JPH068393B2 - Emulsion polymerization resin composition for water vapor permeable film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is useful for various structures such as cement boards, gypsum boards, and slate, coating materials such as wood, cloth, and paper, paints, and water vapor permeation useful as adhesives. The present invention relates to an emulsion polymerized resin composition for a coating film.

[Prior Art] It has been well known that a nonionic surfactant is used as an emulsifier in emulsion polymerization. As a nonionic surfactant for emulsion polymerization, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene fatty acid ester or the like is used.

However, when emulsion polymerization is carried out using these surfactants, the water vapor permeability of the resulting film is poor, and when this is used as a paint or adhesive, the water vapor permeability thereof is poor, resulting in poor adhesion or coating. There is a problem that the film swells, peels off, and dew condensation on the inner wall of the structure easily occurs, and there is a problem that the industrial application range is extremely limited. However, when emulsion polymerization is carried out using a large amount of nonionic surfactant beyond the common sense of those skilled in the art, the water vapor permeability of the obtained emulsion film is considerably improved, while other properties such as water resistance There is a problem that the physical properties are remarkably lowered and the practical value thereof is extremely lowered.

[Problems to be solved by the invention]

The present inventors have conducted extensive studies to solve the above problems found in conventional emulsion polymerization emulsifiers, and as a result, a specific range of certain polyalkylene glycols in the conventional nonionic surfactants for emulsion polymerization described above. By mixing the amounts and carrying out emulsion polymerization of the vinyl-based monomer, it was found that the film of the obtained emulsion has extremely excellent water vapor permeability, and the emulsion-polymerized resin composition of the present invention was completed.

[Means for solving problems]

That is, the emulsion-polymerized resin composition for a water vapor permeable film of the present invention comprises a vinyl-based monomer, a polyoxyalkylene alkyl ether, a polyoxyalkylene alkylphenyl ether, or a polyoxyalkylene fatty acid ester of 60 to 85% by weight and an average molecular weight. Emulsion polymerization is performed in the presence of 1 to 8% by weight of an emulsifier consisting of 40 to 15% by weight of 800 to 6,000 polyalkylene glycol.

[Action]

It is unclear why the emulsion-polymerized resin composition of the present invention exhibits excellent water vapor permeability when formed into a film. However, it is considered that the combination of emulsifiers specified in the present invention affects the physical properties of the produced resin and gives a film having a microstructure suitable for water vapor permeability.

Hereinafter, the configuration of the present invention will be described in detail.

The polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, and polyoxyalkylene fatty acid ester (hereinafter referred to as nonionic emulsifier) used in the present invention have an alkyl group having 4 carbon atoms.
To 20, preferably 8 to 15, the alkylene oxide is selected from ethylene oxide, propylene oxide, and butylene oxide, and the average number of added moles is 3
-80, preferably 20 to 50 mol, and ethylene oxide is suitable for 50% by weight or more of the alkylene oxide. When emulsion polymerization is carried out using an emulsifier outside these specific ranges, aggregates and the like are produced in both cases, and an emulsion in a preferable state cannot be obtained, or even if an emulsion in a good state is obtained. However, the film does not exhibit favorable water vapor permeability, and the intended purpose may not be achieved in some cases.

The polyalkylene glycol is selected from polyethylene glycol alone or a mixture of polyethylene glycol and polypropylene glycol and / or polybutylene glycol. When the mixture is used, it is desirable that 50% by weight or more thereof is polyethylene glycol. Further, the average molecular weight of these polyalkylene glycols is 800 to 6,000, more preferably 2,000 to 4,000. When emulsion polymerization is carried out using a polyalkylene glycol other than these specific ranges, an emulsion in a preferable state cannot be obtained, or even if it is obtained, the film shows favorable water vapor permeability. In addition, it is inconvenient because it does not serve the intended purpose.

The weight ratio of the nonionic emulsifier to the polyalkylene glycol is in the range of 85:15 to 90:40, and more preferably 80:20 to 70:30. The polyalkylene glycol in these mixtures may be either a product that is mixed as a by-product during the production of the nonionic emulsifier, or a product that is intentionally added and mixed after the production. The mixing ratio is 8
When the mixing amount of polyalkylene glycol is less than 5:15, an emulsion in a good state can be obtained by emulsion polymerization using this as an emulsifier, but the obtained film is preferable for its application. It is inconvenient because it does not show water vapor permeability. Also, if the mixing amount of polyalkylene glycol is more than 60:40, it is not possible to obtain an emulsion in good condition such as a large amount of coagulum even if emulsion polymerization is carried out using this as an emulsifier. However, the coating is inferior in physical properties such as water resistance and is not preferable in application.

