JPH0212964B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to new and useful copolymer emulsion compositions. More particularly, the present invention relates to copolymer emulsions containing multiple copolymers capable of reacting with each other within the dispersed copolymer particles. Conventionally, self-crosslinking polymer emulsions were prepared by mixing multiple α,β-ethylenically unsaturated polar monomers that can react with each other with other α,β-ethylenically unsaturated monomers as the main component, and emulsion polymerizing the mixture. Polymer emulsions are used in a variety of applications such as paints, textile processing, adhesives, etc., and in each of these applications they offer improved durability compared to non-crosslinked polymer emulsions. It has been recognized that it is useful. However, in these cases, because the same molecule contains reactive groups that can react with each other, intramolecular crosslinking is likely to occur, and as a result, the desired durability may not be effectively obtained, or emulsion particles may be damaged during film formation. If the fusion is insufficient, the film-forming properties may deteriorate and the desired durability may not be achieved. As a method to improve this, it has been proposed to use a mixture of a plurality of emulsions each containing reactive groups that can react with each other. This method also
Similarly, since they provide useful properties to a certain extent, they have been applied to a variety of uses as mentioned above.
This method is effective when all of the reactive groups are exposed on the surface of each emulsion particle, but the reactivity of the reactive groups within the emulsion particles tends to be poor, and the crosslinking reaction is carried out efficiently and is durable. In some cases, this may be insufficient for the purpose of improving sexual performance. An object of the present invention is to provide a polymer emulsion composition with improved reactivity of the above-mentioned self-crosslinking polymer emulsion. According to the present invention, this object can be achieved by dispersing copolymer particles of a copolymer emulsion consisting of at least two layers A and B;
The layer contains an α,β-ethylenically unsaturated reactive monomer (M 1 ) containing a reactive polar group and an α,β-ethylenic monomer (M ₁ ) which can be radically copolymerized with this monomer and which does not contain a reactive polar group. It is composed of a copolymer (A) with an unsaturated monomer, and the B layer opposite to this A layer has another reactive polar group that is reactive with the reactive polar group of M ₁ . , a copolymer of a β-ethylenically unsaturated reactive monomer (M ₂ ) and an α,β-ethylenically unsaturated monomer that is radically copolymerizable with the monomer and does not contain a reactive polar group ( B), and the above M ₁
and M ₂ are multilayers of dispersed copolymer particles (hereinafter abbreviated as dispersed particles) of a copolymer emulsion, each of which is at least partially reacted with each other through reactive polar groups. A structured copolymer emulsion is provided. In the present invention, the molar ratio of M ₁ and M ₂ is suitably in the range of 0.1 to 20, more preferably 0.5 to 20.
It is 10. In addition, the appropriate weight ratio range of copolymer (A) and copolymer (B) is from 5:95 to 95:5,
More preferably the ratio is 10:90 to 90:10. Furthermore,
The appropriate proportion of M ₁ or M ₂ in the final copolymer composition is 0.05 to 20 parts by weight, respectively, assuming that the total of copolymer (A) and copolymer (B) is 100 parts by weight. , more preferably 0.5 to 5 parts. Examples of the α,β-ethylenically unsaturated reactive monomers (M ₁ ) and (M ₂ ) containing a reactive polar group in the molecule include epoxy derivatives such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether; Vinylsilanes such as trichlorosilane, vinyltriethoxysilane, vinyltris(β-menoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, etc.; acrylic acid, methacrylic acid, maleic acid or its half ester, fumaric acid or its half ester , itaconic acid or its half ester, unsaturated carboxylic acids such as crotonic acid; vinylamides such as acrylamide, N-methylolacrylamide, methacrylamide, N-methylolmethacrylamide, N,N-dimethylolacrylamide; dimethylolitacone; Methylol derivatives such as amides and alkoxylated products thereof; alcohols such as β-hydroxyethyl acrylate or methacrylate; amines such as alkylaminoacrylate or methacrylate; and the like. Furthermore, combinations of (M ₁ ) and (M ₂ ) include the above epoxy derivatives-unsaturated carboxylic acids or alcohols, epoxy derivatives-vinylamides or amines, epoxy derivatives-methylols, vinylsilanes-unsaturated carboxylic acids, etc. Examples include acids or alcohols, vinylsilanes-methylol derivatives, vinylsilanes-vinylamide or amines. Further, each of the constituents of the composition of the present invention,
α,β-ethylenic for preparing copolymer (A) [hereinafter also referred to as emulsion copolymer (A)] and copolymer (B) [hereinafter also referred to as emulsion copolymer (B)] The unsaturated monomer, that is, the above-mentioned M ₁ or M ₂ used in preparing the emulsifying copolymer thereof
Any α,β-ethylenically unsaturated monomer can be used as the monomer that can be radically copolymerized with the monomer and does not contain any reactive polar groups, but a typical example is methyl- , ethyl-, n-propyl-, isopropyl-, n-butyl-, isobutyl-, tert-butyl-, n-amyl-, isoamyl-, hexyl-,
Various (meth)acrylates such as octyl, nonyl, decyl, octadecyl, cyclohexyl, phenyl or benzyl (meth)acrylates.
