JPH11255994A - Composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition slight in the deterioration of stability when left to stand and capable of forming films having good water resistance. SOLUTION: This composition includes (A) a vinyl alcohol-based polymer having one or more functional groups in the molecule selected from primary and secondary amino groups, (B) an aqueous emulsion and (C) an inorganic reducing agent in the weight ratio [(A)+(B)]/(C) of (100:0.001) to (100:100) on a solid basis. Alternatively, the above composition may also include (D) a polyvalent epoxy compound in the weight ratio [(A)+(B)+(C)]/(D) of (100:0.1) to (100:100) on a solid basis.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition, and more particularly, to an aqueous composition having excellent storage stability and capable of forming a water-resistant film.

[0002]

2. Description of the Related Art Conventionally, an aqueous composition containing an aqueous emulsion as a main component has good workability and can be made higher in concentration than an aqueous polymer solution, and since it is aqueous, there is no problem with respect to the environment and fire. For these reasons, they are used in various industrial applications such as adhesives, paints and binders. However, the water resistance of the film formed after drying is low because it is originally water-based, and many studies have been made on a crosslinking system by adding various cross-linking agents for the purpose of improving the water resistance. Many products have been commercialized.

[0003] However, although a remarkable improvement in water resistance can be achieved by using a cross-linked system, there are cases where the shelf stability is reduced. It is one of the big issues as a thing.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a composition capable of forming a highly water-resistant film by improving the storage stability of the composition of the prior art.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on the above objects and found that (A) a molecule having at least one functional group selected from primary and secondary amino groups in a molecule. It comprises a vinyl alcohol polymer, an aqueous emulsion (B) and an inorganic reducing agent (C), and [(A) + (B)] / (C) is 100 based on the weight of solids.
/0.001 to 100/100 or the composition described above contains (D) a polyvalent epoxy compound, and [(A) + (B) + (C)] / (D) is It has been found that a composition having a solid content of 100 / 0.1 to 100/100 is suitable for the intended purpose.

The vinyl alcohol polymer having at least one functional group selected from primary and secondary amino groups in the molecule (A) constituting the composition of the present invention is a primary and / or secondary polymer in the molecule. There is no particular limitation as long as it is a vinyl alcohol polymer containing an amino group. The vinyl alcohol polymer having this functional group can be obtained by various methods. For example, 1. An ethylenically unsaturated monomer having a primary amino group or a secondary amino group, or a primary A method in which an ethylenically unsaturated monomer having a functional group capable of forming an amino group or a secondary amino group is copolymerized with vinyl acetate and then saponified, or 2. an epoxy group such as allyl glucidyl ether is used. A method in which a mercaptan having an amino group is subjected to an addition reaction using a catalyst such as NaOH to an epoxy group in a side chain of a polymer comprising monomers and vinyl acetate, followed by saponification, or a reaction with a hydroxyl group of polyvinyl alcohol. It can be obtained by, for example, a method of reacting a compound having a functional group in a molecule and having a primary or secondary amino group with a vinyl alcohol-based polymer. There is also a method of polymerizing an ethylenically unsaturated monomer having a primary amino group or a secondary amino group in the presence of a vinyl alcohol polymer having a mercapto group. Is obtained.

The vinyl alcohol polymer having at least one functional group selected from primary and secondary amino groups in the molecule of the present invention has a functional group other than the primary or secondary amino group in the molecule. This does not matter as long as the effects of the present invention are not impaired. Monomer units that provide such functional groups include ethylene, isobutylene, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid,
(Anhydride) fumaric acid, (anhydride) maleic acid, (anhydride) itaconic acid, allylsulfonic acid, methallylsulfonic acid, vinylsulfonic acid, acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, Sulfopropyl acrylate, sulfopropyl methacrylate and their alkali salts, acrylamide,
Methacrylamide, trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, ethyl vinyl ether, butyl vinyl ether, N-vinylpyrrolidone, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoro Ethylene and the like. In the presence of thiol compounds such as thiolacetic acid and mercaptopropionic acid,
Those having a functional group at a terminal obtained by polymerizing a vinyl ester monomer such as vinyl acetate may be used.

