JPS58204040A - Polyvinyl alcohol resin composition and its application - Google Patents

Abstract

PURPOSE:To provided a resin compsn. which is easily made water-resistant, consisting of an aceto-acetylated PVA resin and at least one member selected from an isocyanate compd., an epoxy compd., an amine compd., a free radical- generating compd., an oxidizing agent, a polymerizable monomer and a metal salt. CONSTITUTION:A resin compsn. consists of an aceto-acetylated polyvinyl alcohol resin (A) and at least one member (B) selected from an isocyanate compd., an epoxy compd., an amine compd., a free radical-generating compd., an oxidizing agent, a polymerizable monomer and a metal salt. The amount of component B somewhat varies depending on its use and kind, and is usually 0.1-30wt%, pref. 1-10wt% based on that of component A. This resin compsn. is useful for fiber processing agent, adhesive, coating agent, molded articles, etc.

Description

[Detailed Description of the Invention] Polyvinyl alcohol resins can be used for adhesives, paints, coatings, films, etc. by taking advantage of their water-solubility, adhesion properties, and film-forming properties. 8: However, it has the disadvantage of poor water resistance. However, one method to make the polyvinyl alcohol resin completely water-retained is to acetoacetylate the polyvinyl alcohol resin + fingers, and then add a dialdehyde-only resin to this. Many methods have been proposed to make it water resistant by adding various crosslinking agents. However, when conventional water spraying agents are used in combination, there are disadvantages such as the viscosity of the aqueous solution increases, which affects storage stability and coating properties, and the need for advanced heat treatment to make it water resistant. be.

However, as a result of extensive research, the present inventors found that (4) CB) was added to acetoacetylated polyvinyl alcohol resin.
A composition containing at least one compound selected from an incyanate compound, an epoxy compound, an amine compound, a compound having radical generating ability, an oxidizing agent monopolymerizable monomer, and a metal salt is relatively We have completed the present invention by discovering the novel fact that water resistance can be easily made not only by mild heat treatment but also by drying at room temperature.

In the composition of the present invention, the amount of (B) added to the acetoacetylated polyvinyl alcohol resin varies somewhat depending on the purpose and type of use, but is usually 0.1 to 0% by weight, preferably 0.5%. ~20%, particularly preferably 1~
2 ranges of 10% by weight. In the case of polymerizable monomers, it is also possible to use them outside the above range, for example, they can be used in amounts of 10 to 600% by weight.

The composition S is used in various applications when (N and (B)
), but depending on the purpose, it may be possible to coat only the material or mold it, and then post-process it with (B). I will explain it in a Hyogo way.

The acetoacetylated polyvinyl alcohol resin (4) in the present invention is produced by an arbitrary method and is not timed.

As a typical example, it is obtained by addition reaction of digtene to polyvinyl alcohol resin or transesterification reaction of acetoacetate. As the base polyvinyl alcohol resin, in addition to partially saponified polyvinyl esters such as polyvinyl acetate, other monomers mainly composed of vinyl acetate and copolymerizable with this, such as unsaturated carboxylic acids or their parts or "Copolymerized modified" polyvinyl alcohol, which is made by converting copolymers with complete esters, salts, anhydrides, amides, nitriles, unsaturated sulfonic acids or their salts, α-olefins with 2 to 0 carbon atoms, vinyl ethers, etc. Polyvinyl alcohol is acetalized, phretanized, etherified, grafted, phosphoric acid ester/L/coated, etc. ("postfixed" polyvinyl alcohol is also used, the average degree of combination of the polyvinyl alcohol is 60 mol% or more, The average degree of polymerization is preferably 5o to 6000.

