. As the anionic surfactant, for example, alkylbenzene sulfonic acid alkali metal salt, alkyl sulfate alkali metal salt, polyoxyethylene alkylphenol sulfate alkali metal salt, alkyldiphenyl ether disulfonic acid alkali metal salt, dialkylsulfosuccinic acid alkali metal salt, etc. are used. be able to. As the nonionic surfactant, for example, polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ether, polyoxyethylene higher fatty acid ester, ethylene oxide-propylene oxide block copolymer and the like can be used. Further, an acrylic water-soluble oligomer may be used in combination with the anionic surfactant. Known emulsifiers having a radical-polymerizable double bond, which are called reactive emulsifiers, can be used.
Further, a water-soluble polymer compound having an action as a colloid protective agent such as polyvinyl alcohol, hydroxyethylcellulose, hydroxypropylcellulose and the like can be used if necessary. As the amount of these surfactants and water-soluble polymer compounds used increases, the water resistance of the resulting polymer may decrease, so it is preferable that the amount used is small, but at least the polymerization stability and It is preferable to use the minimum amount necessary for maintaining the mechanical stability and chemical stability of the product. The amount used is usually selected in the range of 0.1 to 7 parts by weight with respect to 100 parts by weight of the monomer.

The chain transfer agent is not particularly limited and may be appropriately selected and used from among those commonly used for controlling the molecular weight of ordinary polymerization reactions. Such chain transfer agents include, for example, propyl mercaptan, butyl mercaptan, dodecyl mercaptan having 1 to 30 carbon atoms.
C1 to C30 organic sulfur compounds such as mercaptans with octyl alkyl groups, octyl thioglycolate, thioglycolic acid, and diphenyl sulfide, and carbon tetrachloride, carbon tetrabromide, and bromotrichloromethane. And halogenated hydrocarbons having 1 to 20 carbon atoms are included. These chain transfer agents may be used alone or in combination of two or more.

As the polymerization initiator, a compound that generates radicals at a temperature of 0 to 150 ° C. is usually used. As the polymerization initiator, a water-soluble one is mainly used, but an oil-soluble one may be used. Typical polymerization initiators include water-soluble persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate, inorganic peroxides such as hydrogen peroxide, benzoyl peroxide,
Cumene hydroperoxide, lauroyl peroxide, tert-butyl peroxide, tert-butyl peroxy-
Examples thereof include organic peroxides such as 2-ethylhexanoate and azo compounds such as azobisisobutyronitrile. Further, a so-called redox-based initiator that combines radicals with a reducing agent to generate radicals in the presence of a trace amount of metal ions is also used. Examples of this redox system include hydrogen peroxide-ferrous chloride system, cumene hydroperoxide-sodium ascorbate system and the like. Further, an initiator having an amino group such as azobisisobutylamine can also be used. The amount of these polymerization initiators used is usually 10
It is selected in the range of 0.1 to 2.5 parts by weight with respect to 0 parts by weight. Moreover, the said peroxide may be used individually and may be used in combination of 2 or more type.

The method of supplying the polymerizable monomer to the polymerization site is not particularly limited, and a method of introducing it all at once, a method of adding continuously or intermittently, a method of arbitrarily changing the addition rate, etc. are optional. Can be used for. Further, the monomers may be added as they are, but a method of previously emulsifying and adding may be employed. The method similar to the above can be adopted also as a method of adding the polymerization initiator.

The polymerization reaction is usually carried out at a temperature in the range of 0 to 130 ° C, preferably 30 to 100 ° C. In this way, the polymer emulsion obtained in the first stage preferably has a higher cohesive force than the polymer produced by the subsequent polymerization, and specifically, the toluene insoluble content is preferably 30% or more, and further preferably Is 40% or more.

In the production method of the present invention, a monomer selected from (meth) acrylic acid esters, aromatic vinyl compounds and vinyl group-containing carboxylic acids in the presence of the polymer emulsion obtained as described above. A method in which 10 to 300 parts by weight of a tackifying resin is dissolved in 100 parts by weight of a monomer mixture containing a compound is emulsion-polymerized. This emulsion polymerization may be carried out subsequently to the former stage, or one prepared in advance may be used. The amount of the monomer mixture is 4 per 100 parts by weight of the solid content of the polymer emulsion.
5 to 250 parts by weight. Japanese Unexamined Patent Publication No. 54-2364
In No. 1 or Japanese Examined Patent Publication No. 30351/1990, since the polymer prepared in advance is not used, the effects of the present invention are not exhibited. As the monomer to be used, in addition to the (meth) acrylic acid esters, the aromatic vinyl compounds and the carboxylic acid monomer, a radical polymerizable monomer may be used in combination. As these examples, the same as those described above can be preferably used.