Acrylic esters; various vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate or vinyl versatate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether or hexyl vinyl ether; Various vinyl ethers such as acrylonitrile, methacrylonitrile, maleic dinitrile, or vinyl cyanides (vinyl cyanides) such as vinylidene cyanide; or styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, vinylanisole , α-halostyrene, vinylnaphthalene, and divinylstyrene, as well as isoprene, chloroprene, butadiene, and vinylpyrrolidone. The emulsifier used in producing the emulsion copolymer of the present invention is a known emulsifier. For example, anionic emulsifiers such as sodium dodecylbenzene sulfate, sodium dodecylbenzene sulfonate, and alkylaryl polyether sulfates; polyoxyethylene lauryl ether, polyoxyethylene nonyl phenol ether, and polyoxyethylene-polyoxypropylene block copolymer. A nonionic emulsifier such as a combination of cationic emulsifiers and a cationic emulsifier such as cetyltrimethylammonium bromide and laurylpyridinium chloride can be appropriately selected and used. Furthermore, it is also possible to use a water-soluble oligomer as a dispersant without an emulsifier as described above or in combination with an emulsifier as described above. It is also effective to use water-soluble polymeric substances such as polyvinyl alcohol and hydroxyethyl cellulose together with the emulsifier or to add them to the emulsion after polymerization. Examples of water-soluble polymerization initiators include persulfates such as hydrogen peroxide, ammonium persulfate, and potassium persulfate, and combinations of these polymerization initiators and suitable ring agents such as ascorbic acid, sulfites, or sulfoxylates. Combinations of so-called redox initiators are also included. The method for producing the emulsion of the present invention is not limited to two-stage polymerization, and α, which can react with each other,
Multi-stage polymerization by repeating copolymers (A) and (B) containing β-ethylenically unsaturated reactive monomers (M ₁ ) and (M ₂ ) may also be used. Furthermore, (M ₁ ) and (M ₂ ) are not limited to the single-component system as mentioned above, but are multi-component systems (for example, (M ₁ ): unsaturated carboxylic acids and alcohols, (M ₂ ): epoxy derivative etc.), but monomers that can react with each other within (M ₁ ) or (M ₂ ) are not preferred. A specific method for producing the emulsion of the present invention will be described later, but in general, the polymerization temperature is in the range of 30°C to 90°C, and the final solid content is in the range of 30 to 65% by weight. Polymerization is
It is preferable to carry out the reaction in an atmosphere of an inert gas such as nitrogen. The emulsifier is preferably used only when shaping the polymer (A), and the amount used is preferably 0.5 to 20% by weight based on the total amount of the copolymer (A) and copolymer (B). 1 to 10% by weight, but in some cases polymer
It is also possible to use a small amount during the polymerization of (B) and during the repetition of (A) and (B). In addition, the difference in solubility parameter (SP) between copolymer (A) and copolymer (B) is 0 to 0.6
It is desirable that the In the emulsion having a multilayer structure of the present invention, the polymer (B) is formed using polymer (A) particles as cores, as shown in the Examples below. For example, polymer
When (A) has excellent water resistance, moisture permeability, etc., but lacks mechanical properties, adhesion, or cannot form a film, this polymer can be used according to the present invention. (A) is the core, and on the surface is a polymer with excellent adhesiveness, film-forming properties, and mechanical properties.
