JPS63270704A - Highly polymerized modified polyvinyl alcohol having sulfonic acid group, manufacture thereof and use thereof - Google Patents

Abstract

PURPOSE:To obtain the title modified polyvinyl alcohol suitable for emulsifiers, adhesives, etc., by copolymerizing an N-sulfoalkyl(meth)acrylamide and a vinyl ester in a small amount of an alcohol and saponifying the copolymer. CONSTITUTION:An N-sulfoalkyl(meth)acrylamide of formula I (wherein R1 is H or methyl; R2 is alkylene; and M is H or an alkali metal) and a vinyl ester are copolymerized in an alcohol solvent in an amount of 50% or less based on the weight of the vinyl ester, and the resulting copolymer is saponified. Thereby, a highly polymerized polyvinyl alcohol having sulfonic acid groups is obtained which comprises N-sulfoalkyl(meth)acrylamide repeating units of formula II, vinyl ester repeating units of formula III (wherein R3 is alkyl) and vinyl alcohol repeating units of formula IV (a 4% aqueous solution of which has a viscosity of 5cP or above at 20 deg.C).

Description

Detailed Description of the Invention The present invention provides a novel modified polyvinyl alcohol containing a highly polymerized sulfonic acid group (hereinafter polyvinyl alcohol will be abbreviated as PVA) useful as an emulsifier, especially as an emulsifier for emulsion polymerization of (meth)acrylic acid ester. It provides:

In emulsion polymerization of unsaturated monomers such as acrylic esters and vinyl acetate, various nonionic or anionic surfactants have traditionally been used alone or in combination as emulsifiers, and in some cases, protective colloids such as PVA have been used. is being used.

Emulsions obtained by such methods can be used as adhesives, coatings,
It is extremely useful as a textile processing agent, etc., but has poor storage stability and
It has drawbacks such as poor freeze-thaw stability and dilution stability.

As one of the countermeasures, it has been proposed to use PVA modified with an olefin sulfonate such as edilene sulfonate or allyl sulfonate as an emulsifier. It has been found that when using acid-modified PVA, although the above-mentioned difficulties are significantly improved, a new problem arises in that only emulsions with low viscosity can be obtained. In the case of a low-viscosity emulsion, if the emulsion is applied to a porous substrate such as paper or cloth, the emulsion will penetrate into the substrate rapidly and the yield on the substrate surface will decrease, so it will not be possible to achieve the desired coating film. This may cause problems such as physical properties not being fully exhibited. To avoid this, it is possible to add a thickener to the emulsion, but this requires careful attention to prevent problems such as phase separation with the emulsion and breakage of the emulsion, which is not necessarily advantageous in practical terms. There is a need for the development of emulsifiers that enable the production of emulsions.

However, as a result of intensive research in order to satisfy this request, the present inventors found that the copolymer composition was + CHt C
N-sulfoargyl(meth)CO represented by n 1+-
N II·R1·soiM Acrylamide unit, +CHt CII 'J- 0 C011.

vinyl ester unit, and +CI (!C11:+-
It consists of repeating rr vinyl alcohol units (where R.

; hydrogen or methyl group, R1: alkylene group, R3: alkyl group, M: hydrogen or alkali metal), and the viscosity of a 4% aqueous solution at 20° C. is 5 centivoise or more. Highly polymerized sulfonic acid group-containing modified PVA is an emulsifier. When used as
Furthermore, the present inventors have discovered that the resulting emulsion has remarkable performance, including good performance in terms of storage stability, freeze-thaw stability, and dilution stability, leading to the completion of the present invention.

That is, when an acrylic ester is emulsion polymerized using the above-mentioned modified PVA containing a sulfonic acid group of the present invention as an emulsifier,
An extremely high viscosity emulsion can be easily obtained, and the obtained emulsion has excellent storage stability, freeze-thaw stability, dilution stability, etc., which is equivalent to or even better than when using lefinsulfonate-modified PVA. Therefore, the modified PVA of the present invention has great industrial utility.

Another major feature of the sulfonic acid group-containing modified PVA of the present invention is that it has a high degree of polymerization. That is, the modified PVA has a viscosity of 5 centivoise or more, preferably 10 centivoice or more, in a 4% aqueous solution at 20°C. Modified P with such a high degree of polymerization
Because it is VA, it exhibits the above-mentioned remarkable effect as an emulsifier, and its effect is poor below the above-mentioned viscosity.