In the present invention, the tackifying resin is a terpene resin such as a pinene resin, a dipentene resin and its petroleum resin modified, a rosin resin such as rosin, oxidized rosin, hydrogenated rosin, disproportionated rosin and its glycerin ester,
Coumarone indene resin, alkylphenol resin, aliphatic and aromatic petroleum resin, etc. These tackifying resins may be used alone or in combination of two or more. The combination may be blended or modified.

The amount of tackifying resin is 10
It is 10 to 300 parts by weight, preferably 20 to 200 parts by weight, and more preferably 25 to 150 parts by weight, relative to 0 parts by weight. If it is less than this range, the adhesiveness to various materials, especially plastics, especially polyolefin, becomes poor, and if it exceeds this range, the stability as an emulsion and the cohesive force become insufficient.

The amount of the monomer mixture in which the tackifying resin is dissolved is such that the solid content of the polymer emulsion present in the system is 10 parts.
It is 45 to 250 parts by weight, preferably 50 to 150 parts by weight, based on 0 parts by weight. The solid content of the emulsion referred to here is the weight of the emulsion after drying treatment at 130 ° C. for 3 hours divided by the weight before drying.

The polymer emulsion produced by the above-mentioned production method exhibits superior performance to that obtained by mixing the pre-emulsified tackifying resin with the polymer emulsion. Also,
In Japanese Patent Application No. 2-302770, the amount of the monomer mixture in which the tackifying resin is dissolved is 5 to 40 parts by weight based on 100 parts by weight of the solid content of the polymer emulsion present in the system. If it exceeds, the amount of the monomer that dissolves the tackifying resin increases, and it becomes a low molecular weight acrylic polymer,
It is said that it causes a decrease in cohesive force. Therefore, the adhesive strength is reduced. However, according to the study by the inventors of the present invention, it has been found that, when it is 45 parts by weight or more, the adhesive strength is recovered in the presence of vinyl group-containing carboxylic acids, which is quite surprising.

Also in this emulsion polymerization, a conventionally known method can be adopted similarly to the emulsion polymerization in the former stage, and the method described in the former stage can be adopted as it is. The method of adding the monomer mixture in which the tackifying resin is dissolved to the polymerization system may be the same as it is, but it is preferable to emulsify it in advance. There is no particular limitation on the method for use in the polymerization site, and a method of introducing all at once, a method of continuously or intermittently adding, a method of arbitrarily changing the addition speed, and the like can be arbitrarily adopted.

The nonvolatile content (solid content) in the emulsion of the present invention is not particularly limited, but is usually 20 to 70% by weight, preferably 40 to 60% by weight, and more preferably 45 to 55% by weight. The particle size of the polymer particles is not particularly limited, but is usually 0.01 to 10 μm, preferably 0.05 to 1
μm, more preferably 0.1 to 0.5 μm. In any step of the method for producing an emulsion of the present invention,
Various additives may be added in addition to those used in the above-mentioned ordinary emulsion polymerization. Such additives include preservatives, bactericides, antiaging agents, antioxidants, viscosity modifiers,
Examples include pH adjusters, defoamers, and plasticizers.

The polymer emulsion obtained by the present invention has an excellent balance between adhesive strength and cohesive strength, has good heat resistance and water resistance, and exhibits good adhesion to polyolefin. Therefore, it can be used as various adhesives including contact adhesives and laminating adhesives, pressure-sensitive adhesives and the like. To produce these using the polymer emulsion of the present invention, a conventionally known method can be adopted, and specifically, a crosslinking agent, inorganic particles, an organic filler, a thickener, a defoaming agent, It can be produced by incorporating a preservative and the like.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described with reference to the following examples. The test conditions for adhesiveness are as follows. Adhesive Strength An adhesive was applied to a No. 9 cotton cloth having a width of 1 inch and not subjected to sizing and water repellent treatment with a # 55 bar coater and dried at room temperature for 30 minutes.