By forming (B), it is possible to obtain an emulsion that has excellent water resistance and moisture permeability, as well as excellent adhesiveness, film-forming properties, and mechanical properties. According to the present invention, not only such a combined effect but also
The following synergistic effects can also be expected. For example, Tg
When a hard polymer (A) with a high Tg is used as the core and a soft polymer (B) with a low Tg and high film-forming properties is laminated by chemical bonding, the high An emulsion with excellent elasticity, water resistance, and alkali resistance, low-temperature film-forming properties, and little blocking can be obtained. In general, if the layers are simply physically laminated, only a composite (additive) effect can be expected, whereas in the present invention, the layers are chemically bonded and laminated in this way, so properties other than those of each layer are imparted. It is. Moreover, according to the present invention, an emulsion having a multilayer structure having the above-mentioned properties can be obtained very easily by following a manufacturing method basically similar to the conventional emulsion polymerization method. The emulsion of the present invention thus obtained can be used with various coating agents,
It is useful as an adhesive, fiber processing agent, paper processing agent, etc. Next, specific examples of the present invention will be shown, but the present invention is not limited thereto. Note that parts represent parts by weight. Example 1 In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 100 parts of water and 5 parts of an emulsifier (for example, 3 parts of Emulgen 120 manufactured by Kao Atlas Co., Ltd. and 3 parts of Emulgen 120 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were added. Add 2 parts of Neogen R) and stir well. Next, the reaction vessel is heated to maintain an internal temperature of 80°C, and nitrogen gas is introduced into the vessel. Thereafter, a mixture of 15 parts of isobutyl methacrylate and 0.5 parts of glycidyl methacrylate and a mixture of 0.25 parts of potassium persulfate and 5 parts of water were injected over about 1 hour, and an additional 1
Time to mature. Then a mixture of 84 parts of butyl acrylate and 1 part of acrylic acid and potassium persulfate were added.
A mixture of 0.25 parts and 5 parts of water is poured over a period of about 2 hours, followed by further aging for 45 minutes. Thereafter, it was cooled to obtain a polymer. Comparative Example 1 15 parts of isobutyl methacrylate, 84 parts of butyl acrylate, 1 part of acrylic acid and 0.5 part of glycidyl methacrylate were uniformly mixed and copolymerized to obtain a copolymer emulsion. Comparative Example 2 A first stage copolymer emulsion of 15 parts of isobutyl methacrylate and 0.5 parts of glycidyl methacrylate obtained by a conventional method, and 84 parts of butyl acrylate and 1 part of acrylic acid obtained by a conventional method.
A blended emulsion was obtained by blending the second stage copolymer emulsion with the second stage copolymer emulsion. Comparative Example 3 A core-shell emulsion was prepared according to the method of Example 1, except that 0.5 part of glycidyl methacrylate and 1 part of acrylic acid were not used. Test Example 1 The emulsion obtained in Example 1 and isobutyl methacrylate-butyl acrylate copolymer emulsion (Comparative Examples 1, 2 and 3) having the same copolymer composition were cast on a glass plate at room temperature. and created a film. 1st
The table shows the mechanical properties of these films.

[Table] Example 3
From Table 1, it can be seen that films from emulsions according to the invention have the same polymer composition compared to films from emulsions obtained by conventional bulk loading methods, blended emulsions (same composition) and physically laminated emulsions. (The same applies to emulsifiers, etc.) However, it can be seen that it has excellent strength and elongation with low temperature sensitivity. Furthermore, as shown in Tables 2 and 3, the emulsion of the present invention is significantly superior to other emulsions in terms of film solvent resistance and water resistance.

[Table] Comparative Example 1 Dissolve Swell Dissolve Dissolve Comparative Example 2 Dissolve Dissolve Dissolve Dissolve Comparative Example 3 Dissolve Dissolve Dissolve Dissolve

[Table] Comparative example 2 △ ○ △
△ × × × ×
Comparative example 3 △ ○ △
○ × △ × ×
The test method was as follows. Solvent resistance: Apply the emulsion to a glass plate with a 3 mil applicator, dry at 23°C and 60RH for 1 day, then soak in solvent for 7 days and observe changes. Display the results as: No abnormalities > Swelling > Dissolution. Water resistance: Apply the emulsion to a glass plate with a 3 mil applicator, dry for one day at 23°C and 60RH, then soak in water for 1 to 15 days, and visually observe changes. The results are displayed as 〇 (good) > △ (fair) > × (poor). Example 2 A reaction vessel similar to Example 1 containing 100 parts of water and 7 parts of emulsifier (3 parts of Emulgen 931, 2 parts of Emulgen 120, and 2 parts of Neogen R) was prepared, and 70 parts of emulsifier was prepared.
Maintain the internal temperature at ℃, add 0.2 parts of ammonium persulfate, 0.2 parts of sodium pyrosulfite, 20 parts of styrene, 2-
20 parts of ethylhexyl acrylate and 0.5 part of glycidyl methacrylate are injected over about 1.5 hours and aged for an additional hour. This product was then mixed with 15 parts of styrene and 30 parts of 2-ethylhexyl acrylate.
parts, butyl acrylate 13 parts and acrylic acid 2 parts
0.2 parts of ammonium persulfate and 0.2 parts of sodium pyrosulfite were each injected over 2 hours, aged for 1 hour, and then cooled to obtain a polymer. Example 3 A reaction vessel similar to Example 2 containing 100 parts of water and 7 parts of emulsifier (5.0 parts of Emulgen 120 and 2 parts of Neogen R) was prepared, the internal temperature was maintained at 70°C, and 0.2 parts of ammonium persulfate was added. , sodium pyrosulfite 0.2
10 parts of methyl methacrylate, 10 parts of ethyl methacrylate, 10 parts of isobutyl methacrylate and 0.1 part of γ-methacryloxypropyltrimethoxysilane were injected over about 1 hour, and the mixture was further aged for 1 hour. This product is then added to ethyl acrylate.
