JPH086009B2 - Carboxylated polyolefin chlorinated emulsion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is characterized in that 50% or more of the carboxyl groups of a chlorinated carboxylated polyolefin produced by graft-copolymerizing a chlorinated polyolefin with an unsaturated carboxylic acid are used. The present invention relates to an aqueous emulsion of a carboxylated polyolefin chlorinated product in which the hydrated polymer is used as a part or the whole of the emulsion and which is stable and has good adhesion.

[Conventional technology]

Conventionally, an aqueous emulsion of carboxylated polyolefin chlorinated product with stable and good adhesion using polyolefin chlorinated compound as a base polymer has not been produced yet.
There are aqueous emulsions of carboxylated ethylene vinyl acetate copolymers that are different from the present invention but are used as adhesives. (JP-A-52-142686) [Problems to be solved by the invention] Carboxylated ethylene vinyl acetate copolymer emulsions that have been conventionally used as adhesives and coating agents have low solid content or insufficient stability. There is a problem that it is difficult to put it into practical use as an adhesive, and since the solid content in the emulsion is low, toluene and ethylene vinyl acetate copolymer are further added after carboxylation to increase the concentration of resin, alkali, water. It was necessary to add and emulsify to prepare an emulsion.

The present invention is a polyolefin chlorinated product having good adhesiveness to polyolefin itself is selected as a base polymer, dissolved in an organic solvent such as toluene at a high concentration, carboxylated to impart hydrophilicity, and water and alkali are added. In addition, an emulsion is prepared by emulsification, and the adhesive strength is remarkably large when adhering a polar substance containing a metal such as aluminum or iron with polypropylene or polyolefin, and the content of an organic solvent such as toluene is low, In addition, the object is to obtain an aqueous emulsion having good stability such as room temperature stability and mechanical stability.

[Means for solving the problem]

The first aspect of the present invention is to use α, β-unsaturated carboxylic acid (including its anhydride) and CH ₂ ═CXY for 99 to 50 parts by weight of chlorinated polyolefin having a chlorine content of 5 to 70% by weight. (Where X is the same as or different from Y, X or Y
Is selected from H, Cl, alkyl groups, acetoxy groups, ester groups, amide groups and hydroxyalkyl groups. 1) of a monomer having a) or a prepolymer obtained from the monomer.
When 50 parts by weight of the carboxylated polyolefin chlorinated product obtained by graft copolymerization is emulsified by adding water to a polymer in which 50% or more of the carboxyl groups have been neutralized, the polymer is part of an emulsifier. Or an aqueous emulsion of carboxylated polyolefin chlorinated product.

Generally, aqueous emulsions are roughly classified into two methods. One is a direct emulsion polymerization method, and the other is a method of dispersing a prepolymerized polymer in water. In either method, emulsifiers or protective colloids have been used in the past. Therefore, when a film is produced from an emulsion, the emulsifier considerably remains in the obtained film, which adversely affects the physical and chemical properties of the film and reduces the adhesive performance.

The present invention provides a novel aqueous emulsion of chlorinated carboxylated polyolefin without the above-mentioned conventional drawbacks.

The emulsifier used in the present invention is a high molecular weight polymer and has excellent adhesiveness, water resistance and heat sealability. Therefore, the emulsion obtained by the present invention is a stable one having many characteristics such as adhesiveness and coating property.

The present invention is described in more detail. In the presence of 99 to 50 parts by weight of a chlorine chlorinated product having a chlorine content of 5 to 70% by weight, α, β-unsaturated carboxylic acid (including its anhydride).
And a carboxylated polyolefin chlorinated solution obtained by graft-copolymerizing a monomer having the general formula CH ₂ = CXY (where X and Y are the same as above) or a prepolymer of the monomer using a solvent and a radical initiator. 100 parts by weight, water 1
~ 1000 parts by weight, and 50% or more of the basic substances in the carboxylated polyolefin chlorinated product are added to the basic substance, and if necessary, 0.1 to 50 parts by weight of a surfactant is added and the emulsion is obtained by stirring and emulsifying. It is an aqueous emulsion of chlorinated polyolefin chloride.