Various types of modified PVA containing sulfonic acid groups are known, but none with a high degree of polymerization as the modified PVA of the present invention has been produced. This is due to the drastic decrease in the degree of polymerization during copolymerization of olefin sulfonate salts and vinyl esters, or the lack of a medium with sufficient dissolution ability for both. PVA'! This is because building A is extremely difficult in reality.

Since the N-sulfoalkyl (meth)acrylamide, vinyl ester, and N-sulfoalkyl (meth)acrylamide/vinyl ester copolymer used in the present invention all exhibit good solubility in alcohol solvents such as methanol, the above-mentioned The copolymer can be produced very easily industrially, and the desired modified PVA with a high degree of polymerization can be easily obtained by simply adjusting the amount of solvent used.

Hereinafter, the novel highly polymerized sulfonic acid group-containing modified PV of the present invention
A, its manufacturing method, and uses will be explained in more detail.

As described above, the modified PVA of the present invention is a copolymer consisting of a repeating composition of N-sulfoalkyl (meth)acrylamide units, vinyl ester units, and vinyl alcohol units, and can be written as the following general formula.

C0Ntl-11,-8o, M0CON,
01! In N-sulfoalkyl (meth)acrylamide, which is the first component, the alkylene group (R1) may be an ethylene group, a propylene group, a butylene group, etc., and may be linear or branched. From the viewpoint of stability, it is preferable to use kerala containing a branched alkylene group. Also M
is hydrogen or an alkali metal, but the free sulfonic acid (
If M is hydrogen), the vinyl ester may be decomposed during copolymerization, so an alkali metal such as sodium or potassium is usually preferable. Among such acrylamides, N-sulpoisobutylene acrylamide sodium CI! is used in the present invention. 3 is particularly preferably used.

Examples of the vinyl ester as the second component include vinyl acetate, vinyl propionate, vinyl butyrate, and the like, with vinyl acetate being preferably used.

The third component, vinyl alcohol, is a component produced by saponifying the vinyl ester.

The ratio of each component is not particularly limited and any ratio can be selected, but for example, for emulsifiers, N-sulfoalkyl (meth)acrylamide is 0.1 to 20 mol% (0,001≦
A total coal content range of 80 to 99.9 mol % is suitable. Also, the average degree of saponification, that is, the saponification of the vinyl ester moiety is appropriate. Therefore, the preferred PVA of the present invention has a sulfonic acid group content m of 0.1 to 20 mol% and an average saponification degree of 1.
It is a highly polymerized sulfonic acid group-containing modified PVA having a viscosity of 0 to 99.9 mol % and a 4% aqueous solution at 20°C of 5 centiboise or more, particularly desirably IO centiboise or more.

In producing the above-mentioned modified PVA, first, N-sulfoalkyl (meth)acrylamide and vinyl ester are copolymerized in an alcohol solvent. At this time, the amount of alcohol used must be regulated to 50% or less based on the weight of the vinyl ester so that the viscosity of the modified PVA is 5 centivoise or more.

As the alcohol, lower alcohols such as methanol, ethanol, propatool, etc. are commonly used. These alcohols may contain a small amount of water.

There are no particular restrictions on the method of charging monomers during polymerization.
Any method such as batch charging, split charging, continuous charging, etc. can be adopted, but from the viewpoint of the copolymerization ratio of N-sulfoalkyl (meth)acrylamide and vinyl ester, the vinyl ester is first dissolved in an alcohol solvent, and then the vinyl ester is dissolved in the alcohol solvent. It is advantageous to polymerize while dropping the above-mentioned (meth)acrylamide because it is easier to obtain a copolymer with a uniform composition. In the copolymerization, known lanocal polymerization catalysts such as azobisisobutyronitrile, acedel peroxide, benzoyl peroxide, and lauroyl peroxide are used as catalysts. Polymerization temperature is usually 50°
A temperature of about C to boiling point is desirable.