The content of the primary amino group and / or the secondary amino group in the vinyl alcohol polymer having at least one functional group selected from primary and secondary amino groups in the molecule of the present invention is not particularly limited. Can be appropriately selected according to various situations, but usually 0.1 to 30 mol%, preferably 0.5 to 30 mol% as a monomer unit containing the functional group.
~ 25 mol%. If the amount of the functional group is less than 0.1 mol%, the effect of introducing the functional group may not be sufficiently exhibited, while if it exceeds 30 mol%, the inherent properties of polyvinyl alcohol may not be sufficiently exhibited. Also,
The degree of polymerization of the vinyl alcohol-based polymer having a functional group varies depending on the purpose of use and cannot be determined uniquely, but is preferably 100 or more, more preferably 200 to 8000. The saponification degree of the vinyl alcohol polymer is not particularly limited, but is preferably 50 mol% or more, and more preferably 80 to 99.9 mol%.

The aqueous emulsion (B) constituting the composition of the present invention is not particularly limited as long as the polymer is dispersed as a dispersoid in an aqueous medium containing water as a main component. Aqueous emulsions obtained by emulsion polymerization of one or more monomers selected from diene and diene monomers in the presence of various conventionally known emulsion dispersion stabilizers, and self-emulsifications such as polyurethane emulsions An aqueous emulsion obtained by post-emulsification using an emulsifying dispersant or the like is used. Among them, an aqueous emulsion obtained by emulsion polymerization of one or more monomers selected from ethylenically unsaturated monomers and diene monomers in the presence of conventionally known various emulsion dispersion stabilizers Are generally preferably used, and particularly, a polyvinyl acetate emulsion, an ethylene-vinyl acetate emulsion, a poly (meth) acrylate emulsion, and a styrene-butadiene emulsion are preferably used.

One or two or more monomers selected from ethylenically unsaturated monomers and diene monomers which are suitably used as the aqueous emulsion (B) constituting the composition of the present invention can be prepared by a conventional method. In an aqueous emulsion obtained by emulsion polymerization in the presence of various emulsion dispersion stabilizers, the ethylenically unsaturated monomer unit and the diene unsaturated monomer unit constituting the dispersoid may be radically polymerizable. There are no particular restrictions. As the ethylenically unsaturated monomer, ethylene, propylene, olefins such as isobutene, vinyl chloride, vinylidene chloride, vinyl fluoride, halogenated olefins such as vinylidene fluoride, vinyl formate, vinyl acetate, vinyl propionate, Vinyl esters such as vinyl versatate and vinyl pivalate, acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, acrylic acid t-
Butyl, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, acrylates such as hydroxypropyltrimethylammonium acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate,
I-propyl methacrylate, n-butyl methacrylate,
Methacrylic esters such as i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, hydroxypropyltrimethylammonium methacrylate, acrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, acrylamide-2-methylpropanesulfonic acid and its sodium salt acrylamide,
Trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, 3-acrylamidopropyltrimethylammonium chloride, 3-methacrylamidopropyltrimethylammonium chloride, N-methylacrylamide, N-ethylacrylamide, diacetoneacrylamide, acrylonitrile,
Nitriles such as methacrylonitrile, allyl compounds such as allyl acetate and allyl chloride, styrene-based monomers such as styrene, α-methylstyrene, P-methylstyrenesulfonic acid and its sodium and potassium salts, and other N-vinyl Pyrrolidone and the like, and diene monomers include butadiene, isoprene, chloroprene and the like.

The dispersant for the aqueous emulsion is not particularly limited, and a conventionally known anionic, cationic, amphoteric or nonionic surfactant, a vinyl alcohol polymer (polymerization degree 100 to 8000, saponification degree 50 to 100) %) Or a water-soluble polymer such as hydroxyethylcellulose.

In carrying out the emulsion polymerization for obtaining the aqueous emulsion, the above-mentioned monomer is added temporarily or continuously in the presence of water, the above-mentioned dispersant, and the polymerization initiator, and heated, A usual emulsion polymerization method such as stirring can be carried out, or a method in which a monomer is preliminarily mixed and emulsified with an aqueous dispersant solution can be continuously added. When two or more types of monomers are emulsion-copolymerized, two or more types of monomers may be mixed and used in advance. A so-called multi-stage polymerization in which a monomer is emulsion-polymerized may be performed.

The amount of the dispersant used in the emulsion polymerization for obtaining the aqueous emulsion is not particularly limited, but is preferably 0.1 to 50 parts by weight per 100 parts by weight of the monomer.
More preferably, it is in the range of 2 to 20 parts by weight.

The polymerization initiator for emulsion polymerization of the above-mentioned aqueous emulsion is not particularly limited. For example, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, 2,2'- Azobis (2-amidinopropane) dihydrochloride, cumene hydroperoxide, benzoyl peroxide, isopropylbenzene peroxide or the like alone or sodium bisulfite, tartaric acid, L-ascorbic acid, formaldehyde sodium sulfoxylate, ferrous sulfate, etc. Used in a redox system in combination with a reducing agent.