Α grafted to the above chlorinated polyolefin,
β-unsaturated carboxylic acid (including its anhydride) and general formula CH ₂ = CXY (where X and Y are the same as above) or when the amount of the prepolymer used is less than 1 part by weight or 50 parts by weight If it is used over the range, a stable emulsion having excellent adhesiveness cannot be obtained. At the time of emulsification, it is industrially advantageous to enter the emulsion step in a state where the chlorinated carboxylated polyolefin is dissolved or dispersed in a solvent.

The carboxylated polyolefin chlorinated product of the present invention includes a chlorinated product obtained by graft-copolymerizing polyolefin with an α, β-unsaturated carboxylic acid such as maleic anhydride or fumaric anhydride.

The polyolefin chlorinated product used in the present invention is obtained by uniformly or non-uniformly chlorinating polyethylene, polypropylene, ethylene-propylene copolymer or the like with a chlorination rate of at least 5% by weight and at most 70% by weight. Chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene-propylene copolymer, chlorinated ethylene-vinyl acetate copolymer and the like.

When the chlorine content of the chlorinated polyolefin used in the present invention is less than 5% by weight, the solubility in an organic solvent or water is extremely low, and it cannot be used as the adhesive of the present invention.
Further, when the chlorine content exceeds 70% by weight, the obtained carboxylated polyolefin chlorinated product emulsion has a remarkably low adhesive strength, which makes it difficult to put into practical use, and likewise cannot be used as the adhesive of the present invention.

As the α, β-unsaturated carboxylic acid (including the anhydride thereof) used for the synthesis of the carboxylated polyolefin chlorinated product of the present invention, acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, Examples thereof include unsaturated carboxylic acids having an ethylene bond at the α and β positions such as maleic acid monomethyl ester and fumaric acid monoethyl ester, and α, β-unsaturated carboxylic acid anhydrides such as maleic anhydride. These can be used alone or as a mixture.

Particularly when acrylic acid, maleic anhydride or a mixture thereof is used as the α, β-unsaturated carboxylic acid, the obtained graft copolymer is excellent in the function as an emulsifier when the carboxylic acid is neutralized, The performance of the emulsion is also excellent and its industrial value is high.

Further, it is advisable to combine α, β-unsaturated carboxylic acid so that the acid value of the carboxylated polyolefin chlorinated product of the present invention is 10 to 300 mgKOH / g, preferably 30 to 150 mgKOH / g.

General formula for graft copolymerization with α, β-unsaturated carboxylic acid
CH ₂ = CXY (where X is the same as or different from Y, X or Y
Is H, Cl, alkyl group, acetoxy group, ester group, amide group or hydroxyalkyl group. Examples of the unsaturated monomer having a) include ethylene, propylene, isobutene, octene-1, butene-1, vinyl chloride, vinylidene chloride, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate,
Examples thereof include methyl methacrylate, ethyl methacrylate, vinyl chloroacetate and the like.

The prepolymer of the present invention has a general formula CH ₂ = CXY (however,
X is the same as or different from Y, and X or Y is selected from H, Cl, an alkyl group, an acetoxy group, an ester group, an amide group and a hydroxyalkyl group. A compound having a certain degree of polymerization synthesized using a monomer having

The polymerization initiator for producing the carboxylated polyolefin chlorinated product of the present invention is a conventional radical initiator,
For example, di-alkyl peroxide such as di-cumyl peroxide, -di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl peroxy octoate, t-butyl peroxy acetate, t-butyl peroxyisobutyrate. There are peroxyesters such as rate, organic peroxides such as benzoyl peroxide, diacyl peroxide such as acetyl peroxide, and azo compounds such as azobisisobutyronitrile. The amount of these radical initiators used is 0.1 to 15 parts by weight based on the weight of the monomer mixture. The polymerization is preferably carried out at room temperature to 100 ° C.

