JPH083408A - Ethylene-vinyl acetate resin emulsion composition - Google Patents

Abstract

PURPOSE:To provide an ethylene-vinyl acetate resin emulsion compsn. excellently balanced among water resistance, adhesion, heat resistance and cold resistance. CONSTITUTION:This ethylene-vinyl acetate resin emulsion compsn. comprises 100 pts.wt. (in terms of solid) ethylene-vinyl acetate resin emulsion and 0.5-30 pts.wt. glycol ether incorporated thereinto in the presence of 0.1-10 pts.wt. polyvinyl alcohol.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ethylene-vinyl acetate resin emulsion composition, and more particularly to an ethylene-vinyl acetate resin emulsion composition excellent in water resistance, adhesiveness, and balance between heat resistance and cold resistance.

[0002]

2. Description of the Prior Art Ethylene-vinyl acetate resin emulsions are used for processing adhesives, adhesives, paints, fibers, paper, and coatings.
It is widely used as a binder for various materials and as an admixture for cement mortar. Thus, a dispersant and an emulsifier are required when producing an ethylene-vinyl acetate resin emulsion which is widely used.

[0003]

Thus, the widely used ethylene-vinyl acetate resin emulsions also have drawbacks. That is, when an ethylene-vinyl acetate resin emulsion is produced, a dispersant and an emulsifier are required as described above, which may impair water resistance and adhesiveness. If the amount of the dispersant and the emulsifier is reduced in order to improve the water resistance and the adhesiveness, it becomes difficult to produce a stable emulsion.

The present invention has the above-mentioned problems of the prior art,
It is an object of the present invention to provide an ethylene-vinyl acetate resin emulsion composition that solves difficult points and is excellent in water resistance, adhesiveness, and balance between heat resistance and cold resistance.

[0005]

As a result of various studies, the present inventors have found that the above object of the present invention can be achieved by incorporating a specific compound into an ethylene-vinyl acetate resin emulsion. The present invention has been reached.

That is, the ethylene-vinyl acetate resin emulsion composition of the present invention contains polyvinyl alcohol
0.5 to 30 parts by weight of glycol ethers is added to 100 parts by weight of the solid content of the ethylene-vinyl acetate resin emulsion in the presence of 1 to 10 parts by weight.

The present invention will be described in detail below. Examples of the ethylene-vinyl acetate resin emulsion in the present invention include ethylene-vinyl acetate resin emulsions and copolymer resin emulsions with ethylene and other monomers copolymerizable with vinyl acetate. As the monomer, for example, fatty acid vinyl other than vinyl acetate (vinyl butyrate, etc.), (meth) acrylic acid esters [methyl, ethyl, 2-ethylhexyl ester of (meth) acrylic acid, etc.], olefins other than ethylene, Halogen-containing monomers (vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, etc.), aromatic monomers (styrene, alkyl-substituted styrene, etc.) alkyl vinyl ethers, acrylamides, polymerizable unsaturated Carboxylic acid monomers, for example, monobasic acid monomers [acrylic acid, (meth)
Acrylic acid, (iso) acrylic acid, (iso) crotonic acid], polybasic monomers (maleic acid, fumaric acid, itaconic acid) and their partial esters, polymerizable polybasic anhydrides (maleic anhydride, etc.) , Dienes (butadiene, chloroprene, etc.) and the like. These may be used alone or in combination of two or more.

Examples of the glycol ethers in the present invention include ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol dipropyl ether, ethylene glycol monobutyl ether. , Ethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monoethyl ether, propylene glycol diethyl ether, propylene glycol monopropyl ether, propylene glycol dipropyl ether, propylene glycol monobutyl ether, propylene glycol dibu Ether and the like. The glycol ethers further include diethylene glycol monomethyl ether, which is a condensation product of ethylene glycol, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dihexyl ether,
Triethylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, pentaethylene glycol diethyl ether, hexaethylene glycol dipropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether, hexapropylene glycol dimethyl ether, Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol and the like can also be mentioned. These may be used alone or in combination of two or more.