When emulsion polymerization is performed using the emulsifier of the present invention, the amount used in the emulsion is 1 to 8% by weight, preferably 2 to 6% by weight. When the amount used is 1% by weight or less, the obtained film does not show favorable water vapor permeability, and conversely, when the amount used exceeds 8% by weight and more than that, a good emulsion cannot be obtained. Or even if it is obtained, the water resistance of the formed film is extremely poor, and both are inconvenient.

The emulsifier used in the present invention may be only a mixture of a nonionic emulsifier and a polyalkylene glycol, but other nonionic surfactants, anionic surfactants, water-soluble polymers within a range not impairing the effects of the present invention. Etc. may be used together. Examples of other nonionic surfactants include ethylene oxide propylene oxide block copolymers and sorbitan derivatives. Examples of anionic surfactants include long-chain alkyl sulfates, long-chain alkylbenzene sulfonates, polyoxyethylene alkyl sulphates and the like. Examples of water-soluble polymers include polyvinyl alcohol and hydroxyethyl cellulose. When these compounds are used in combination, 0.02 to 5 parts by weight is suitable for 1 part by weight of the nonionic emulsifier in the emulsifier of the present invention.

The polymerized resin which is the main component of the emulsion-polymerized resin composition of the present invention may be a polymer of an emulsion-polymerizable vinyl-based monomer, and is not particularly limited, among which an acrylic acid ester resin, an acrylic acid ester. Copolymer resins, styrene copolymer resins, vinyl acetate resins, vinyl acetate copolymer resins, ethylene-vinyl acetate copolymer resins and the like are preferable from the physical properties of the formed film. Specific examples of vinyl monomers used in these resins include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid such as methyl methacrylate, or esters of methacrylic acid; bromide. Vinyl halides such as vinyl, vinyl chloride and vinylidene chloride; vinyl esters such as vinyl acetate and vinyl propionate; vinyl aromatic monomers such as styrene and vinyl toluene; monoolefins such as ethylene and butadiene, or conjugated diolefins. Α, β unsaturated amides such as acrylonitrile; α, β unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid; vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane , Γ-methacryloxypropyltrimethoxy Cicilla,
There are vinylalkoxysilanes such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyldiethoxysilane, and glycidoxyalkoxysilanes, which are used alone or in combination of two or more kinds. .

In the emulsion polymerization of the present invention, the polymerization initiator used includes, for example, hydrogen peroxide solution, potassium persulfate, ammonium persulfate, etc., and if necessary, sodium hydrogen sulfite, ascorbic acid, tartaric acid, sodium thiosulfate, etc. You may use together the reducing agent of.

As a method for producing the emulsion-polymerized resin composition of the present invention, conventionally known emulsification means can be applied as the emulsion-polymerization means itself. For example, the concentration of the vinyl monomer is 20 to 70% by weight, and the emulsifier is 1.4 to 20 parts by weight per 100 parts by weight of the vinyl monomer. Furthermore, if necessary, a pH adjuster,
A polymerization degree regulator and other auxiliary additives may be used.
Examples of the auxiliary additive include various antifoaming agents, preservatives, thickeners, film-forming aids, solvents, film-forming aids, water repellents, etc., which are appropriately added and used according to their use. In particular, addition and use of various water repellents such as fluorine-based, silicone-based, polyethylene wax-based, paraffin wax-based, etc., in addition to the water vapor permeability of the formed film for the purpose of the present invention, the water repellency and water resistance of the film preferable for its application. It is effective as a means to improve the sex.

Emulsion polymerization resin composition of the present invention, mortar, slate,
Gypsum board, calcium silicate board, hard board, lightweight cellular concrete, asbestos cement board, wood wool cement board,
It is useful as a building material such as pulp cement board and dolomite plaster, and as a coating agent, paint and adhesive for industrial base materials such as paper, fiber, woven fabric, leather and wood.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to specific examples.

