Water-resistant composition

[Detailed Description of the Invention]

A, Field of the Invention The present invention relates to a waterproof constituent and it is related with the waterproof constituent consisting of the water-soluble polymer which has a primary amino or a first-class ammonium salt machine in a molecule in more detail and the amino group or an ammonium salt machine, and a water resistance-ized agent that has reactivity. B, prior art Conventional Si water solubility Bolimani is widely used as each food binder, adhesives, or a finishing agent, and it is known especially that polyvinyl alcohol (polyvinyl alcohol is written as PvA below) has the outstanding performance which does not allow imitation of other paste agents in film formability and intensity. however -- including PVA, since water-soluble polymer is water solubility, the first class has the fault that water resistance is low -- Conventional Si -- although various methods have been examined for the object of improving this The result which that it is still satisfied and there is nothing [ vine ] examined wholeheartedly in order for the problem book artificers whom Ah C1 invention tends to solve in the present condition to conquer the fault of above-mentioned water-soluble polymer, The constituent which consists of the water-soluble polymer which has a primary amino or a first-class ammonium salt machine in a molecule and the amino group or an ammonium salt machine, and a water resistance-ized agent that has reactivity finds out excelling in water resistance remarkably, and came to complete the present invention. The means for solving D1 problem That is, the present invention relates to a waterproof constituent and relates to the waterproof constituent which consists of the water-soluble polymer which has a primary amine machine or a first-class ammonium salt machine in a molecule in more detail and the amino group or an ammonium salt machine, and a water resistance-ized agent that has reactivity. As the water-soluble polymer which has a primary amino or a first-class ammonium salt machine in the molecule used by the present invention, Polyolefin which various things can use it, for example, has the above-mentioned - class amine machine or an ammonium salt machine, Denaturation polyacrylamide, denaturation poly (meta) acrylic acid, this salt or partial ester, denaturation polyvinyl alcohol, denaturation starch, cellulose system derivatives or these Chestnut 7 A, block polymer, etc. are mentioned. Denaturation polyvinyl alcohol is suitably used also in this water-soluble polymer in respect of adhesiveness, film formability, intensity, water resistance, and solvent resistance, and the average degree of polymerization is usually chosen from the range of 100~300.0, preferably 200~2500, and, as for the degree of average saponification, 70~100 Morti is Good Mol There. Since adhesive strength runs short of average degrees of polymerization by less than 100 and the degree of average saponification becomes difficult to melt into water in less than 70 Momoru, it is not desirable. What has a first-class ammonium salt machine in respect of the viscosity stability in the inside of the solution which has water resistance-ized agent * also in above-mentioned water-soluble polymer is used preferably. Or [ that methods arbitrary as a method of manufacturing above-mentioned water-soluble polymer carry out and hang ], The independent polymerization of the Olefin unsaturated monomer which has a substitution machine which can generate a primary amino or a first-class ammonium salt machine by the Olefin unsaturated monomer or hydrolysis which has ■-class amino group or a first-class ammonium salt machine suitably is carried out, or they are these and acryl amide, (Meta) Acrylic acid or this derivative, vinyl ester, etc. are made to copolymerize. The method of making the aldehyde etc. which have a primary amino or a first-class ammonium salt machine introduce into the water-soluble polymer which is made to further hydrolyze by a case or has ■ hydroxyl group or an amide machine by a 7 Seta 1 Le-ized reaction, or using the Hofmann rearrangement reaction of ■ amide machine further, etc. are mentioned. As the example of the Olefin unsaturated monomer which has a substitution machine which can generate a primary amino or a first-class ammonium salt machine by seven above-mentioned first-class friends, a first-class ammonium salt machine, or hydrolysis, For example, N-vinyl imide etc. which are denoted by the vinyl amine denoted by a following formula (1), its organic acid or inorganic acid salt, N-vinyl amide denoted by (■), and (Ill) a formula are mentioned. CH2=C-(CH2) -NH2(I) -- [ -- as for a hydrogen atom or methyl group R2, in 3, a hydrogen atom or low-grade Alkyl machine % n shows 2~4 here, respectively, as for theta~4 and m. ] When zero acid catalyst which can use acid or alkali is used as a catalyst in the case of making an above-mentioned copolymer hydrolyze, The primary amino generated by hydrolysis of the amide machine in the monomeric unit shown by above-mentioned (It) or (III) can also be used as first-class ammonium salt by reaction * Cheating with an acid catalyst succeedingly. When using an alkali catalyst, it