In addition, in carrying out such polymerization, other unsaturated monomers copolymerizable with the monomer other than the above two components, such as styrene, alkyl vinyl ether, (meth)acrylamide, ethylene, propylene, α-hexene, α- Olefins such as octene, unsaturated acids such as (meth)acrylic acid, crotonic acid, (anhydrous) maleic acid, fumaric acid, itaconic acid, and their alkyl esters and alkali salts.
It is also possible to have dust present in an amount of 0 mol % or less.

The copolymer thus polymerized is saponified according to a conventional method.

That is, for saponification, the copolymer is dissolved in alcohol or hydrous alcohol and saponified with acid or alkali. Examples of the alcohol include methanol, ethanol, propatool, etc., but methanol is preferably used. The concentration of copolymer in alcohol is usually 20-7
It is selected from the range of 0% by weight. As saponification catalysts, alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, sodium methylate, sodium ethylate, potassium methylate, alkaline catalysts such as Alcolade, or acid catalysts such as sulfuric acid and hydrochloric acid are used. . The amount of such catalyst used is usually 0.1 to 5.0 per vinyl acetate.
Mol% is appropriate. The temperature during the saponification reaction is not particularly limited, but is usually selected from the range of 10 to 50°C, preferably 20 to 40°C. The saponification reaction is carried out for 0.1 to 5 hours.

When carrying out emulsion polymerization of an unsaturated monomer using the modified PVA obtained by the above method as an emulsifier, the unsaturated monomer is added temporarily or continuously in the presence of water, an emulsifier, and a polymerization catalyst. Any conventional emulsion polymerization method such as heating, stirring, etc. can be carried out. The amount of modified PVA used is:
It varies somewhat depending on the amount of modification of the PVA, the resin content of the required emulsion, etc., and is usually selected from a range of about 1 to 8% by weight and 4H% based on the entire emulsion polymerization reaction system. As a polymerization catalyst, potassium persulfate, ammonium persulfate, etc. are used alone or in combination with acidic sodium sulfite, and hydrogen peroxide-tartaric acid, hydrogen peroxide-iron salt, hydrogen peroxide-ascorbic acid-iron salt are also used. , hydrogen peroxide-Rongalit, hydrogen peroxide-Rongalit iron salt, and other redox catalysts are used. In addition, although the above-mentioned modified PVA alone can produce the above-mentioned remarkable effects, if necessary, a nonionic activator such as a polyoxydiethylene-alkyl ether type, a polyoxine ethylene-alkylphenol type, a polyhydric alcohol ester type, etc. , or various PVA and PVA derivatives known as emulsifiers and protective colloids,
Alternatively, an anionic activator such as higher alcohol sulfate can be used in combination as appropriate. Furthermore, plasticizers such as phthalate esters and phosphate esters, sodium carbonate, sodium acetate,
It may be used in combination with a PHM stabilizer 6 such as sodium phosphate.

Examples include butadiene monomers, which are unsaturated monomers to be subjected to emulsion polymerization. Examples of the ethylenically unsaturated monomer include vinyl acetate, acrylic ester, methacrylic ester, vinyl chloride, hnylidene chloride, acrylonitrile, styrene, ethylene, etc., and homopolymerization or copolymerization of these monomers can be carried out.

In particular, when acrylic monomers such as acrylic esters or methacrylic esters are homopolymerized or copolymerized, an emulsion with particularly good mechanical stability, storage stability, pigment miscibility, etc. can be obtained, which is a remarkable effect. Therefore, emulsion polymerization of acrylic monomers is preferably carried out.

As a butadiene monomer, butanoene-1,3,2-
Examples include methylbutadiene-1,3,2,3-dimethylbutadiene-1,3,2-chlorobutadiene-1,3, which are used alone or in combination with ethylenically unsaturated monomers.

Among these, butadiene-1,3 and styrene, butadiene-1,3, styrene and (meth)acrylic acid, butane-1,3 and acrylonitrile, butadiene-1,3,
3, acrylonitrile, styrene, butadiene-1,3
and acrylonitrile and (meth)acrylic ester, butadiene-1,3 and methyl methacrylate, butadiene-
It is advantageous to carry out the polymerization with a combination of 1.3, methyl methacrylate and (meth)acrylic acid.

The emulsion thus obtained can be used as it is or, if necessary, with the addition of water-soluble polymer substances such as PVA and CMC, for a wide range of applications such as adhesives, paints, fiber processing agents, paper processing agents, etc., and its industrial utility value is This is extremely high.