The amount of glycol ethers added is
Solid content of ethylene-vinyl acetate resin emulsion 100
0.5 to 30 parts by weight, preferably 2.
It is 0 to 10 parts by weight. If the amount added is less than 0.5 parts by weight, it is difficult to obtain the effect on water resistance, adhesiveness, and balance between heat resistance and cold resistance. On the other hand, if it exceeds 30 parts by weight, water resistance and adhesiveness The addition amount is in the range of 0.5 to 30 parts by weight as described above, because it causes a decrease in the balance between heat resistance and cold resistance and polymerization stability.

Examples of the dispersant and emulsifier used in the present invention include water-soluble polymers such as completely or partially saponified polyvinyl alcohol, methyl cellulose and hydroxyethyl cellulose, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether. And nonionic surfactants such as tellurium and polyoxyethylene polyoxypropylene block copolymers, anionic surfactants such as lauryl sulfate ester salts and alkylbenzene sulfonates, etc., and these are used alone or in combination. be able to.

As the polyvinyl alcohol in the present invention, those generally used can be used, and examples thereof include those having an average degree of polymerization of 200 to 4,500 and a saponification degree of 65 mol% or more. Further, other monomers such as acrylamide, polyvinyl alcohol modified with maleic anhydride, or a part of polyvinyl alcohol chemically modified by means such as carboxylation or sulfonation may be used.

The addition amount of polyvinyl alcohol is 0.1 to 10 parts by weight, preferably 0.5 to 10 parts by weight based on 100 parts by weight of the solid content of the ethylene-vinyl acetate resin emulsion.
5 parts by weight. The addition amount of polyvinyl alcohol is 0.
If it is less than 1 part by weight, the emulsifying power is not sufficient and aggregates are frequently generated during the polymerization reaction, while if it exceeds 10 parts by weight, thickening occurs during the polymerization reaction and stirring is hindered. Also, since stable polymerization is difficult due to abnormal heat generation, the addition amount is in the range of 0.1 to 10 parts by weight as described above.

The amount of polyvinyl alcohol added is
It is also strongly related to the amount of glycol ethers added at the same time. That is, since the glycol ethers themselves have an emulsifying power, in a system in which a large amount of glycol ethers are used in combination, the emulsion stability is maintained even if the amount of polyvinyl alcohol added is small. Further, in this case, the effect on the adhesiveness due to the reduction of the amount of polyvinyl alcohol is further improved. On the other hand, on the contrary, in a system in which the addition amount of glycol ethers is small, the addition amount of polyvinyl alcohol cannot be extremely reduced in order to maintain the stability of emulsion.

Examples of the polymerization initiator used for obtaining the composition of the present invention include persulfates such as ammonium persulfate, hydrogen peroxide, and various organic peroxides. In addition, a redox-based initiator obtained by combining these with a reducing agent can also be used.

As the polymerization method used to obtain the composition of the present invention, known emulsion polymerization methods are used, and examples thereof include a monomer sequential addition method, a batch charging method and a two-step polymerization method. Is not limited to.

Further, the emulsion of the present invention includes
Additives that are commonly used can be added to the composition of the present invention. Examples of this additive include organic solvents (aromatics such as toluene and xylene, alcohols, ketones, esters, halogen-containing solvents, etc.), plasticizers, suspending agents, thickeners, flow agents. There are property improvers, antiseptics, rust preventives, defoamers, fillers, wetting agents, coloring agents and the like.

[0017]

In the ethylene-vinyl acetate resin emulsion composition of the present invention, by containing glycol ethers in the ethylene-vinyl acetate resin emulsion, a stable composition can be obtained even when the amount of the dispersant and the emulsifier added is small. Moreover, the composition has improved water resistance, adhesiveness, and a balance between heat resistance and cold resistance.