As the inorganic reducing agent (C) constituting the composition of the present invention, sodium sulfite, potassium sulfite, aluminum sulfite, ammonium sulfite, zinc sulfite,
Calcium sulfite, magnesium sulfite, chromium sulfite, sodium bisulfite, ammonium bisulfite,
Examples thereof include calcium bisulfite, potassium bisulfite, ammonium pyrosulfite, sodium pyrosulfite, potassium pyrosulfite and the like, and these are used alone or in combination of two or more.

The method of adding the inorganic reducing agent is not particularly limited, but usually, the inorganic reducing agent is used by dissolving it in an appropriate amount of water. The dissolution concentration is not particularly limited, but is preferably 5 to 50% because of easy handling. A predetermined amount of the obtained aqueous solution of the inorganic reducing agent is added to the aqueous emulsion, and the mixture is stirred and used.

The first invention of the present invention relates to (A) a vinyl alcohol polymer having at least one functional group selected from primary and secondary amino groups in a molecule, (B) an aqueous emulsion, and (C) an inorganic emulsion. It is a composition composed of a system reducing agent. Here, (A) a vinyl alcohol polymer having at least one functional group selected from primary and secondary amino groups in the molecule, (B) an aqueous emulsion, and (C) an inorganic reducing agent, [(A) + (B)] / (C) = 100 / 0.001-1 based on the weight of solid content
00/100, preferably 10/100
0 / 0.01 to 100/90. When the proportion of (C) is less than 0.001, the composition has insufficient storage stability, and when it exceeds 100, the water resistance of the film decreases. In this case, the ratio of (A) the vinyl alcohol polymer having at least one functional group selected from primary and secondary amino groups in the molecule and (B) the aqueous emulsion is not particularly limited, but is preferably used. Is (A) /
(B) = 0.1 / 99.9 to 70/30. If the compounding ratio is out of this range, the film water resistance may not be sufficiently exhibited.

The second invention of the present invention comprises (A) a vinyl alcohol polymer having at least one functional group selected from primary and secondary amino groups in the molecule, (B) an aqueous emulsion, and (C) This is a composition comprising an inorganic reducing agent and (D) a polyvalent epoxy compound.

The polyhydric epoxy compound (D) constituting the composition of the present invention includes bisphenol A diglycidyl ether, bisphenol A diβ-methyl glycidyl ether, bisphenol F diglycidyl ether, tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol Diglycidyl ether, brominated bisphenol A diglycidyl ether, chlorinated bisphenol A diglycidyl ether, hydrogenated bisphenol A
Glycidyl ether type such as diglycidyl ether, diglycidyl ether of bisphenol A alkylene oxide adduct, novolak glycidyl ether, polyalkylene glycol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol diglycidyl ether, epoxy urethane resin, etc .; P-oxybenzoate Glycidyl ether / ester type such as acid glycidyl ether / ester; glycidyl ester such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahexaphthalate, diglycidyl acrylate, diglycidyl dimer, etc. Type: glycidyl aniline, tetraglycidyl diaminodiphenylmethane, triglycidyl isocyanurate Glycidylamine type such as triglycidylaminophenol; linear aliphatic epoxy resin such as epoxidized polybutadiene and epoxidized soybean oil; 3,4 epoxy-6 methylcyclohexylmethyl-3,4 epoxy-6 methylcyclohexanecarboxylate; 4
Epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, bis (3,4-epoxy-6methylcyclohexylmethyl) adipate, vinylcyclohexenediepoxide, dicyclopentadiene oxide, bis (2,3-epoxycyclopentyl) ether, Examples include alicyclic epoxy resins such as limonenedioxide and polyamide epichlorohydrin. Of these, water-soluble polyvalent epoxy compounds are preferred.

In the second invention of the present invention, (A) a vinyl alcohol polymer having at least one functional group selected from primary and secondary amino groups in the molecule, (B) an aqueous emulsion, and (C) an inorganic polymer In the composition comprising the reducing agent and the polyhydric epoxy compound (D), the constituent ratio is [(A) + (B) + (C)] / (D), which is 100 / 0.1 to 100 based on the weight of the solid content. / 100, preferably 100 / 0.2 to 100/90. When the proportion of (D) is less than 0.1, the effect of improving the water resistance of the film, which is the purpose of adding (D), is not sufficiently exhibited, and when it exceeds 100, the disadvantage of adding (D) is disadvantageous. , The storage stability of the composition is significantly deteriorated, and it is no longer suitable for the purpose of the present invention. In this case, (A) a vinyl alcohol polymer having at least one functional group selected from primary and secondary amino groups in the molecule, (B) an aqueous emulsion, and (C) an inorganic reducing agent Is the same as the first invention of the present invention.