Although the emulsifier has been described above as a use of the modified PVA of the present invention, the PVA is useful for various uses other than as an emulsifier. For example, the modified PVA of the present invention is added as a thickener to an aqueous emulsion obtained by emulsion polymerization of ethylenically unsaturated monomers or butadiene monomers in the presence of various surfactants or water-soluble protective colloids. When added,
Similar to when used as an emulsifier, an extremely high viscosity aqueous emulsion can be obtained, and the emulsion has the effect of significantly improving storage stability, freeze-thaw stability, dilution stability, etc., and the modified PVA of the present invention It is also useful as a thickening agent for aqueous emulsion additions.

In addition, the modified PVA of the present invention is a conventional sulfonic acid-modified PVA.
Since the degree of polymerization is significantly higher than that of VA, it can exhibit remarkable effects in various applications where conventional products had many practical problems. Specific uses include the following.

(1) Water-soluble fibers for molded products, films, sheets, pipes, dupes, leak-proof membranes, temporary coatings, and chemical laces.

Attempts have been made to introduce sulfonic acid activity into PVA in order to improve the antistatic properties, antifogging properties, and water dispersibility of PVA molded products, reduce dew condensation, and improve moldability. It is being Conventionally, in order to introduce such sulfonic acid groups, (meth)allylsulfonic acid (sodium) and vinyl acetate are copolymerized and the resulting copolymer is saponified. Modification by oxidation tends to reduce the strength of the molded product, so a solution is needed.

The modified PVA of the present invention overcomes these drawbacks and provides molded products with excellent moldability and no reduction in mechanical strength.

(2) Adhesives: Adhesives for wood, paper, aluminum foil, plus deck, adhesives, rewetting agents, binders for non-woven fabrics, fibrous binders, binders for various building materials such as gypsum board and fiberboard, and various powders. Binder for granulation, cement and mortar additive cutting, pot melt adhesive, pressure sensitive adhesive.

Attempts have been made to introduce sulfonic acid groups in order to improve the adhesive strength of PVA-based adhesives or to make the adhesive water-dispersible and water-soluble in order to facilitate waste paper recovery when the adhesive is paper, etc. It is being Conventionally, such a sulfonic acid group has been introduced by copolymerizing (meth)allylsulfonic acid (sodium) and vinyl acetate and saponifying the resulting copolymer. However, modification with allylsulfonic acids is not always sufficient to achieve the initial objective, and in particular, the improvement in adhesive strength is not sufficient. The modified PVA of the present invention has significantly improved adhesive strength compared to the PVA, and also has excellent water dispersibility and water solubility.

(3) Coating agent-related clear coating agent for paper, pigment coating agent for paper, internal sizing agent for paper, sizing agent for textile products, warp sizing agent,
Textile processing agents, leather finishing agents, paints, anti-fog agents.

For example, attempts have been made to use PVA containing sulfonic acid groups to improve its surface properties in paper processing agent applications, or to improve binding horns to fibers in warp sizing agent applications, and to improve desizing properties. There is. Conventionally, in order to introduce such a sulfonic acid group, (meth)allylsulfonic acid (storium) and vinyl acetate are copolymerized and the resulting copolymer is saponified. PVA modified with acids cannot necessarily be said to have sufficient effects. The modified PVA of the present invention improves these drawbacks and allows paper processing with excellent surface properties, efficient fiber sizing, etc. to be carried out.

(4) Blend agents for hydrophobic resins Antistatic agents for hydrophobic resins, hydrophilicity imparting agents, composite fibers, films, and other additives for molded products.

Modified PVA containing sulfonic acid groups is blended with hydrophobic resins such as polyethylene, polypropylene, polyvinyl chloride, nylon, polystyrene, polyamide, polyester, etc. in order to impart antistatic properties, hydrophilicity, or improve moldability of the resins. That is what is being attempted. Conventionally, PVA produced by saponifying a copolymer obtained by copolymerizing (meth)allylsulfonic acid (sodium) and vinyl acetate has been used as the PVA, but when using PVA modified with allylsulfonic acids. There is a tendency for the mechanical strength of the blend molded product to decrease, and a solution to this problem is required. When the modified PVA of the present invention is used, such defects are improved and molded products with high strength can be obtained.