The polymerization can be carried out by any of solution, suspension, emulsification and bulk polymerization methods. In the case of solution polymerization, aromatic hydrocarbons such as benzene, toluene and xylene and aliphatic hydrocarbons such as hexane and cyclohexane are used as a solvent. , CCl ₄ ,
A chlorinated hydrocarbon such as methylene chloride is used.

The carboxylated polyolefin chlorinated product, which is the emulsifier compound of the emulsion of the present invention, is based on the polyolefin chlorinated product with respect to α, β-unsaturated carboxylic acid (including its anhydride) and the general formula CH ₂ = CXY (provided that X, (Y is the same as above)
Is a polymer composition containing a monomer having or a graft copolymerization of a prepolymer of the monomer and a polymer composed of these monomers, having an acid value of 10 to 300 mgKOH / g, and a basic substance It becomes an emulsifier when emulsifying the carboxylated chlorinated polyolefin by the addition.

The carboxylated polyolefin chlorinated product contains 50% or more, preferably 80 to 100%, of the carboxyl groups contained in the polymer in the chemical calculation due to the basic substance.
When it is neutralized, it has an excellent function as an emulsifier, and the performance of the obtained emulsion is excellent.

Examples of the basic substance used for the above neutralization include alkali metal, alkali metal salt, alkali metal oxide, alkoxide, alkali metal base, ammonia or ammonium hydroxide, ammonium salt, ethylamines, propylamines, ethanolamine. , Ethylenediamines, piperidine, pyrrolidine, pyrroles, polyethyleneimine and the like.

In order to make the carboxylated polyolefin chlorinated product of the present invention more valuable in terms of stability and particle size, it is preferable to add a surfactant. As the surfactant, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyethyl alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, poly ( There are nonionic surfactants such as oxyethylene-oxypropylene) block copolymers, and examples of the anionic surfactant include higher alkyl sulfates, alkyls, aryl polyoxyethylene sulfates, higher fatty acid salts, alkyls. Examples include aryl sulfonates and alkyl phosphate salts.

The amount of the surfactant used is effective if, for example, 0.001 to 20% is added to chlorinated polypropylene.
When more than one type of surfactant is used, the mixing ratio is, for example, anionic surfactant: nonionic surfactant = 1: 0 to 5
You can choose from a wide range.

Further, water-soluble polymer substances such as conventionally used poval, hydroxyethyl cellulose, sodium alginate, etc. are also used as the protective colloid.

Since the emulsion of the present invention has a low content of conventional surfactants and protective colloids, the original characteristics of the resin constituting the emulsion are exhibited, and it is useful as an adhesive, an ink, a paint vehicle, and a coating agent.

〔Example〕

Example 1 Using a 4-necked flask having an internal volume of 2 l, the graft copolymerization reaction of the present invention was carried out as follows.

Chlorinated polypropylene (chlorination degree 28% by weight, Mw = 5000〜
50000) 60% toluene solution (manufactured by Toyo Kasei Co., Ltd.) (Chlorinated polypropylene 300g, Toluene 200g) 500g Acrylic acid 30g 2-Hydroxyethyl methacrylate 6g Kayaester 0-50 (polymerization initiator peroxide) 3g (Manufactured by Kayaku Nuri Co., Ltd.) After charging a flask with a toluene solution of chlorinated polypropylene, 30 g of acrylic acid and 6 g of 2-hydroxyethyl methacrylate were added, and the temperature was raised to 90 ° C. with stirring,
Nitrogen was replaced sufficiently. Then, the polymerization initiator is injected to start the polymerization, and thereafter, the remaining amount of the polymerization initiator is 1 /
Polymerization was performed for 6 hours in total by sequentially adding 3 portions. Solid content 6
2.7 parts were measured with a B-type viscometer. Viscosity is 8.3 poise / 25 ℃
A toluene solution of acrylic acid-modified chlorinated polypropylene was obtained.