The second invention in the composition of the present invention comprises (D) a polyepoxy compound for the purpose of enhancing the water resistance of the film of the first invention. However, while the polyepoxy compound improves the water resistance of the film, it slightly deteriorates the storage stability, so that it may be restricted depending on the use. Therefore, the first invention and the second invention of the present invention can be selectively used according to the requirements of various uses.

The composition of the present invention may contain, if necessary, various polyvinyl alcohols, starch, modified starch, oxidized starch, sodium alginate, carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, maleic anhydride-isobutene copolymer, maleic anhydride. Water-soluble polymer compounds such as acid-styrene copolymer, maleic anhydride-methylvinyl ether copolymer, and urea-formalin resin, urea-melamine-formalin resin, phenol-formalin resin, etc. are also appropriately provided that the performance is not impaired. Can be used. Further, the composition of the present invention, a conventionally known plasticizer such as dibutyl phthalate,
Various additives such as solvents such as toluene, preservatives, fungicides, defoamers, fillers such as clay, kaolin, talc, calcium carbonate, wood flour, extenders such as flour, and pigments such as titanium oxide. It can be appropriately added as needed.

The composition of the present invention has little decrease in storage stability and has high film water resistance. Therefore, the use of the composition of the present invention, wood, plywood, paper,
It is suitably used as an adhesive or treatment agent for plastics, fibers, inorganic substances, etc., various paints, molded products such as films and sheets, and cement additives.

[0024]

The present invention will be described more specifically below with reference to examples and comparative examples. In Examples and Comparative Examples,
“Parts” and “%” are based on weight unless otherwise specified.

Example 1 (A) Primary amino group-containing PV obtained by copolymerizing vinyl formamide and vinyl acetate and then saponifying the copolymer.
A (degree of polymerization 1050, degree of saponification 98.5 mol%, primary amino group content 3.0 mol%), (B) ethylene-vinyl acetate copolymer emulsion {"OM-4200,
Manufactured by Kuraray Co., Ltd., solid content concentration 55%, P as dispersant
Uses VA. (C) Consists of sodium bisulfite.
(A) / (B) = 10/90 on the basis of solid weight,
The composition was prepared at a ratio of [(A) + (B)] / (C) = 100/1, and adjusted to a solid concentration of 45% with water to obtain a composition. Using this, a test was performed under the following conditions. The results are shown in Tables 1 and 2.

[Test conditions] Storage stability: Put the above composition in a closed container, 5 ° C
And in a constant temperature bath at 40 ° C. for 3 months. The viscosity before and after standing was measured at a standing temperature using a BH type viscometer, and the thickening ratio was determined as follows. In addition, changes in appearance were observed. 1. Thickening ratio = (composition viscosity after standing) / (composition viscosity before standing) Film water resistance: The above composition was cast on a Teflon sheet and dried at 20 ° C. for 7 days to produce a 500 μm thick film. This film was punched out into a circle having a diameter of 2.5 cm, and the water absorption was measured when immersed in water at 20 ° C. for 24 hours. 2. Water absorption = (weight after immersion−weight before immersion) / (weight before immersion) Adhesion test: An adhesion test was performed using the above composition under the following conditions. Adhering material: Rice hemlock / rice hemlock (masa-grain) Coating amount: 250 g / m2 (both sides applied) Deposition time: 1 minute Pressing condition: 20 ° C., 24 hours, pressure 10 kg / cm2 Compressive shear bonding according to JIS K-6852 Measure strength Normal strength: Measured as it is after curing for 7 days at 20 ° C. Repeated boiling: After curing for 7 days at 20 ° C., immerse test pieces in boiling water for 4 hours, and then dry in air at 60 ° C. for 20 hours Then, it was immersed in boiling water for 4 hours, immersed in water at room temperature until cooled, and subjected to the test in a wet state.