Modified PVΔ is added in an amount of about 5 to 95% by weight.

(5) Pigment dispersion stabilizer for suspension-related paints, India ink, watercolor colors, adhesives, etc.
Dispersion stabilizer for disastrous polymerization of various vinyl compounds such as vinyl chloride, vinylidene styrene chloride, (meth)acrylate, vinyl acetate, etc. Next, the present invention will be explained in more detail with reference to examples.

Illustration! Production of modified PVA containing sulfonic acid groups 834 parts of vinyl acetate and 158 parts of methanol were charged into a polymerization reactor equipped with a reflux condenser, a dropping funnel, a thermometer, and a stirrer, and the temperature was raised while stirring to produce azobisisobutylene at 60°C. A solution of 0.30 parts of lonitrile dissolved in 50 parts of methanol was added to initiate polymerization. From the start of polymerization,
N-sulfoisobutylene acrylamide sodium salt 4
Polymerization was continued while adding dropwise 196 parts of a 23% methanol solution in which 6 parts were dissolved. After 5 hours, the polymerization was stopped when the polymerization rate reached 60%. The copolymerization solution was purified according to a conventional method to obtain an N-sulfoisobutylene acrylamide sodium salt/vinyl acetate copolymer.

A 30% methanol solution of the copolymer was prepared, and a methanol solution of 20 mmol of sodium hydroxide was added to the vinyl acetate group at 40° C. to perform a saponification reaction. The produced modified PVA was separated, washed, and dried to obtain the desired product.

The characteristic values of the obtained modified PVA were as follows.

(Sulfonic acid group content 3.0 mol%, average saponification degree 94
9 mol% average PVA) 4% aqueous solution viscosity at 20°C, 30.5 centivoise rR (cm-') 1660 and 1540 (secondary amide group) 1040
and 630 (sulfonic acid group) NMR (δppm
) 1.7 -C1, From the above, the amide bond is not cleaved by saponification of the copolymer, and the presence of the sulfonic acid group is confirmed.

Emulsion polymerization of butyl acrylate After reflux cooling, volume 5 equipped with dropping funnel, thermometer and stirrer.
Add 138.4 parts of a 3.9% aqueous solution of the above modified PVA and 9 parts of a 9% aqueous solution of dibasic sodium phosphate as a PH adjuster to a cc glass polymerization vessel and rotate at a speed of 20 Or, p, m. The internal temperature was raised to 65°C. Next, 11 parts of butyl acrylate and 10 parts of a 4% aqueous solution of potassium persulfate were added to initiate emulsion polymerization. Initial polymerization was carried out for 35 minutes, and then 98.1 parts of butyl acrylate was continuously added dropwise over 4 hours while adjusting the internal temperature of the polymerization vessel to 70°C, and 3.5 parts of a 4% aqueous solution of potassium persulfate was added to 2 parts. The emulsion polymerization was continued in divided batches. The internal temperature was kept at 75° C. and the aging reaction was carried out for 1 hour, and then the remaining monomer was expelled to obtain an emulsion of butyl polyacrylate.

Table 1 shows the measurement results of various properties of this emulsion.

As a control example, a nonionic surfactant (manufactured by Nippon A11 Fats Co., Ltd., Nippon Nonion P) was used instead of the copolymer.
-230) 2.1 and 0.8 g of an anionic surfactant (Nizantrax If-45, manufactured by Nihon Uramari Co., Ltd.) were used together (Control Example 1), 3 mol% modification of sodium allylsulfonate 1) VA (Average degree of saponification 95 mol%, 20
The results of an experiment conducted in the same manner as in Example 1 except that a 4% aqueous solution having a viscosity of 2.0 cm at °C (Control Example 2) was used are also shown.

Table 1 Note 1) The storage stability is based on the emulsion at a temperature of 60°C.
After leaving it in a constant temperature chamber kept at ℃ for 5 days, let it cool for 3 hours and observe the appearance. Those with no change are classified as A, those with emulsion destruction are designated as E, and those with emulsion destruction are designated as B and C. The evaluation was divided into three stages: , D.