can be made for hydrolysis of an above-mentioned amide machine to be able to generate a primary amino, and also to make this react with acid at Yo See class ammonium salt. In an above-mentioned hydrolysis reaction, it is except hydrolysis of an above-mentioned amide machine (1). Other monomeric units of (n)6 Rude which form a copolymer with the monomer shown by (Ill) a formula can be simultaneously partial, or it can hydrolyze them completeness 1. As aldehyde which has the primary amino or the first-class ammonium salt machine used in the method of above-mentioned ■, it is for example, amino acetaldehyde, Although amino butylaldehyde, these Dialkylacetate tar, such ammonium salt, etc. are mentioned, it is not limited to this. If the content of the primary amino in above-mentioned water-soluble polymer or a first-class ammonium salt machine is more than 0.05-mol charge, there will be no restriction in particular, but it usually Mortimol 0.1~20 times, and To is chosen from the range of 0.5~10-mol charge. - When the content of a class amino group or a first-class Ammonitum base is less than 0.05 Momoru, even if still larger, comparatively [ the ], the effect expected cannot be acquired more than 20 Momoru that it is hard to acquire the effect of the present invention. Any may be sufficient as long as it is a compound which reacts to - class amino group or a first-class ammonium group, and can crosslink these as a water resistance-ized agent used by the present invention, For example, mono-aldehyde, such as formaldehyde and acetaldehyde, glyoxal, Many value aldehyde, such as glutaraldehyde and dialdehyde starch, Methylol melamine, Aldehyde system compounds, such as a reaction thing of ammonia, such as methylol compounds, such as dimethylol urea, and hexamethylenetetramine, and formaldehyde, Although the water-soluble salt of metal, such as polybasic acid, such as a maleic anhydride, fumaric acid, oxalic acid, and sulfuric acid, aluminum, iron, copper, zinc, titanium, magnesium, chromium, and zirconium, etc. are mentioned, When water-soluble polymer is denaturation PVA system polymer especially (a #'i aldehyde system compound is used preferably.) The rate of a weight compounding ratio of water-soluble polymer and the above-mentioned water resistance-ized agent which have seven first-class friends or a first-class ammonium salt machine has a water resistance-ized agent (solid content conversion) preferred for 0.5~50 copies, preferably 1~20 copies to 100 copies of above-mentioned water-soluble polymer in the molecule used in the present invention. In less than 0.5 copy, it is ineffective, and a coat cannot use it weakly in 50 or more copies. Although the waterproof constituents of the present invention are conditions with indispensable the water-soluble polymer which has a primary amino or a first-class ammonium salt machine in a molecule like Above and the amino group or the ammonium salt machine, and the water resistance-ized agent that has reactivity being included, Other solvent, various additive agent, and water solubility resin or a polymers water dispersing element can be made to contain according to a use besides it. Although water is preferably used as a solvent, Solvents, such as various alcohol, ketone, Dimethylform amide, and dimethyl sulfoxide, can also be used together and used for this, and it is as an additive agent, Various antifoaming agents, various dispersing agents, nonionicity, or an anionic surface-active agent, The Silang coupling agent or a place regulation agent is mentioned, and it is Dimethyl cellulose in Calvo as water-soluble resin, Cellulose derivatives, such as hydroxyethyl cellulose, the poly (meta) acrylic acid, Acrylic (meta) polymers, such as poly hydroxy (meta) acrylate or its copolymer, and polyacrylamide, Polyvinyl pyrrolidone or its # Thunder 100 million, Carboxy zero joint-right Sugiyoshi PVA, sulfuric acid machine content denaturation PVA, sulfonic group content denaturation PVA PVA derivatives, such as phosphate group content denaturation PVA and quarternary-ammonium-salt machine content denaturation PVA, first-class PVA, etc. are mentioned. As a polymers water dispersing element, water dispersing elements, such as an acrylics polymer, a copolymer, an ethylene-vinyl acetate copolymer, a vinyl ester system polymer, a copolymer, and a styrene butadiene copolymer, are mentioned. 0 which dissolves or distributes and is used for the water in which the waterproof constituent of the present invention contains water or the above-mentioned organic solvent The waterproof constituent of the present invention employs water resistance efficiently, and film formability and tunic Strong * Rude are Vehicle for the adhesives for an inorganic substance or organic matters or a binder, and paints. It is used effective in the processing agent of minerals material or organic material, for example, a surface coat agent, and is used also for the use for which water-soluble resin was used conventionally [, such as a film and a sheet, ] further again. The effect of E operation and an invention Although the waterproof constituent of the present invention is not necessarily solved enough about a reason excellent in film formability and film strength - and