The acid value of the carboxylated polypropylene chlorinated product obtained here was 83.5 mg KOH / g.

The toluene solution obtained above is used as reaction solution A.

Next, in a mixer-type emulsifier, quickly add 100 g of reaction solution A (40 ° C) water (40 ° C) 187 g ammonia water (purity 18.5%) 5 g Neugen EA-170 (surfactant, Daiichi Kogyo Seiyaku Co., Ltd.) 4 g The mixture was charged and vigorously stirred for 10 minutes while keeping the temperature at 40 ° C to obtain a white emulsion. The solid content of this emulsion is 23.5% by weight, the particle size is 0.5-7μ,
There was no change when left in the laboratory at room temperature for a month. The emulsion obtained in Example 1 was applied to 60μ, a biaxially oriented polypropylene film (OPP) untreated surface (manufactured by Toyobo Co., Ltd.), a 15μ aluminum foil and a cardboard so that the application amount of the adhesive was 8 g / m ^2. Then, heat sealing was performed and a peeling test was performed. The results are shown in Table 1.

Example 2 A reaction solution was synthesized in the same manner as in Example 1, but only the amount of acrylic acid was changed from 30 g to 72 g. Further, the same emulsification operation was carried out except that the amount of aqueous ammonia at the time of emulsification was changed from 5 g to 7 g, and a white stable aqueous emulsion having a solid content of 24.5% by weight was obtained. Using this emulsion, peel strength was measured in the same manner as in Example 1. The results are shown in Table 1.

Example 3 Example 1 except that the type of chlorinated polypropylene was changed.
I went the same way. That is, the degree of chlorination of chlorinated polypropylene
28% by weight, Mw = 50000-800000 (manufactured by Toyo Kasei Kogyo Co., Ltd.) was used. The peel strength was measured using this emulsion in the same manner as in Example 1. The results are shown in Table 1.

Example 4 The same procedure as in Example 1 was carried out except that 2 g of maleic anhydride was further added in the reaction solution synthesis.
An emulsion similar to that of Example 1 was obtained. The heat sheet strength was measured using this emulsion, and the results are shown in Table 1.

Example 5 The same procedure as in Example 1 was carried out except that 5 g of 2-hydroxyethyl acrylate was further added during the synthesis of the reaction solution in Example 1, and an emulsion similar to that in Example 1 was obtained. . The peel strength was measured using this emulsion. The results are shown in Table 1.

Example 6 The same procedure as in Example 1 was carried out except that 5 g of 2-hydroxylethyl acrylate and 3 g of maleic anhydride were added during the reaction solution synthesis. An emulsion was obtained. The peel strength was measured using this emulsion, and the results are shown in Table 1.

Example 7 Example 1 except that the type of chlorinated polypropylene was changed.
I went the same way. The emulsion of the present invention was produced using chlorinated polypropylene, the degree of chlorination was 34% by weight, and Mw = 5000 to 50000 (manufactured by Toyo Kasei Co., Ltd.), and the peel strength was measured in the same manner as in Example 1, and the result was obtained. Is shown in Table 1.

Example 8 Example 1 except that the type of chlorinated polypropylene was changed.
I went the same way. That is, the chlorinated polypropylene having a chlorination degree of 24% by weight and Mw of 5000 to 50000 (manufactured by Toyo Kasei Kogyo Co., Ltd.) was used to produce the emulsion of the present invention, and the peel strength was measured in the same manner as in Example 1. The results are shown in Table 1.

Example 9 Example 1 except that the type of chlorinated polypropylene was changed.
I went the same way. That is, chlorinated polypropylene, chlorination degree
The emulsion of the present invention was produced using 30% by weight and Mw = 50000-500000 (produced by Toyo Kasei Co., Ltd.), and the peel strength was measured in the same manner as in Example 1 and the results are shown in Table 1. .