Note 2) Freeze-thaw stability is determined by keeping emulsion approximately 509 at a temperature of -15℃ for 16 hours, then heating it at 30℃ for 1 hour in a constant temperature water bath.
After standing for a period of time, the appearance was observed by stirring with a glass rod. Those with no change were graded A1, those with emulsion destruction were graded E, and the grades in between were divided into three grades: B, C%D, and evaluated.

Note 3) Dilution stability is determined by adding distilled water to dilute the resin content to 3%, placing it in a glass tube with an inner diameter of 7 mm and a length of 1 m, and then measuring the supernatant after leaving it for 24 hours. Liquid (upper layer)
Observe the depth of the layer (lower layer) that has settled at the bottom of the tube, and select AlB, C, D, and E in descending order of stability.
It was evaluated by

Examples 2 to 5 Emulsion polymerization of various ethylenically unsaturated monomers was carried out according to Example 1 using modified PVA as shown in Table 2. The results are shown in Table 2.

Table 3 Example 11~! 4 Using N-sulfoisobutylene acrylamide sodium salt modified PVA produced according to Example I, it was blended with low density polyethylene and a 30μ film was produced by T-die melt extrusion at 200-210°C. Table 4 shows the physical properties of the film.

Table 4 Examples 15 to 16 N-sulfoisobutylene acrylamide sodium salinity PVA (modified ff 12.9 mol%, degree of saponification 88.
A 100 μm film was obtained by blending hard polyvinyl chloride and nylon 12 with a mixture of hard polyvinyl chloride and nylon 12 using a mixture of 2% aqueous solution and 4% aqueous solution dust (5.9 centipoise). Table 5 shows the physical properties of this film.

Table 5 Examples 17-2 ■ The performance as a rewetting adhesive was evaluated using 9N-sulfoisobutylene acrylamide sodium salt modified 1) VA prepared in accordance with Example 1. Table 6 shows the results.

Table 6 Re-wet crab re-wet agent was applied with a hot-melt coat to Raft Gi for packing tape (manufactured by Tomoe Paper Co., Ltd.) Coating amount: 1209/m
Use a sample tape by cutting it into 5 mm pieces and leaving it overnight.Next, use a roller-type water dispenser to add water to one end of the sample tape (fft209/m).
Glue with finger pressure onto a mount set on a scale with a capacity of 1 to 1.5. The adhesive tape attached to the backing paper is peeled off after 2 seconds, 30 seconds, and 60 seconds after water is applied, and the initial adhesive strength (g/l 5
mm).

Water solubility of rewetting agent: A small piece of tape (+
5+nIIIX 35mmX 0, 1mm) at 30℃
Observe changes over time when immersed in water.

Examples 22 to 26 9N-sulpoisobutylene acrylamide sodium salt modified PVA produced according to Example 1 was evaluated for its performance as a pressure-sensitive adhesive. The results are shown in Table 7.

Table 7 Adhesive crab polyester film I OOn+mX 10
Apply the adhesive on an area of 0mm at a rate of 120y/m', set the measurement angle to 30° with a T and Dow ball tack measuring machine, and measure the adhesive measurement distance at 1100mm+ for run-up! The adhesion force was measured using the ball when the steel ball was stationary at 00 mm, and the adhesion force was expressed by the ball number of the measured steel ball.

Water solubility of adhesive: Adhesive applied ml 209 parts m
A piece of polyester film (20 mm x 20
mm x O, I mm) was immersed in water at 30° C., and the change in the adhesive over time was observed.

Examples 27 to 31 The following pot-melt adhesives were prepared using N-sulfoisobutylene acrylamide sodium salt modified PVA and evaluated.

Preparation of adhesive N-sulfoisobutylene acrylamide sodium 3
．． Modified P with saponification degree of 94.9 mol% modified by 0 mol%
An adhesive was prepared by melt-mixing 100 parts of VA, 45 parts of sorbitol with 10 moles of ethylene oxide, and 35 parts of polymerized rosin mannitriester resin using a mixer at 170°C. (Example 27) N-sulfoisobutylene acrylamide sodium chloride modified with 5.0 mol% saponification degree of 35.7 mol% VA 100 parts, sorbitol ethylene oxide
An adhesive was prepared by melt-mixing 20 parts of O mol adduct, 40 parts of polymerized rosin mannitriester resin, and 20 parts of DBP at 170°C. (Example 28) In Example 29, modified P V with a degree of saponification of 98.1 mol % and modified with 5.0 mol % was prepared in the same manner as in Example 27.
In Example 30, A was modified with a degree of saponification of 9 by 1.0 mol%.
Adhesives were prepared using 7.6 mol% of each of modified P and Δ.