[0018]

EXAMPLES Examples of the present invention will now be described in detail, but the present invention is not limited to these examples. Example 1 470 g of polyvinyl alcohol (Denka Poval B-17 manufactured by Denki Kagaku Kogyo Co., Ltd .: average degree of polymerization 170)
0, saponification degree 88 mol%), a polyvinyl alcohol aqueous solution consisting of 90 g of sodium acetate and 40 kg of pure water, and sodium sulfoxide 54 as a promoter.
g, ethylenediaminetetraacetic acid (EDTA) 4 g, ferrous sulfate 2 g and pure water 800 g, the total amount of the mixture, 3-methyl-3-methoxy-1-butanol 2.35 kg (Kuraray Co., Ltd. trade name Solfit), and 31.6 kg of pre-added vinyl acetate was charged into a 130 L capacity polymerization can. Then, the inside of the polymerization vessel was replaced with nitrogen gas under stirring, and then 8.7 kg of ethylene was charged while heating.

After the completion of the ethylene charging, the internal liquid temperature reached 55 ° C., and from that time, ammonium persulfate (APS) 3 was added.
% Aqueous solution 6 kg was continuously added to the polymerization system over 6 hours. About 3 hours after the start of addition of the above APS aqueous solution, about 2
After that, 15.3 kg of vinyl acetate, which was added later, was continuously added to the polymerization system.

After completion of the polymerization, the solid content and pH were adjusted with pure water and aqueous ammonia to obtain an ethylene-vinyl acetate copolymer emulsion composition having a weight ratio of ethylene and vinyl acetate of 15:85. The adhesive property and water resistance of the obtained emulsion composition were measured. Table 1 below shows the polymerization recipe and the physical properties of the emulsion (Em). The results of the adhesive properties and water resistance of the emulsion composition obtained are shown in Table 2 below.

Examples 2-9 Type and amount of polyvinyl alcohol, and 3-methyl-3
Example 1 with various amounts of -methoxy-1-butanol
An emulsion composition was prepared in the same manner as above, and the adhesive property and water resistance of the obtained emulsion composition were measured.
The polyvinyl alcohol used in Example 7 together with the trade name Denka Poval B-17 was Denka Poval B-05 manufactured by Denki Kagaku Kogyo Co., Ltd.
(Average degree of polymerization 550, degree of saponification 88%). Table 1 below
Polymerization formulation and emulsion (Em) in each Example
The physical properties of The results of the adhesive properties and water resistance of the emulsion compositions obtained in each example are shown in Table 2 below.

[0022]

[Table 1] Note 1) Polymer composition: EVA; ethylene: vinyl acetate = 15: 85% by weight However, in Example 14, ethylene: vinyl acetate = 23:
77% by weight EVA-BA; ethylene: vinyl acetate: butyl acrylate = 10: 85: 5% by weight 2) B-17: Denki Kagaku Kogyo Co., Ltd. polyvinyl alcohol (trade name Denka Poval B-17); average polymerization Degree 1700, saponification degree 88% (wt%): means 17 parts by weight of B-17 with respect to 100 parts by weight of solid content of ethylene-vinyl acetate resin emulsion.

3) B-05: Polyvinyl alcohol manufactured by Denki Kagaku Kogyo Co., Ltd. (trade name: Denka Poval B-0)
5); average degree of polymerization 550, degree of saponification 88% (wt%): means part by weight of B-05 with respect to 100 parts by weight of solid content of the ethylene-vinyl acetate resin emulsion.

4) 3-Methyl-3-methoxy-1-butanol: Kuraray Co., Ltd. trade name Solfit (% by weight): 3-methyl-3-methoxy based on 100 parts by weight of solid content of ethylene-vinyl acetate resin emulsion. -1 means parts by weight of 1-butanol.

5) Ethylene glycol monobutyl ether: trade name butyl cellosolve (manufactured by Wako Pure Chemical Industries, Ltd.) (% by weight): It means the parts by weight of ethylene glycol monobutyl ether based on 100 parts by weight of the solid content of the ethylene-vinyl acetate resin emulsion.