water resistance, it is the water resistance of the present invention. When the primary amino or the first-class ammonium salt machine in the water-soluble polymer which has a primary amine machine or a first-class ammonium salt machine is dried and a coat is formed in the molecule used in a constituent, while reacting to a water resistance-ized agent easily and generating bridge construction combination When especially the above-mentioned water-soluble polymer is the above-mentioned denaturation PVA, in order for the hydroxyl group in the PVA to also react to a water resistance-ized agent partially and to form a coat with high bridge construction density, that from which the coat excellent in intensity and water resistance is obtained is presumed. The present invention is not limited by this, although an example is given to below and the present invention is explained to it in more detail. the key which does not have a notice in particular among an example -- Si "Chi" and a "part" express a weight standard. Example I Denaturation PVA which carries out the alkali saponification of the copolymer of N-vinyl aceto amide and acetic acid vinyl, carries out 4-mol charge content of the primary amino, and has a primary amino in the degree image of 98.5 mol of saponification of an acetic acid vinyl unit, and the molecule of degree of polymerization 1750 was acquired. 101 solution of denaturation pvA which dissolves this denaturation PVA in the water containing the primary amino under denaturation PVA and lactic acid of an equimolar amount, and has a first-class ammonium ° base was prepared. Subsequently, this solution 11C40'16 glyoxal was added at 1010 rate to 27 denaturation by solid content conversion, and it dried by 50 degreeC after flow casting for 4 hours, and created the sheet-shaped thing. The obtained sheet-shaped thing was immersed in underwater [ of 40 degreeC ] for 24 hours, and the degree of swelling and the elution rate were measured. A result is shown in the 1st table. Example 2~6 replacing with denaturation PVA and lactic acid which were used in Example 1 -- following water-soluble polymers and acid -- business -- it carried out like Example 1 except '' being. A result is united and it is shown in the 1st table. Example 2: 8 Contains of the primary amino produced by carrying out the alkali saponification of the copolymer of N-vinyl succinic acid imide and acetic acid vinyl was carried out, and glycolic acid was used as acid using 27 denaturation of saponification degree 99 Morti of an acetic acid vinyl unit, and degree of polymerization 500. Example 3: 4-mol charge content of the first-class two Ammonium base produced by saponifying the copolymer of vinyl amine and acetic acid vinyl using a chloride catalyst was carried out, and saponification degree 88 Morti of 1 acetic-acid vinyl unit and denaturation F'VA of degree of polymerization 1200 were used. Example 4: 0 using denaturation PVA which carries out 8-mol charge content of the degree image of 98.5 mol of saponification, and the first-class ammonium salt machine produced by Acetal-izing PVA of degree of polymerization 1100 by amino acetaldehyde in aqueous hydrochloric acid Example 5: Acetic acid was used as acid using the denaturation polyacrylamide which carries out 0.5-mol charge content of the primary amino obtained by the Hofmann rearrangement reaction of polyacrylamide. Example 6: It is the primary amine machine produced by carrying out Hoffmann transition of the PVA-acryl amide block copolymer (PVA/polyacrylamide = 1/1 (weight ratio)) produced by polymerizing acryl amide under the denaturation PvA existence which has a thiol group at the end, 3Including morti+/ e Benzoic acid was used as acid using the a P V A-Vo 11 acryl-amide ° block copolymer. Comparative example 1~2 It carried out like Example 1 except replacing with denaturation PVA and acid of Example 1, and using the following water-soluble polymer. A result is united and it is shown in the 1st table. First-class PVA in comparative example 1 D (Kuraraybo bar PMA-117) Comparative example 2: Polyacrylamide The of degree of polymerization 2000 One table example 7~13 0 results performed like Example 1 are shown in the 2nd table except using a water resistance-ized agent as replaced with the glyoxal used in Example 1 and shown in the 2nd table, and a combination rate. Comparative example 3~4 It is Implementation except replacing with, as it replaces with addition Pleasure of glyoxal used in Example 1 and is shown in the 2nd table. Two tables Example 14 100 copies of 15 Chi solution of denaturation PVA was created using denaturation PVA and glycolic acid which were used in Example 2. After having received this in clay, receiving denaturation PVA in 20 copies and glyoxal and adding 5%, it cast, it dried by 100 degreeC for 1 hour, and created the sheet-shaped thing. This sheet-shaped thing was maintaining the coat shape which was insoluble also in hot water of 95 degreeC and became brave. Comparative example 5 It carried out like Example 14 except replacing with denaturation PVA used in Example 14, and using first-class PVA (Kuraraybo bar PVA-105). This sheet-shaped thing was remelted to the inside of a short time by the heat underwater of 95 degreeC.