Example 2 In Example 1, an aniline group obtained by copolymerizing allyl glycidyl ether and vinyl acetate as (A), adding 2-aminothiophenol using NaOH as a catalyst, and further saponifying the mixture was used. PVA (degree of polymerization 10
00, degree of saponification 97.0 mol%, aniline group modification amount 2.
A composition was prepared in the same manner as in Example 1 except that 1 mol%) was used. Using this, a test was performed in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 3 In Example 1, a secondary amino group-containing PVA (polymerization degree: 1250, saponification degree: 93.5 mol) obtained by copolymerizing methyl vinylacetamide and vinyl acetate as (A) and then saponifying it. %, Secondary amino group content 4.0 mo
1%) was obtained in the same manner as in Example 1 except that 1%) was used.
Using this, a test was performed in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 4 In Example 1, (B) was used as fully saponified PVA (PV
A-117 (manufactured by Kuraray Co., Ltd.) was used in the same manner as in Example 1 except that a polyvinyl acetate emulsion having a solid content of 8% (solid content: 52%) was used. Using this, a test was performed in the same manner as in Example 1. Tables 1 and 2 show the results.
Shown in

Example 5 A composition was prepared in the same manner as in Example 1 except that a styrene-butadiene copolymer emulsion (SN-307, manufactured by Sumitomo Dow, solid content concentration: 48%) was used as (B). Prepared. Using this, a test was performed in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 6 In Example 1, a copolymer of methyl methacrylate and butyl acrylate (copolymerization ratio: 50/5) using (B) an anionic emulsifier (Sandet BL, manufactured by Sanyo Chemical Industries) as a stabilizer was used.
0% by weight) A composition was prepared in the same manner as in Example 1 except that an emulsion (solid content concentration: 50%) was used. Using this, a test was performed in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 7 In Example 1, the mixing ratio of (A) and (B) was 40 /
A composition was prepared in the same manner as in Example 1 except that the composition was changed to 60.
Using this, a test was performed in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 8 In Example 1, the mixing ratio of (A) and (B) was 5/9.
A composition was prepared in the same manner as in Example 1 except that the composition was changed to 5. Using this, a test was performed in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 9 In Example 1, the mixing ratio of (C) was changed to [(A) +
Example 1 except that (B)] / (C) = 100/20
A composition was prepared in the same manner as described above. Using this, a test was performed in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 10 A composition was prepared in the same manner as in Example 1 except that sodium pyrosulfite was used as (C). Using this, a test was performed in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 11 A composition was prepared in the same manner as in Example 1 except that sodium sulfite was used as (C). Using this, a test was performed in the same manner as in Example 1. Table 1 shows the results.
It is shown in FIG.

Example 12 In Example 1, (D) ethylene glycol diglycidyl ether was converted to [(A) + (B) + (C)] / (D) =
A composition was prepared in the same manner as in Example 1 except that the composition was blended at a ratio of 100/5. Using this, a test was performed in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Comparative Example 1 A composition was prepared in the same manner as in Example 1 except that (C) sodium bisulfite was not used. Using this, a test was performed in the same manner as in Example 1. Table 1 shows the results.
It is shown in FIG.

Comparative Example 2 In Example 1, the compounding ratio of (C) was changed to [(A) +
A composition was prepared in the same manner as in Example 1, except that (B)] / (C) = 100/120. Using this, Example 1
The test was performed in the same manner as in the above. The results are shown in Tables 1 and 2.

Comparative Example 3 In Example 1, an unmodified PVA (P) was used instead of (A).
A composition was prepared in the same manner as in Example 1 except that VA-117 (produced by Kuraray Co., Ltd.) was used. Using this, Example 1
The test was performed in the same manner as in the above. The results are shown in Tables 1 and 2.

Comparative Example 4 A composition was prepared in the same manner as in Example 1 except that (A) was not used. Using this, a test was performed in the same manner as in Example 1. The results are shown in Tables 1 and 2.

COMPARATIVE EXAMPLE 5 In Comparative Example 2, (D) ethylene glycol diglycidyl ether was converted to [(A) + (B) + (C)] / (D) =
A composition was prepared in the same manner as in Comparative Example 2, except that the composition was blended at a ratio of 100/120. Using this, a test was performed as in Comparative Example 2. The results are shown in Tables 1 and 2.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

As described above, the composition of the present invention has little decrease in storage stability and high film water resistance. Therefore,
The composition of the present invention is useful as an adhesive or treating agent for wood, plywood, paper, plastic, fiber, inorganic substance, etc., various paints, molded articles such as films and sheets, cement additives and the like.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 31/04 C08L 31/04 ZB 33/06 33/06 53/02 53/02 63/00 63/00 A

Claims (2)

[Claims] 1. A (A) vinyl alcohol polymer having at least one functional group selected from primary and secondary amino groups in a molecule, (B) an aqueous emulsion and (C)
Consisting of an inorganic reducing agent, and [(A) + (B)] /
(C) is 100 / 0.001 to 100 on the basis of solid content weight
/ 100. 2. The composition according to claim 1, further comprising (D) a polyepoxy compound, and [(A) + (B) +
(C)] / (D) is 100 / 0.1-
A composition that is 100/100.