The acetoacetylation ratio for the resin is 0.05
Although it is possible to maintain water solubility at mol% or more, it is usually 0.1 to 40 mol%, especially 062
It is often selected from the range of ~20 mol%. If the acetoacetylation rate is too low, the purpose of water resistance cannot be achieved. Furthermore, even if the acetoacetylation rate is introduced higher than necessary, the effect of imparting water resistance is not improved further, and the water solubility is often exceeded. Further, the residual vinyl acetate group is suitably 40 mol% or less, preferably 50 mol% or less. 9th CB) Compounds used for the purpose of imparting water resistance are exemplified, but the present invention is limited only to such examples. Inocyanate compounds (e.g. tolylene diisocyanate, hydrogenated tolylene diisocyanate, trimethylolpropane-tolylene diisocyanate adduct, triphenylmethane triisocyanate, methylene diisocyanate)
4-phenylmethane triisocyanate, inphorone diisocyanate, ketoxime-blocked or phenol-blocked products) Epoxy compounds (ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin di- or triglycidyl ether, 1,6-
Hexanesiol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diglycidylamine) Amine compounds (urea, melamine, and their methylolated products, hexamethylene diamine, triethanolamine) Compounds with radical generating ability ( benzoin alkyl ethers such as hydrogen peroxide, potassium persulfate, ammonium persulfate, benzoyl peroxide, succinic peroxide, t-butyl peroxide maleic acid, butyl hydroperoxide benzoin methyl ether, benzoin isopropyl ether; f) Organic iodine compounds such as methyl sulfide, benzyl sulfide, and decylphenyl sulfide, diazonium salts, tetrazonicum chloride, complex salts of these with zinc chloride, or condensates thereof, azobisisobutyronitrile, 2. 2'-Azobis(2-amidinopropane) hydrochloride, dyes such as methylene blue or combinations thereof with p-1 luenesulfonate ions, virilicum salts or thiavirillicum salts, ammonium dichromate, acetophenone, benzophenone,
Benzyl, 7-enanthrene, thioxanthone, dichloropropylphenyl ketone, acitraquinone, 2-chloroanthraquinone, 2-bromoanthraquinoneanthraquinone sodium β-sulfonate, 1,5-dinitroanthraquinone, 1,2-penzanthraquinone, phenanthrenequinone , 5-benzoylacenaphthene, 5-nitroacenaphthene, 1,4-naphthoquinone, 1,8-phthaloylnaphthene, 2-nitrofluorene, p-nitroaniline, biclamide) Oxidizing agent (calcium dichromate, dichromium ammonium acid, calcium perchlorate) Polymerizable monomer slag (2- and droxyethyl acrylate, 2-
- and droxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, N-vinylpyrrolidone, 2-hydroxyethyl acryloyl 7-o-7ate, acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide , N-methoxymethylacrylamide, N-ethoxymethylacrylamide, ethylene glycol monoacrylate, dipropylene glycol monoacrylate, N,N-dimethylaminoethyl acrylate, styrene, vinyltoluene, monochlorostyrene, diallylphthalate, vinyl acetate, glycidyl methacrylate) Metal salts (aluminum, iron, copper, zinc, tin, titanium,
Chlorides, bromides, nitrates, sulfates of polyvalent metals such as nickel, antimony, magnesium, vanadium, and chromium;
Acetate. Examples of salts such as cupric chloride, aluminum chloride, ferric chloride, tin chloride, zinc chloride, chloride, magnesium chloride, aluminum sulfate, vinegar, and chromium acetate) The composition consisting of A) and Φ) is used for various purposes as described below. This composition exhibits unique effects in each application and is extremely useful industrially.In this case, the composition may contain fillers, colorants, surfactants, fibers, foaming agents, and antifoaming agents as required. , other water-soluble resins, water-dispersible resins (
For example, various emulsions), thixotropy improving agents, etc. may be added, and these agents can also be used as post-treatment agents after treatment with the compositions of Φ and Φ). The F1 application will be specifically explained below.

fi + fiber processing agent (binder for non-woven fabrics, sizing processing, hard finishing processing, waist finishing processing, flame retardant processing, water repellent processing,
Pigment printing, anti-wrinkle processing, anti-shrunk processing, flexible processing, dimensional stability, anti-fading, 70mm x 1, abrasion resistance,
(Improving tensile toughness, stain resistance, etc.) The processing agent is used to improve the flexibility, elasticity, dry cleaning resistance, mechanical strength, layering properties, etc. of each fiber or (i) textile. It can impart remarkable effects.Moreover, it has excellent water resistance, has good washing fastness, and its effects are permanent.

Fibers of the present invention: When using a product treatment agent, the treatment agent is applied or sprayed onto the fiber or fabric to be processed using a roll coater or the like, or the fiber or fabric is coated with the composition. After immersing it in the liquid, it is squeezed appropriately to adjust the amount of resin attached, and then heated and dried. When performing more advanced treatment by adding a crosslinking agent/waterproofing agent, the treatment is usually 100 to 17
Heating at a temperature of about 0 degrees Celsius will cause the vines to progress sufficiently.