Comparative Example 1 60% toluene solution of chlorinated polypropylene (chlorination degree 28% by weight, Mw = 5000-50000) in a mixer-type emulsifier (manufactured by Toyo Kasei Co., Ltd.) 100 g water (40 ° C.) 187 g Neugen EA-170 (Daiichi Kogyo Seiyaku Co., Ltd.) 10 g was rapidly charged and vigorously stirred for 10 minutes while keeping the temperature at 40 ° C. to obtain a white emulsion. The solid content of this emulsion is 24.1% by weight and the particle size is 1.5-20μ.
When left for a while, some began to separate. The emulsion obtained in this comparative example was applied to a 60μ biaxially oriented polypropylene film (OPP) untreated surface (manufactured by Toyobo Co., Ltd.) 15μ aluminum foil and cardboard so that the amount of adhesive applied was 8g / m ² and heat-sealed. The peeling test was performed and the results are shown in Table 1.

All point material breakage is the result that the polypropylene film used is damaged after the peeling test and accurate peel strength cannot be measured.

[Effect] The effects of the present invention are summarized as follows.

(1) The aqueous emulsion of a carboxylated polyolefin chlorinated product of the present invention which uses a carboxylated polyolefin chlorinated product in which a carboxyl group is neutralized as an emulsifier is a stable emulsion having an adhesive property which is characteristic of the carboxylated polyolefin chlorinated product. It is also useful as an adhesive, ink, paint vehicle, coating agent and paint.

(2) The water-based emulsion of the present invention is excellent in water-resistant heat sealability.

(3) The peel strength of the product of the present invention is 60μ as shown in Table 1.
OPP (untreated surface) comrades are 580g / cm, which is remarkably large. On the contrary, the undenatured product has 10 g / cm under the same conditions.

Further, while the peel strength of the 60 μOPP (untreated surface) / 15 μ aluminum foil of the present invention is 380 g / cm, which is remarkably large, the unmodified product under the same conditions is 187 g / cm.

Furthermore, while 60 μOPP (untreated surface) / paper of the present invention is remarkably large at 500 g / cm, unmodified product is 100 g / cm under the same conditions.
Is.

(4) Room temperature stability is stable for 3 months or more, but unmodified product is separated within 1 hour.

(5) It is possible to manufacture particles having a particle size of 7 μm or less.

Claims (3)

[Claims] 1. An α, β-unsaturated carboxylic acid (including its anhydride) and CH ₂ ═CXY based on 99 to 50 parts by weight of a chlorinated polyolefin having a chlorine content of 5 to 70% by weight. (Where X is the same as or different from Y, and X or Y is
It is selected from H, Cl, alkyl groups, acetoxy groups, ester groups, amide groups and hydroxyalkyl groups. 1) to 50 parts by weight of a prepolymer of the monomer is graft-copolymerized to obtain a highly hydrophilic carboxylated polyolefin chlorinated product, and the carboxyl group in the obtained carboxylated polyolefin chlorinated product is obtained.
An aqueous emulsion of a chlorinated carboxylated polyolefin, characterized in that, when water is added to a polymer of which 50% or more has been neutralized for emulsification, the polymer serves as a part or all of the emulsifier. 2. An aqueous solution of a chlorinated polyolefin chloride according to claim 1, wherein a chlorinated polyolefin obtained by uniformly or non-uniformly chlorinating polyethylene, polypropylene or an ethylene-propylene copolymer is used as the chlorinated polyolefin. Emulsion. 3. An α, β-unsaturated carboxylic acid is acrylic acid,
Methacrylic acid, maleic acid, fumaric acid, itaconic acid, the general formula of CH ₂ = CXY (where X or Y are the same or different, X or Y is H, Cl, alkyl group, acetoxy group, ester group, A monomer having an amide group or a hydroxyalkyl group) is an alkyl ester of acrylic acid or methacrylic acid, a hydroxyalkyl ester or ethylene, propylene, styrene, butene-1, octene-1, vinyl chloride, vinyl acetate. An aqueous emulsion of a chlorinated carboxylated polyolefin according to claim 1.