The water vapor permeability of various emulsion coatings in the specific examples is JIS Z 0208 as a test sample after coating the emulsion on Kent paper with a bar coater (# 50) and drying at 100 ° C. for 15 minutes.
The moisture proof packaging material was measured according to the moisture permeability test-method A.

Example 1 108.8 parts by weight of water was added to a reaction vessel equipped with a thermometer, a stir bar, a reflux condenser, and a dropping funnel, the temperature was raised to 70 ° C., and the system was replaced with nitrogen gas. On the other hand, a mixture of 33.75 parts by weight of polyethylene oxide lauryl ether having 40 moles of ethylene oxide added and 11.25 parts by weight of polyethylene glycol having an average molecular weight of 3,000 was dissolved in 365.5 parts by weight of water, and 95.3 parts by weight of styrene and 2- Ethylhexyl acrylate 434.1 parts by weight, methacrylic acid 10.3
539.7 parts by weight of the mixed monomer of 53 parts by weight is added, stirred, well emulsified, and added to a dropping funnel. Next, 46.0 parts by weight of this emulsion was added to the reactor, and 10.6 parts by weight of a 10% by weight aqueous solution of ammonium persulfate and 10.6 parts by weight of a 10% by weight aqueous solution of sodium hydrogen sulfite were used as a polymerization initiator. Uniform dropping was carried out for 3 hours from separate dropping funnels. After completion of the dropping, aging reaction was performed at 70 ° C. for 1 hour to obtain a desired emulsion.

Example 2 In the same manner as in Example 1, the number of moles of ethylene oxide added was 30 instead of polyoxyethylene lauryl ether.
Emulsion polymerization was carried out using the polyoxyethylene nonylphenyl ether of 1 to obtain the desired emulsion.

Example 3 51.4 parts by weight of methyl methacrylate as a monomer, n
-Emulsion polymerization was performed in the same manner as in Example 1 except that 478.0 parts by weight of butyl acrylate was used to obtain a desired emulsion.

Example 4 51.4 parts by weight of methyl methacrylate as a monomer, n
-Emulsion polymerization was performed in the same manner as in Example 2 except that 478.0 parts by weight of butyl acrylate was used to obtain a desired emulsion.

Example 5 Example 1 except that 360.0 parts by weight of styrene and 169.4 parts by weight of 2-ethylhexyl acrylate were used as monomers.
Emulsion polymerization was carried out in the same manner as above to obtain the desired emulsion.

Example 6 336.7 parts by weight of methyl methacrylate as a monomer, n
-Emulsion polymerization was carried out in the same manner as in Example 3 except that 192.7 parts by weight of butyl acrylate was used to obtain the desired emulsion.

Comparative Example 1 42.75 parts by weight of polyethylene glycol lauryl ether having an addition mole number of ethylene oxide of 40 and an average molecular weight of 3,000
Emulsion polymerization was carried out in the same manner as in Example 1 except that 2.25 parts by weight of polyethylene glycol was used to obtain an emulsion.

Comparative Example 2 42.75 parts by weight of polyoxyethylene nonylphenyl ether having 30 moles of ethylene oxide added and an average molecular weight of 3,0
Emulsion polymerization was carried out in the same manner as in Example 1 except that 2.25 parts by weight of polyethylene glycol of 00 was used to obtain an emulsion.

Comparative Example 3 42.75 parts by weight of polyethylene glycol lauryl ether having an addition mole number of ethylene oxide of 40 and an average molecular weight of 3,000
Emulsion polymerization was carried out in the same manner as in Example 3 except that a mixture of 2.25 parts by weight of polyethylene glycol was used to obtain an emulsion.

Comparative Example 4 Emulsion polymerization was carried out in the same manner as in Example 4 except that a mixture of 42.75 parts by weight of polyoxyethylene oxide nonylphenyl ether having 30 moles of ethylene oxide added and 2.25 parts by weight of polyethylene glycol having an average molecular weight of 3,000 was used. , An emulsion was obtained.