A mixture of 30 parts of butyl acrylate, 10 parts of 2-ethylhexyl acrylate, 29 parts of 2-ethylhexyl acrylate, and 1 part of acrylic acid, as well as 0.2 parts of ammonium persulfate and 0.2 parts of sodium pyrosulfite were each injected over 2 hours, aged for 1 hour, and then cooled. , a polymer was obtained. Example 4 A reaction vessel similar to Example 2 containing 100 parts of water and 7 parts of emulsifier (5 parts of Emulgen 120 and 2 parts of Neogen R) was prepared, the internal temperature was maintained at 70°C, and 0.2 parts of ammonium persulfate was added. , sodium pyrosulfite 0.2
parts, 20 parts of styrene, 10 parts of acrylonitrile, 2-
20 parts of ethylhexyl acrylate and 0.5 part of glycidyl acrylate are injected over about 1.5 hours and aged for an additional hour. Thereafter, a mixture of 15 parts of styrene, 33 parts of 2-ethylhexyl acrylate, and 2 parts of acrylic acid, as well as 0.2 parts of ammonium persulfate and 0.2 parts of sodium pyrosulfite were injected into the product for 1.5 hours each, aged for 1 hour, and then cooled. A polymer was obtained. Example 5 A reaction vessel similar to Example 2 containing 100 parts of water and 6.5 parts of emulsifier (5 parts of Emulgen 120 and 1.5 parts of Neogen R) was prepared, the internal temperature was maintained at 60°C, and 0.2 parts of ammonium persulfate was added. , sodium pyrosulfite 0.2
parts, 18 parts of methyl methacrylate, 20 parts of styrene,
20 parts of butyl acrylate and 2 parts of methoxymethylolamide are injected over 2 hours and aged for a further 1 hour. This product is then injected with a mixture of 15 parts of styrene, 23 parts of butyl acrylate and 2 parts of acrylic acid, as well as 0.2 parts of ammonium persulfate and 0.2 parts of sodium pyrosulfite, each for 1.5 hours;
After aging for 1 hour, the mixture was cooled to obtain a polymer. Comparative Examples 4 to 7 Using the same emulsifier composition and monomer composition as in Examples 2, 3, 4, and 5, polymerization was carried out by batch charging for about 4 hours, followed by cooling to obtain an emulsion. The corresponding relationships are Comparative Example 4 and Example 2, Comparative Example 5 and Example 3, Comparative Example 6 and Example 4,
and Comparative Example 7 and Example 5. Test Example 2 The strength and elongation, solvent resistance, and water resistance of the films of Examples 2 to 5 and Comparative Examples 4 to 7 were compared according to the method described above. The results are shown in Table 4. These results show that the emulsion according to the present invention is significantly superior to conventional products in all physical properties. Next, the emulsion according to the present invention was mixed with a commercially available self-crosslinking acrylic emulsion (Voncoat 3226 and Voncoat manufactured by Dainippon Ink and Chemicals Co., Ltd.).
3385) and the physical properties of each film were compared. Table 5 shows the results. These results show that the emulsion of the present invention has superior film properties after heat treatment, even when compared with commercially available self-crosslinking acrylic emulsions of similar hardness.

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Claims (1)

[Claims] 1. The dispersed copolymer particles of the copolymer emulsion are composed of at least two layers, A and B, and the A layer contains an α,β-ethylenically unsaturated reactive monomer (M ₁ ) containing a reactive polar group. , is composed of a copolymer (A) of this and an α,β-ethylenically unsaturated monomer that can be radically copolymerized and does not contain a reactive polar group, and the B layer has the reactivity of M ₁ above. an α,β-ethylenically unsaturated reactive monomer (M ₂ ) having a reactive polar group that is reactive toward a polar group, and which is capable of radical copolymerization with the monomer (M 2 );
and is composed of a copolymer (B) with an α,β-ethylenically unsaturated monomer that does not contain a reactive polar group,
Moreover, the above-mentioned M ₁ and M ₂ are formed by dispersing copolymer particles of a copolymer emulsion forming a multilayer structure, characterized in that at least a portion of them have reacted with each other through reactive polar groups. copolymer emulsion composition.