6) Remarks: M; Solfit was dissolved in a monomer to carry out emulsion polymerization. Emulgen; polyoxyethylene nonyl phenyl ether (Emulgen 931 manufactured by Kao Corporation, HLB17.
2) 7) Solid content: Evaporation residue after drying at 105 ° C. for 3 hours 8) Viscosity: BM type rotational viscometer, value at 12 ° rotation at 30 ° C. 9) Mechanical stability: Maron stability tester (10 Kg) 1
(000 rpm, 5 minutes)

[0027]

[Table 2] Note 10) Adhesive properties: Adhesive properties were evaluated with plywood (3 mm thick) and semi-rigid vinyl chloride sheets A and B. The test body is
Under a temperature condition of 20 ° C or 5 ° C, 100 g / m ² (wet) of the emulsion composition is applied to the plywood surface with a bar coater, and it is attached to a semi-rigid vinyl chloride sheet, and after degassing, it is pressed with a C clamp for 5 hours. Then, the test specimen of 20 ° C adhesion was aged at 20 ° C for 7 days, and the test specimen of 5 ° C adhesion was aged at 5 ° C for 3 days, and further aged at 20 ° C for 7 days.
It was submitted to the test.

11) Adhesiveness: The above test body was cut into a width of 25 mm, and 180 ° peel strength was measured (peeling strength 200 mm / min). At the same time, the wood breaking rate was measured by observing the vinyl chloride sheet.

12) Heat resistant cleave: 60
In a 90 ° peeled state in a ℃ atmosphere, a static load of 500 g / 25 mm was applied, and the peeled length after 10 minutes and 30 minutes was measured.

13) Cold resistance: The above test specimen was left in an atmosphere of -10 ° C. for one day and then shock-peeled by hand to determine the state of destruction. Judgment of cold resistance: ○ If the sheet is cut, the blade will be broken even if a knife is inserted. ○ ～ △ If the sheet is cut and a knife is inserted, a mixed fracture of the wooden fracture and the interface will be destroyed. △ If the sheet is cut and a knife is inserted, the interface will be destroyed. Interface (mirror surface) destruction 14) Water resistance: Measured according to the water drop test of JIS K 6828.

Example 10 An emulsion composition was prepared in the same manner as in Example 2 except that butyl acrylate was copolymerized in addition to ethylene and vinyl acetate. The composition of ethylene, vinyl acetate and butyl acrylate is by weight,
It was 10: 85: 5. The adhesive property and water resistance of the obtained emulsion composition were measured. Table 3 below shows the polymerization formulation and the physical properties of the emulsion (Em). In addition, Table 4 below shows the results of measured adhesive properties and water resistance of the obtained emulsion composition.

Example 11 An emulsion was prepared in the same manner as in Example 2 except that 3-methyl-3-methoxy-1-butanol was dissolved in pre-added vinyl acetate and post-added vinyl acetate. A composition was prepared and the adhesive properties and water resistance of the resulting emulsion composition were measured. Table 3 below shows the polymerization formulation and the physical properties of the emulsion (Em). In addition, Table 4 below shows the results of measured adhesive properties and water resistance of the obtained emulsion composition.

Example 12 In Example 2, 235 g (0.5% / vinyl acetate) of polyvinyl alcohol (an equal amount mixture of the trade name DENKA POVAL B-17 and the trade name DENKA POVAL B-05) 235 g of polyoxyethylene nonyl phenyl ether (trade name: Emulgen 931: H manufactured by Kao Corporation)
An emulsion composition was prepared in the same manner as in Example 2 except that the emulsifier aqueous solution was prepared according to LB17.2), and the adhesive property and water resistance of the obtained emulsion composition were measured. Table 3 below shows the polymerization formulation and the physical properties of the emulsion (Em). In addition, Table 4 below shows the results of measured adhesive properties and water resistance of the obtained emulsion composition.

Example 13 In Example 2, instead of 3-methyl-3-methoxy-1-butanol, ethylene glycol monobutyl ether (trade name butyl cellosolv manufactured by Wako Pure Chemical Industries, Ltd.)
An emulsion composition was prepared in the same manner as in Example 2 except that was used, and the adhesive property and water resistance of the obtained emulsion composition were measured. Table 3 below shows the polymerization formulation and the physical properties of the emulsion (Em). In addition, Table 4 below shows the results of measured adhesive properties and water resistance of the obtained emulsion composition.

Example 14 An emulsion composition was prepared in the same manner as in Example 8 except that the amount of ethylene was increased. The composition of ethylene and vinyl acetate is the weight ratio,
It was 23:77. The adhesive property and water resistance of the obtained emulsion composition were measured. Table 3 below shows the polymerization formulation and the physical properties of the emulsion (Em). In addition, Table 4 below shows the results of measured adhesive properties and water resistance of the obtained emulsion composition.