The fibers that can be processed in the present invention include natural fibers such as cotton, silk, and wool! In addition to I4-1, it includes various synthetic threads such as polyamide, polyester, polyacrylic, polytetravinyl, and polypropylene threads.

・, 2) Adhesive-related wood 1 Adhesives for paper, aluminum foil, plastics, etc., adhesives, rewetting agents, IS-shaped binders, binders for various building materials such as gypsum board and fiberboard, various powder granules binder for,
Additive for cement and mortar, pressure-sensitive FMJ, and anionic dye fixing agent.In such applications, a far superior contact force can be obtained compared to polyvinyl alcohol. (3) Clear coating agent for coating paper, Pigment coating agents for paper, internal sizing agents for paper, sizing agents, leather finishing agents, coatings,
Antifogging agents, metal corrosion inhibitors, galvanizing brighteners, antistatic agents, conductive agents, etc. In such applications, a coating film with greater strength can be obtained immediately compared to when polyvinyl alcohol is used.

(4) Molded articles, films, sheets, vibrators, tube leak-proof membranes, temporary coatings These molded articles have excellent water resistance and mechanical strength.

(5) Blend agent for hydrophobic resins Atsushi Seki Anti-static of hydrophobic resins (arsenic agent and wood-improving agent, 4-I
I&M, additives for films and other molded products te+! ---
Flocculants for suspensions and dissolved substances in water, lifting agents for valve slurries (7) Shisei Kaihinki (8) Photosensitive agents, electrosensitive agents, 9) Others , ion exchange resin, ion exchange relationship key 1
The composition of the present invention will be specifically explained using the example of a dog.

Preparation of Polyvinyl alcohol and diketene were reacted in an acetic acid solvent to produce the following two types of hinoki.

(Al-1; average degree of polymerization 1700, residual acetate group 1 mol%
Acetoacetylated polyvinyl alcohol resin with a degree of acetoacetylation of 8 mol%.

臥)-2: Acetoacetylated polyvinyl alcohol-based tree with average polymerization f 11QO5 residual vinegar residue 1 mol %, acetoacetyl r 12 + 5 mol %.

The following compounds similar to (B) were used and mixed with the liquid to prepare a composition (10% by weight aqueous solution) 1 (Bl-
1; Tolylene diisocyanate [λ/ζ′R[7% IN amount added] fBl-2; Isophorone diisocyanate [1% by weight added to Q+] (Bl-5; Trimethylo-I regloban-torylene Diisocyanate adduct [1% by weight added to (A)] FB+-4; Ethylene glycol diglycidyl ether [5% by weight added to (A)] (Bl-5; Polyethylene glycol diglycidyl ether [(5) ) 5 weight 96 addition J (Bl-6; Methylolmelamine [1,5 weight 96 addition to (to)) fBl-7i 1,000 methylesidiamino [125 weight % addition to Kan] (Bl- 8; Ammonium persulfate [1% added per car per prisoner m- (Bl-9; 2,2'-Azobis(2-amine/propane) hydrochloride [A) (added to 5 Tosan 96] (Bl-9) 10-Ammonium dichromate [redacted] (1% by weight added to tBl) tBl-+1; 2-hydroquine ethyl acrylate [(
Addition of 100% hydrogen acid to 3) (combined use of 2% by weight of peroxybenzoyl) fBl-12;
Magnesium C (5% by weight added to Al) fBI-1; Nickel chloride [1.5% by weight to (A)]
(Bl-14; Ferric chloride [added at 96% by weight to (A)] Example 1 The water resistance of the above-mentioned #1 composition was measured.

The results are shown in Table 1. As a control example, ayatoacetyl (f-polyvinyl alcohol y (7 generations/f
-Water resistance was also measured for polyvinyl alcohol (Hiramisaki polymerization 9+700, average weight 99 moles 96).
t1 The results are also shown.

Table 1 (Measurement method; 2) The CB+ composition was formed into a cast film at room temperature, heat treated at 100°C for 5 seconds, and then exposed to boiling water for 21 hours. Survival rate (to)
was measured.