This is applied to a predetermined base material at 20 ° C. and 65%
In a humidity atmosphere, a 4.5 kg roller was reciprocated once to make a pressure bond, and after being left under the same conditions for 24 hours, the tensile strength at the time of peeling at a speed of 100 mm / min was measured using a Tensilon type constant speed tensile tester. It was measured. The base material is a polyethylene plate degreased with ethanol and a soft vinyl chloride plate. Heat-resistant creep resistance A 500g weight is hung on one end of a cotton cloth sample with an adhesion length of 100mm created under the same conditions as above, and the shear width after a specified time or the time until falling is displayed. did. Heat resistance The sample prepared above is allowed to stand in an atmosphere of 80 ° C., and this is immediately subjected to a tensile test under the same conditions, and its peel strength is measured. Water resistance The sample prepared above is immersed in water at 20 ° C. for 3 days, and immediately subjected to a tensile test under the same conditions, and its peel strength is measured.

Reference Example 1 80 g of butyl acrylate, 17 g of methyl methacrylate, 3 g of methacrylic acid were mixed with 1 part of sodium polyoxyethylene nonylphenyl ether sulfate.
g and distilled water 0.5 g ammonium persulfate 50
It was mixed with g and sufficiently emulsified with an emulsifying machine. Next, a thermometer,
50 g of distilled water was placed in a three-necked flask equipped with a stirrer and a reflux condenser, and the internal temperature was kept at 85 ° C. Next, the above emulsion was continuously charged into this flask over 2 hours. During this time, the internal temperature was kept at 80 ° C. After the addition of the emulsion, the reaction was continued at the same temperature for 1 hour. The solid content of the obtained emulsion was 50% and the particle size was 350 nm. This emulsion is
(A) It may be called liquid.

[0028]

Example 1 50 g of a disproportionated rosin ester was dissolved in a monomer mixture solution of 35 g of butyl acrylate, 14.5 g of methyl methacrylate, and 0.5 g of methacrylic acid, and this was further mixed with polyoxyethylene nonylphenyl ether. 0.15 g of sodium sulfate and 0.2 g of ammonium persulfate were mixed with 50 g of distilled water and sufficiently emulsified with an emulsifying machine. This emulsion is called liquid (B).

In a three-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 200 g of the liquid (A) obtained in Reference Example 1 and 50 g of distilled water were placed, and the internal temperature was set to 80.
C. The emulsion (B) solution prepared above was continuously charged into this flask over 2 hours. During this time, the internal temperature was kept at 80 ° C. After the addition of the emulsion, the stirring was continued at the same temperature for 1.5 hours. The solid content of the resulting emulsion was 50%, the particle size was 440 nm, and the polymerization rate was 100%. The pH of this emulsion was adjusted to 8.0 with aqueous ammonia. This emulsion is designated as "E1".

E1 was tested for its adhesiveness to a soft PVC plate under the above-mentioned test conditions. As a result, the adhesive strength was 5 kg.
The heat-resistant creep dropped in 3 hours, the heat resistance was 2 kg, and the water resistance was 2 kg.

[0031]

[Embodiment 2] The amount of the liquid (B) used in Embodiment 1 was set to 0.
An emulsion was obtained in exactly the same manner as in Example 1 except that the amount was 5 times. The solid content of the resulting emulsion is 50
%, The particle diameter was 400 nm, and the polymerization rate was 100%.
The pH of this emulsion was adjusted to 8.0 with aqueous ammonia. This emulsion is designated as "E2".

As for E2, the adhesive performance to the soft vinyl chloride board was tested as in Example 1, and as a result, the adhesive strength was 4 kg.
The heat-resistant creep dropped in 3 hours, the heat resistance was 2.2 kg, and the water resistance was 2.2 kg.

[0033]

[Third Embodiment] The amount of the liquid (B) used in the first embodiment is set to 2.
An emulsion was obtained in exactly the same manner as in Example 1 except that the amount was tripled. The solid content of the resulting emulsion is 50
%, The particle diameter was 460 nm, and the polymerization rate was 100%.
The pH of this emulsion was adjusted to 8.0 with aqueous ammonia. This emulsion is designated as "E3".

E3 was tested for adhesive performance to a soft vinyl chloride plate as in Example 1, and as a result, adhesive strength was 4 kg,
The heat-resistant creep dropped in 2 hours, the heat resistance was 1.8 kg, and the water resistance was 2 kg.

[0035]

Example 4 50 g of the monomer mixture solution of the solution (B) in Example 1 was added to 80 g, and 20 g of the disproportionated rosin ester was added to 20 g.
An emulsion was obtained in the same manner as in Example 1 except that the amount was changed to g. The solid content of the resulting emulsion is 50
%, The particle diameter was 450 nm, and the polymerization rate was 100%.
The pH of this emulsion was adjusted to 8.0 with aqueous ammonia. This emulsion is designated as "E4".