Example 15 The emulsion composition according to Example 8 was solvent modified. The composition of the emulsion, toluene and xylene is the weight ratio,
It is 100: 2.5: 2.5. The adhesive property and water resistance of the obtained emulsion composition were measured. Table 3 below shows the polymerization formulation and the physical properties of the emulsion (Em). In addition, Table 4 below shows the results of measured adhesive properties and water resistance of the obtained emulsion composition.

[0037]

[Table 3] Note 1) to 9): Same as Note 1) to 9) in Table 1 above.

[0038]

[Table 4] Note 10) to 14): Same as Note 10) to 14) in Table 2 above.

Comparative Example 1 Emulsion polymerization was carried out in the same manner as in Example 1 except that 3-methyl-3-methoxy-1-butanol was not added. However, the emulsified state was poor and a coagulated product was deposited one day after the polymerization. Polymerization recipe and polymerization stability are shown in Table 5 below.

Comparative Examples 2 to 4 Type and amount of polyvinyl alcohol, and 3-methyl-3
Example 1 with various amounts of -methoxy-1-butanol
Emulsion polymerization was carried out in the same manner as above to prepare an emulsion composition, but stable polymerization could not be carried out except in the case of Comparative Example 2. Therefore, only the emulsion composition obtained in Comparative Example 2 was measured for adhesive properties and water resistance. Table 5 below shows the polymerization formulation and the physical properties or polymerization stability of the emulsion (Em) in each Comparative Example.
Table 6 below shows the results of the adhesive properties and water resistance of the emulsion composition obtained in Comparative Example 2.

Comparative Example 5 Vinyl chloride sheet / adhesive agent commonly used for plywood (trade name: Bond CV3105, manufactured by Konishi Co., Ltd.)
The adhesive properties and water resistance of W) were measured. This product contains 5 to 10% by weight of an organic solvent (aromatic hydrocarbon). Table 5 below shows the physical properties of the emulsion (Em), and Table 6 below shows the results of the measured adhesive properties and water resistance.

[0042]

[Table 5] Note 1) to 9): Same as Note 1) to 9) in Table 1 above.

[0043]

[Table 6] Note 10) to 14): Same as Note 10) to 14) in Table 2 above.

[0044]

In the composition of the present invention, ethylene-
Since the vinyl acetate resin emulsion contains glycol ethers, the composition of the present invention can provide an emulsion composition excellent in water resistance, adhesiveness, and balance between heat resistance and cold resistance, Its industrial value is high.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI technical display location // C08L 71/02 LQE (72) Inventor Hiroaki Yoshikawa 2-1-9 Akamidai, Konosu City, Saitama Prefecture −106 (72) Inventor Kenji Idemoto 201-4-201 Goseki, Urawa-shi, Saitama Prefecture (72) Inventor Takatoshi Tanaka, No. 6, Goi Minami Coast, Ichihara City, Chiba Denki Kagaku Kogyo Co., Ltd. Chiba Plant (72) Invention Hideki Hirano 6 Goi Minamikaigan, Ichihara-shi, Chiba Electrochemical Industry Co., Ltd. Chiba Plant (72) Inventor Hiroki Yamamoto 6 Goi Minamikaigan, Ichihara City, Chiba Electrochemical Industry Co., Ltd. Chiba Plant

Claims (2)

[Claims] 1. An amount of 0.5 to 30 parts by weight of glycol ethers is added to 100 parts by weight of the solid content of the ethylene-vinyl acetate resin emulsion in the presence of 0.1 to 10 parts by weight of polyvinyl alcohol. A characteristic ethylene-vinyl acetate resin emulsion composition. 2. A solid content of 100 parts by weight of a copolymer resin emulsion of ethylene, vinyl acetate and another monomer copolymerizable with ethylene and vinyl acetate in the presence of 0.1 to 10 parts by weight of polyvinyl alcohol. And 0.5 to 30 parts by weight of glycol ethers are contained in the resin emulsion composition.