JP2003096211A - Sheet-like material and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet-like material and a method of manufacturing the same which can be handled excellently, generates no agglomeration of polymer microparticles in a coating liquid, causes no tack between the sheet-like materials when piled up and of which no polymer microparticle peels off. SOLUTION: A polymer microparticle dispersion obtained by adding an inorganic electrolyte to a microparticle dispersion of a copolymer which has an ethylenically unsaturated monomer having a nonionic hydrophilic group and an ethylenically unsaturated hydrophobic monomer is applied onto a supporting member and dried to obtain the sheet-like material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a sheet-like material in which polymer particles are coated on a support and a method for producing the same.

[0002]

2. Description of the Related Art A sheet-like material is generally prepared by providing layers for various purposes on the surface of a support such as a plastic film, a glass plate, a synthetic paper, and a paper. For example, it has improved mechanical properties such as slipperiness, and has functionality such as image formation and reception and retention of images (inks, pigments, dyes, etc.). The functional layer is formed on the support for the purpose of protecting the layer.

Such a functional layer is provided by applying a coating solution containing a binder. In recent years, in consideration of environmental costs, the use of an organic solvent in the coating solution is stopped, Aqueous coating liquids are being used.

Therefore, it is necessary to use a water-soluble polymer or a water-dispersed polymer (for example, latex) as the binder in the coating liquid, but the functional layer formed by these aqueous coating liquids is an organic solvent. It is more likely to contain water than the one coated with the system coating liquid, and for example, when the sheet-shaped materials are stacked in a high-humidity atmosphere, a problem that the sheet-shaped materials adhere to each other easily occurs.

However, as a method for preventing such adhesion, particles (matting agent) having a diameter larger than the thickness of the binder have been incorporated.

For example, in the case of silver halide photographic light-sensitive materials, such matting agents include inorganic substances such as silicon dioxide, magnesium oxide, titanium dioxide and calcium carbonate, polymethylmethacrylate, polystyrene and ethylcellulose acetate propio. In many cases, polymer fine particles of an organic substance such as nate (hereinafter, also referred to as polymer matting agent or matting agent) are contained.

However, although the use of such a matting agent is effective in preventing adhesion, the matting agent may come off during handling of the sheet-shaped material, and the equipment handling the sheet-shaped material may become dirty.
There is a problem that the quality of the sheet material is deteriorated, such that the sheet material comes into contact with the peeled matting agent and the surface of the sheet material is scratched, or the matting agent is peeled off.

The exfoliation of the matting agent can be solved by using a matting agent obtained by copolymerizing an ethylenically unsaturated monomer containing a hydrophilic group.

However, the polymer fine particle dispersion liquid containing a hydrophilic group has a drawback that the redispersibility is poor and the handleability is deteriorated when the polymer fine particles in the dispersion liquid once settles when left standing.

Regarding the handling property of the dispersion liquid after standing, a means such as addition of gelatin or a thickener may be used, but when the coating liquid is heated, agglomeration of polymer fine particles occurs, or When the aggregated matting agent is contained in the hydrophilic binder layer to form a sheet-like material, the polymer matting agent is easily peeled off.

Further, in a silver halide photographic light-sensitive material having a hydrophilic binder layer containing a polymer matting agent in which polymer fine particles are agglomerated, the polymer matting agent is peeled off in the hydrophilic binder layer, resulting in an image. There has been a problem that pinholes (fine holes) are generated and the quality is deteriorated.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is that the handling property is good and the polymer fine particles do not aggregate in the coating liquid.
Another object of the present invention is to provide a sheet-shaped material that does not stick to each other due to the overlapping of the sheet-shaped materials and has no polymer fine particles coming off, and a method for producing the same.

[0013]

The above object of the present invention can be achieved by the following constitutions.

1. Supports polymer particle dispersion obtained by adding an inorganic electrolyte to a copolymer particle dispersion containing an ethylenically unsaturated monomer having a nonionic hydrophilic group and a hydrophobic ethylenically unsaturated monomer. A sheet-shaped material which is applied on the body and dried.

2. Supports polymer fine particle dispersion obtained by adding an inorganic electrolyte to a copolymer fine particle dispersion having an ethylenically unsaturated monomer having a nonionic hydrophilic group and a hydrophobic ethylenically unsaturated monomer A method for producing a sheet-shaped material, which comprises applying the composition on a body and drying the composition.

3. The copolymer fine particle dispersion obtained by polymerizing an ethylenically unsaturated monomer having a nonionic hydrophilic group and a hydrophobic ethylenically unsaturated monomer in the presence of an inorganic electrolytic substance is applied on a support, A method for producing a sheet-shaped material, which comprises producing by drying.

4. 2. The sheet-shaped material as described in 1 above, wherein the polymer fine particle dispersion contains polyvinylpyrrolidone.

5. The sheet-shaped material as described in 1 or 4 above, wherein the content of the inorganic electrolytic substance is 0.1 to 10 mass% with respect to the total mass of the polymer particle dispersion.

6. The method for producing a sheet-shaped material as described in 2 or 3 above, wherein the content of the inorganic electrolytic substance is 0.1 to 10 mass% with respect to the total mass of the polymer particle dispersion.