E4 was tested for adhesion performance to a soft PVC plate as in Example 1, and as a result, the adhesion strength was 5.5 k.
g, heat-resistant creep drops in 2.5 hours, heat resistance is 2k
g, water resistance was 2.5 kg.

[0037]

Example 5 50 g of the monomer mixture of the liquid (B) in Example 1 was added to 60 g, and 50 g of the disproportionated rosin ester was added to 40 g.
An emulsion was obtained in the same manner as in Example 1 except that the amount was changed to g. The solid content of the resulting emulsion is 50
%, The particle diameter was 420 nm, and the polymerization rate was 100%.
The pH of this emulsion was adjusted to 8.0 with aqueous ammonia. This emulsion is designated as "E5".

E5 was tested for adhesion performance to a soft PVC plate as in Example 1. As a result, the adhesion strength was 5 kg,
The heat-resistant creep dropped in 3 hours, the heat resistance was 2 kg, and the water resistance was 2 kg.

[0039]

Example 6 An emulsion was prepared in the same manner as in Example 1 except that 50 g of the monomer mixture of the liquid (B) in Example 1 was changed to 60 g and 50 g of disproportionated rosin ester was changed to 40 g of hydrogenated rosin ester. Got The solid content of the resulting emulsion is 50%, the particle size is 440 nm, and the polymerization rate is 1
00%. The pH of this emulsion was adjusted to 8.0 with aqueous ammonia. This emulsion is "E6"
And

E6 was tested for adhesion performance to a soft vinyl chloride plate as in Example 1. As a result, the adhesion strength was 5 kg,
The heat-resistant creep dropped in 3 hours, the heat resistance was 2.5 kg, and the water resistance was 2.5 kg. As a result of testing the adhesive performance of E6 to the polyester plate, the adhesive strength is 2k.
g, heat-resistant creep drops in 1 hour, heat resistance is 1.2k
g, water resistance was 1.2 kg.

[0041]

Example 7 An emulsion was obtained in the same manner as in Example 1 except that 50 g of the monomer mixture of the liquid (B) in Example 1 was changed to 60 g and 50 g of the disproportionated rosin ester was changed to 40 g of terpene phenol. It was The solid content of the resulting emulsion is 50%, the particle size is 460 nm, and the polymerization rate is 1
00%. The pH of this emulsion was adjusted to 8.0 with aqueous ammonia. This emulsion is "E7"
And

E7 was tested for adhesion performance to a soft PVC plate as in Example 1, and as a result, the adhesion strength was 6 kg,
Heat-resistant creep drops in 3.2 hours, heat resistance is 2.5k
g, water resistance was 2.5 kg. As a result of testing the adhesive performance of the E7 to the polyester plate, the adhesive strength was 2 kg, the heat-resistant creep dropped in 1 hour, and the heat resistance was 1.
The water resistance was 2 kg and the water resistance was 1.2 kg.

[0043]

Example 8 80 g of butyl acrylate, 17 g of methyl methacrylate and 3 g of methacrylic acid were mixed with 50 g of distilled water in which 1 g of sodium polyoxyethylene nonylphenyl ether sulfate and 0.5 g of ammonium persulfate were dissolved,
It was sufficiently emulsified with an emulsifying machine. Next, 100 g of distilled water was put into a three-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and the internal temperature was kept at 85 ° C. Next, the above emulsion was continuously charged into this flask over 2 hours. During this time, the internal temperature was kept at 80 ° C. After the addition of the emulsion, the reaction was continued at the same temperature for 1 hour. Liquid (B) separately prepared, that is, butyl acrylate 35
g, methyl methacrylate 14.5 g, methacrylic acid 0.
Disproportionated rosin ester 5 was added to a monomer mixture consisting of 5 g.
0 g was dissolved, and this was further mixed with 50 g of distilled water in which 0.15 g of sodium polyoxyethylene nonylphenyl ether sulfate and 0.2 g of ammonium persulfate were dissolved, and an emulsified solution sufficiently emulsified with an emulsifier was used for 2 hours. It was continuously charged. During this time, the internal temperature was kept at 80 ° C. After the addition of the emulsion, the stirring was continued at the same temperature for 1.5 hours. The solid content of the resulting emulsion was 50%, the particle size was 440 nm, and the polymerization rate was 100%. The pH of this emulsion was adjusted to 8.0 with aqueous ammonia. This emulsion is designated as "E8".