Comparative Example 5 3.75 parts by weight of polyethylene oxide lauryl ether having an addition mole number of 40 of polyethylene oxide and an average molecular weight of 3,
000 of polyethylene glycol was used in a mixture with 1.25 parts by weight of polyethylene glycol, and 102.5 parts by weight of styrene and 466.9 parts by weight of 2-ethylhexyl acrylate were used as monomers to carry out emulsion polymerization in the same manner as in Example 1 to obtain a desired emulsion. It was

Comparative Example 6 81.0 parts by weight of polyethylene oxide lauryl ether having a mole number of polyethylene oxide added of 40 and an average molecular weight of 3,
Emulsion polymerization was carried out in the same manner as in Example 1 except that a mixture of 000 and 27.0 parts by weight of polyethylene glycol was used as a monomer, and 84.0 parts by weight of styrene and 382.4 parts by weight of 2-ethylhexyl acrylate were used. Although an emulsion can be obtained, the polymerization stability is poor and there are many lumps, which is a problem in practical use.

The results of the above Examples and Comparative Examples are summarized in Table 1.

Example 7 A stainless steel autoclave having an internal volume of 1.5 and equipped with a stirrer, 474.3 parts by weight of water, and a polyethylene oxide lauryl ether having 40 moles of ethylene oxide added.
A mixture of 33.75 parts by weight and 11.25 parts by weight of polyethylene glycol having an average molecular weight of 3,000 is filled and the stirring speed is 250 rpm.
Nitrogen substitution was carried out while stirring at 2, then ethylene substitution was carried out, and the subsequent ethylene pressure was set to 50 kg / cm ² , and the autoclave was heated to 70 ° C.

Next, 458.7 parts by weight of vinyl acetate and 10.6 parts by weight of a 10% by weight aqueous ammonium persulfate solution and 10.6 parts by weight of a 10% by weight aqueous sodium hydrogen sulfite solution were uniformly added separately over 3 hours. Then, the temperature is raised to 85 ° C. and aging is carried out for 1 hour, and the ethylene: vinyl acetate copolymerization ratio (weight ratio) is 1
A copolymer resin emulsion of 5:85 was obtained.

Example 8 Emulsion polymerization was performed in the same manner as in Example 1 except that 539.7 parts by weight of vinyl acetate was used as a monomer and methyl methacrylate was removed, to obtain a desired emulsion.

Example 9 Emulsion polymerization was carried out in the same manner as in Example 1 except that 78.4 parts by weight of vinyl acetate and 461.3 parts by weight of n-butyl acrylate were used as monomers, and methyl methacrylate was removed to obtain a desired emulsion.

Comparative Example 7 Emulsion polymerization was carried out in the same manner as in Example 7 except that a mixture of 42.75 parts by weight of polyethylene oxide lauryl ether having 40 moles of added ethylene oxide and 2.25 parts by weight of polyethylene glycol having an average molecular weight of 3,000 was used to form an emulsion. Obtained.

Comparative Example 8 Emulsion polymerization was carried out in the same manner as in Example 8 except that a mixture of 42.75 parts by weight of polyethylene oxide lauryl ether having 40 moles of ethylene oxide added and 2.25 parts by weight of polyethylene glycol having an average molecular weight of 3,000 was used to form an emulsion. Obtained.

Comparative Example 9 Emulsion polymerization was carried out in the same manner as in Example 9 except that a mixture of 42.75 parts by weight of polyethylene oxide lauryl ether having 40 moles of ethylene oxide added and 2.25 parts by weight of polyethylene glycol having an average molecular weight of 3,000 was used. Obtained.

The above results are summarized in Table 2.

Example 10 Emulsion polymerization was carried out in the same manner as in Example 1 except that 90.3 parts by weight of styrene, 428.5 parts by weight of 2-ethylhexyl acrylate, and 10.6 parts by weight of vinyltris (2-methoxyethoxy) silane were used as monomers. A desired emulsion was obtained.

[Effects of the Invention] The emulsion-polymerized resin composition of the present invention has a very small amount of coarse particles and agglomerates generated during emulsion polymerization, and an emulsion in a good state can be obtained.
It has good mechanical stability and freeze stability, and the resulting coating shows significantly superior water vapor permeability compared to coatings from conventional emulsion-polymerized resin compositions, so paints and coating materials for various substrates, Alternatively, as an adhesive between various adherends, its practical value is extremely high.

Claims (1)

[Claims] 1. A vinyl-based monomer comprising 60 to 85% by weight of polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether or polyoxyalkylene fatty acid ester and 40 to 15% by weight of polyalkylene glycol having an average molecular weight of 800 to 6,000. An emulsion-polymerized resin composition for a water vapor permeable film, which is obtained by emulsion polymerization in the presence of 1 to 8% by weight of an emulsifier consisting of