Bad writing example 2 ^)-1 and tBl-1, (Al-1 and CB+-7, tA
l-1 and (Bl-12, Mu)-2 and (B1-9.(Al
-27 (combined with Bl-6, :) 8 shearing% aqueous solution, golden tone, tower i, thickness 5 dennies, fiber length approx. 50
Dry-dried 100 f/' door web made by drying polyethylene resin 7-tonat single #C fiber with Rashidum web 7 bar and squeezing it with the above solution J, soaked in water, and masiru, 1 f80
Pre-soft dry at ℃ for 20 minutes, then dry at 150℃ for 11 minutes.
- The amount of resin deposited after drying was determined by the amount of resin sprayed before treatment (2) The solid content was 096
Table 2 shows the measurement results for the various materials of the n + non-woven fabric. Squeeze the liquid so that the amount of adhesion or the amount of cloth bundled is 496. This is dried at 80°C for 10 minutes to give a hard finish. The hardness was measured.All household electric washing machines: 12 o, dO'C, 50 minutes of washing with a neutral detergent, then dried at room temperature. Hardness: (
1- conversion. The washability test was carried out 1 time, 5 times, and 10 times for each occasion. The results are shown in Table 1.

Table 5 Example 5 Porridge, Table 1 (・A 10% aqueous solution of the composition shown above was prepared, and a film with a thickness of 80 μm was produced on a glass plate by the flow side method Vζ.This film About 7 j]
After soaking in hot water of C for 1 hour, Shimadzu Autograph IM-
110n type (load cell 5Kq, load cell 100:
Mechanical strength was completely measured using W/1lfi)b. , the results are shown in the fourth barley.

Table 4: Example 4: Glass-wood adhesion and wood-wood adhesion of the compositions shown in Table 5 were evaluated and reported in Table 5.

＠ 5 Table ◎Glass-wood contact cracking (material tester) Apply 0.5 g of 10% composition in water to the center of the piece (7. Overlap the glass wires, apply a load of 100 g, and heat at 40°C for 24 hours. After drying for 2 hours at
rJrn-Ji) O Wood-wood adhesion force: Apply a 15% composition aqueous solution to a mortar-grained veneer at a ratio C of 52'j/-, apply a load of lOh, and heat at 40°C for 24 hours at 60°C. After drying for 6 hours at
Immersed in boiling water for 1 hour and measured shear strength using Autograph iC.

Implementation-15 6th wheat ζ The composition shown was subjected to paper making 1, the next '-+4! Press +F to fully demonstrate the size press, [.

Paint ■2 pieces; speed 90-/vrm, nip, 1 king 11
F-Q... - Dry 1'fll I I 5 C2m 1 quintillion paper; test paper (tsubo it 6 4 f, /rrf, sa ・
1' degree sec.

Density 0.67) Calender finish; 80°C, 50mm. , 2
Pos5 coating density; 596"-19 Coated paper's total number 6: C shows, - Oil absorption; JIS-8130 Air permeability: King Prayer type air permeability tester IGT Pick Strength: Depends on IGT printing suitability tester.

Claims (1)

[Scope of Claims] 1 (A) Acetoacetylated polyvinylene alcohol resin and (B) incyanate compound, epoxy compound, amine compound, compound having radical generating ability, oxidizing agent, polymerizable A polyvinyl alcohol-based resin composition comprising at least one compound selected from metal salts. 2 (4) Acetoacetylated polyvinyl alcohol resin and (2) a compound selected from incyanate compounds, epoxy compounds, amine compounds, compounds with radical generating ability, oxidizing agents, polymerizable monomers, and metal salts A fiber processing agent whose main ingredient is a polyvinyl alcohol resin composition consisting of at least one of the following. 5) Acetoacetylated polyvinyl alcohol resin and (B) at least a compound selected from isocyanate compounds, epoxy compounds, amine compounds, compounds with radical generating ability, oxidizing agents, polymerizable monomers, and metal salts. (4) An acetoacetylated polyvinyl alcohol resin and (B) an incyanate compound, an epoxy compound, an amine compound, and a radical-generating agent. A coating agent whose main ingredient is a polyvinyl alcohol-based resin composition consisting of at least one compound selected from the group consisting of acetoacetylated polyvinyl alcohol resin, an oxidizing agent, a polymerizable monomer, and a metal salt. B) A polyvinyl alcohol resin composition comprising at least one compound selected from incyanate compounds, epoxy compounds, amine compounds, compounds capable of generating radicals, oxidizing agents, polymerizable monomers, and metal salts. A molded product whose main ingredient is