The results are shown in Table 8.

No. 8 Surface Adhesive Crab Cut high-quality paper to 50 mm x 50 mm, and apply adhesive in a line about 3 mm wide at a distance of 20 mm from one end. Immediately after that, corrugated paper cut to the same size is overlapped and glued together.

The high-quality paper of this test piece was folded together from the adhesive part, and the 12 sheets of paper and the cardboard part were set in an autograph and the tensile speed was 30.
Peel strength was determined at 0 mm/min and used as adhesive strength.

Water solubility: 30 pieces of adhesive (20X20XImm)
Observe changes over time when immersed in water at ℃.

Examples 32 to 36 N-sulfoisobutylene acrylamide sodium salt-modified PVA produced according to Example 1 was used to bond wood and its performance was evaluated. The results are shown in Table 9.

No. 9 Adhesive strength: Apply a 10% aqueous solution to a birch test piece,
Apply a bonding pressure of 1.5 kg/cm" using a tightening tool 4
After being left at room temperature for one day, it was measured using an autograph at 20° C. and 65% R■.

Examples 37 to 40 Size press coating was performed according to Example 1 using N-sulfoisobutylene acrylamide sodium salt modified PVA under the following conditions.

Coating conditions: speed 90 m/min, nip pressure 11 kg
/ am drying at 115°C, 2m1n base paper; papermaking for testing (tsubo fi 6497m'', size degree 3sec.

Density 0.67) Calender finish; 80℃, 50kg/am,
2poss coating density: 3% The physical properties of the obtained coated paper are shown in the following table.

Note) Measuring method Oil absorption: JIS-8130 Air permeability: Oken type air permeability tester IGT Pick strength, IGT printability tester example 41
~45 Polyester/cotton = 65735 blended yarn and No. 45 single yarn were sized under the following conditions, and the physical properties of the sized yarn and 19
The weaving results of 0 broads were tested.

(1) Glue recipe; (glue concentration 9%) (2) Gelatinization conditions: Pour 600Q of water into a 1600μ volume crusher, add 9 to modified PVA63, and 27K to cornstarch while stirring.
After adding g, disperse at room temperature for 10 minutes. Thereafter, it is heated to 95°C or higher for about 30 minutes and gelatinized for about 50 minutes. Finally, dissolve 9 in oil agent 3.6 and add water.
o Finish to 12.

(3) Gluing conditions Using a hot air and cylinder drying method, glue temperature: 90°C, speed: 50 yds/min, squeezing pressure: own weight (I OOkg) + I, 5 &/
am2, drying temperature: 90-100°C (pot air)
, 100-120°C (cylinder).

(4) Weaving conditions.

TOYODΔ GL-8 tip change, I 70 r
pm 169-72% [I Ll, 15-20°C The results obtained are shown below.

Claims (1)