As for E8, the adhesive performance to the soft vinyl chloride board was tested as in Example 1. As a result, the adhesive strength was 5 kg.
The heat-resistant creep dropped in 3 hours, the heat resistance was 2 kg, and the water resistance was 2 kg. As a result of testing the adhesive performance of E8 to the polyester plate, the adhesive strength is 2.5 kg,
Heat-resistant creep drops in 1.5 hours, heat resistance is 1.3k
g, water resistance was 1.3 kg.

[0045]

Comparative Example 1 The amount of the liquid (B) used in Example 1 was adjusted to 0.
An emulsion was obtained in exactly the same manner as in Example 1 except that the amount was doubled. The solid content of the resulting emulsion is 50
%, The particle diameter was 350 nm, and the polymerization rate was 100%.
The pH of this emulsion was adjusted to 8.0 with aqueous ammonia. This emulsion is designated as "H1".

With respect to H1, the adhesion performance to the soft vinyl chloride plate was tested as in Example 1, and as a result, the adhesion strength was 3 kg,
The heat-resistant creep dropped in 30 minutes, the heat resistance was 0.5 kg, and the water resistance was 0.5 kg.

[0047]

Comparative Example 2 An emulsion was obtained in the same manner as in Example 1 except that the amount of the liquid (B) used in Example 1 was tripled. The solid content of the resulting emulsion is 50%,
The particle diameter was 560 nm and the polymerization rate was 100%. The pH of this emulsion was adjusted to 8.0 with aqueous ammonia. This emulsion is designated as "H2".

With respect to H2, the adhesion performance to the soft vinyl chloride board was tested as in Example 1, and as a result, the adhesion strength was 2 kg,
The heat-resistant creep dropped in 2 hours, the heat resistance was 0.5 kg, and the water resistance was 0.5 kg. Used in the above examples,
The disproportionated rosin ester is pentaline 4850 (trade name: manufactured by Rika Hercules Co., Ltd.), the hydrogenated rosin ester is ester gum H (trade name: manufactured by Arakawa Chemical Industry Co., Ltd.), and the terpene phenol is YS Polystar T30.
(Product name: Yasuhara Chemical Co., Ltd.) was used.

[0049]

When the emulsion of the present invention is used as an adhesive, it has an excellent balance of adhesive strength and cohesive strength, so that it exhibits adhesive strength that can withstand handling in a short time after adhesion, even though it is water-based. However, the curing time to reach the final strength is short and the strength does not change much.

Since it is excellent in heat resistance and water resistance, it is widely used as an adhesive and its raw material in construction fields such as walls and floor materials, civil engineering fields such as mortar and concrete, automobile interior materials, packaging materials, casing materials, etc. it can. In the production of the emulsion, it is not necessary to introduce a special or new device, and it is not necessary to disperse and blend the tackifying resin in the emulsion. Therefore, the manufacturing process can be omitted. As a result, production efficiency is good and it can be used with peace of mind regardless of whether it is a site product or a line product.

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Claims (2)

[Claims] 1. A polymer emulsion obtained by emulsion polymerization of one monomer or a mixture of two or more monomers selected from (meth) acrylic acid esters, aromatic vinyl compounds and vinyl group-containing carboxylic acids. In the presence of 100 parts by weight of one monomer or a mixture of two or more monomers selected from (meth) acrylic acid esters, aromatic vinyl compounds, vinyl group-containing carboxylic acids, and tackifying resins 10 to 30.
An emulsion composition obtained by emulsion-polymerizing 45 to 250 parts by weight of a mixture in which 0 parts by weight is dissolved, based on 100 parts by weight of the solid content of the polymer emulsion. 2. A polymer emulsion obtained by emulsion polymerization of one monomer or a mixture of two or more monomers selected from (meth) acrylic acid esters, aromatic vinyl compounds and vinyl group-containing carboxylic acids. In the presence of 100 parts by weight of one monomer or a mixture of two or more monomers selected from (meth) acrylic acid esters, aromatic vinyl compounds, vinyl group-containing carboxylic acids, and tackifying resins 10 to 30.
A method for producing an emulsion composition, which comprises emulsifying 45 to 250 parts by weight of a mixture obtained by dissolving 0 part by weight with respect to 100 parts by weight of a solid content of the polymer emulsion.