[Claims] 1. The copolymer composition has ▲ mathematical formulas, chemical formulas, tables, etc. ▼
N-sulfoalkyl (meth)acrylamide unit represented by
Consists of repeating vinyl ester units shown by ▼, which have mathematical formulas, chemical formulas, tables, etc., and vinyl alcohol units, which are shown by ▼ (here, R_1; hydrogen or methyl group; R_2; A highly polymerized sulfonic acid group-containing modified polyvinyl alcohol having an alkylene group (R_3; alkyl group; M; hydrogen or alkali metal) and a viscosity of a 4% aqueous solution at 20°C of 5 centipoise or more. 2. The modified polyvinyl alcohol according to claim 1, wherein the highly polymerized sulfonic acid group-containing modified polyvinyl alcohol is a sodium salt of a saponified N-sulfoisobutylene acrylamide-vinyl acetate copolymer. 3. CH_2=CR_1・CONH・R_2・in an alcohol solvent of 50% or less based on the weight of vinyl ester
A highly polymerized sulfonic acid characterized by copolymerizing N-sulfoalkyl (meth)acrylamide represented by SO_3M (R_1, R_2, M are the same as above) and vinyl ester, and saponifying the resulting copolymer. Method for producing group-containing modified polyvinyl alcohol. 4. Copolymer composition ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
N-sulfoalkyl (meth)acrylamide unit represented by
Consists of repeating vinyl ester units shown by ▼ (There are mathematical formulas, chemical formulas, tables, etc.) and vinyl alcohol units shown by (▼ There are mathematical formulas, chemical formulas, tables, etc.) (R_1, R_2, R_3, M are the same as above) ), and the viscosity of a 4% aqueous solution at 20°C is 5
An emulsifier made of modified polyvinyl alcohol containing a highly polymerized sulfonic acid group with a centipoise or higher. 5. Copolymer composition ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
N-sulfoalkyl (meth)acrylamide unit represented by
Consists of repeating vinyl ester units shown by ▼ (There are mathematical formulas, chemical formulas, tables, etc.) and vinyl alcohol units shown by (▼ There are mathematical formulas, chemical formulas, tables, etc.) (R_1, R_2, R_3, M are the same as above) ), and the viscosity of a 4% aqueous solution at 20°C is 5
A thickener made of modified polyvinyl alcohol containing a highly polymerized sulfonic acid group with a centipoise or higher. 6. Copolymer composition ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
N-sulfoalkyl (meth)acrylamide unit represented by
Consists of repeating vinyl ester units shown by ▼ (There are mathematical formulas, chemical formulas, tables, etc.) and vinyl alcohol units shown by (▼ There are mathematical formulas, chemical formulas, tables, etc.) (R_1, R_2, R_3, M are the same as above) ), and the viscosity of a 4% aqueous solution at 20°C is 5
A molded product made of modified polyvinyl alcohol containing a highly polymerized sulfonic acid group with a centipoise or higher. 7. Copolymer composition ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
N-sulfoalkyl (meth)acrylamide unit represented by
Consists of repeating vinyl ester units shown by ▼ (There are mathematical formulas, chemical formulas, tables, etc.) and vinyl alcohol units shown by (▼ There are mathematical formulas, chemical formulas, tables, etc.) (R_1, R_2, R_3, M are the same as above) ), and the viscosity of a 4% aqueous solution at 20°C is 5
An adhesive made of modified polyvinyl alcohol containing a highly polymerized sulfonic acid group with a centipoise or higher. 8. Copolymer composition ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
N-sulfoalkyl (meth)acrylamide unit represented by
Consists of repeating vinyl ester units shown by ▼ (There are mathematical formulas, chemical formulas, tables, etc.) and vinyl alcohol units shown by (▼ There are mathematical formulas, chemical formulas, tables, etc.) (R_1, R_2, R_3, M are the same as above) ), and the viscosity of a 4% aqueous solution at 20°C is 5
A coating material made of modified polyvinyl alcohol containing a highly polymerized sulfonic acid group having a centipoise or higher. 9. Copolymer composition ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
N-sulfoalkyl (meth)acrylamide unit represented by
Consists of repeating vinyl ester units shown by ▼ (There are mathematical formulas, chemical formulas, tables, etc.) and vinyl alcohol units shown by (▼ There are mathematical formulas, chemical formulas, tables, etc.) (R_1, R_2, R_3, M are the same as above) ), and the viscosity of a 4% aqueous solution at 20°C is 5
A blending agent for hydrophobic resins made of modified polyvinyl alcohol containing a highly polymerized sulfonic acid group with a centipoise or higher. 10. N-sulfoalkyl (meth)acrylamide unit whose copolymer composition is represented by ▲Mathematical formula, chemical formula, table, etc.▼,
Consists of repeating vinyl ester units shown by ▼ (There are mathematical formulas, chemical formulas, tables, etc.) and vinyl alcohol units shown by (▼ There are mathematical formulas, chemical formulas, tables, etc.) (R_1, R_2, R_3, M are the same as above) ), and the viscosity of a 4% aqueous solution at 20°C is 5
A suspension dispersion stabilizer made of modified polyvinyl alcohol containing a highly polymerized sulfonic acid group having a centipoise or higher.