7. 6. The sheet-shaped material as described in 1, 4, or 5, wherein the inorganic electrolytic substance is at least one compound selected from sodium chloride, sodium sulfate, magnesium sulfate and calcium chloride.

8. 7. The method for producing a sheet material according to the above 2, 3 or 6, wherein the inorganic electrolytic substance is at least one compound selected from sodium chloride, sodium sulfate, magnesium sulfate and calcium chloride.

9. 1, wherein the polymer fine particles in the dispersion have an arithmetic average particle diameter of 3 to 15 μm,
The sheet-shaped material according to 4, 5, or 7.

10. 2. The arithmetic mean particle size of the polymer fine particles in the dispersion is 3 to 15 μm,
9. The method for producing a sheet material according to 3, 6, or 8.

The present invention will be described in detail below. The sheet-like material and the method for producing the same according to the present invention are obtained by adding an inorganic electrolytic substance to copolymer fine particles having an ethylenically unsaturated monomer having a nonionic hydrophilic group and a hydrophobic ethylenically unsaturated monomer. It is characterized in that the obtained polymer fine particle dispersion is applied on a support and dried. The arithmetic average particle diameter of the polymer fine particles in the polymer fine particle dispersion of the present invention is preferably 3 to 15 μm from the viewpoint of more exerting the effect of the present invention. The value of the arithmetic mean particle size is
It is a value measured by the device in Examples described later.

The method for producing a sheet-like material according to the third aspect of the present invention is a method for producing an ethylenically unsaturated monomer having a nonionic hydrophilic group and a hydrophobic ethylenically unsaturated monomer in the presence of an inorganic electrolyte. It is characterized in that a copolymer fine particle dispersion liquid containing a monomer is applied onto a support and dried to produce.

Preferred specific examples of the ethylenically unsaturated monomer having a nonionic hydrophilic group of the present invention include the following monomers.

For example, 2-hydroxyethyl acrylate, polyethylene glycol monoacrylate (polymerization degree of polyethylene glycol: 2 to 20), 2-hydroxy-propyl acrylate, poly (2-methylethylene glycol) monoacrylate (poly (2-methyl Polymerization degree of ethylene glycol: 2 to 20), 2,3-dihydroxypropyl acrylate, 2-N-pyrrolidone ethyl acrylate, 2-hydroxyethyl acrylate, polyethylene glycol monomethacrylate (polymerization degree of polyethylene glycol: 2 to 20), 2-hydroxy-propyl methacrylate, poly ((2-methylethylene glycol) polymerization degree: 2-20), 2,3-dihydroxypropyl methacrylate, 2-N-pyrrolidone ethyl methacrylate DOO, N- vinylpyrrolidone, N-
Vinyl oxazolidone, acrylamide, N-2-hydroxyethyl acrylamide, N, N-diethanol acrylamide, N- (2- (polyethylene glycol)
Ethyl) acrylamide (Polymerization degree of polyethylene glycol: 2 to 20), N, N- (2,2 '-(Polyethylene glycol) diethyl) acrylamide (Polymerization degree of polyethylene glycol: 2 to 20), N-methyl acrylamide, N -Ethyl acrylamide, N-propyl acrylamide, methacryl acrylamide, N-2-hydroxyethyl methacrylamide, N, N-diethanol methacrylamide, N- (2- (polyethylene glycol) ethyl) methacrylamide (degree of polymerization of polyethylene glycol: 2 ~ 20), N, N- (2,2 '-(polyethylene glycol) diethyl) methacrylamide (polyethylene glycol polymerization degree: 2 to 20), N-
Methyl methacrylamide, N-ethyl methacrylamide, N-propyl methacrylamide, p-hydroxymethyl styrene, p- (2-hydroxyethyl) styrene, p- (2-hydroxyethyloxycarbonyl) styrene, p- (polyethylene glycoloxy) Carbonyl) styrene (Polyethylene glycol polymerization degree: 2
20), p-((polyethylene glycol) oxymethyl) styrene (polyethylene glycol polymerization degree: 2
20) and the like, but the present invention is not limited thereto.

The hydrophobic ethylenically unsaturated monomer is not particularly limited, but examples thereof include acrylic acid esters such as methyl acrylate, ethyl acrylate, (i-) propyl acrylate, (i, s, t-). )
Butyl acrylate, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, myristyl acrylate, lauryl acrylate, stearyl acrylate, phenyl acrylate, cresyl acrylate, benzyl acrylate, phenylyl Acrylate,
Glycidyl acrylate, dimethylaminoethyl acrylate, 2-naphthyl acrylate, etc .; as methacrylic acid esters, methyl methacrylate, ethyl methacrylate, (i-) propyl methacrylate, (i,
s, t-) butyl methacrylate, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, myristyl methacrylate, lauryl methacrylate, stearyl methacrylate, phenyl methacrylate, cresyl methacrylate, Benzyl methacrylate, phenethyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate,
2-naphthyl methacrylate, etc .; vinyl acetates, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl pivalate, vinyl caproate, vinyl benzoate, etc .; acrylamides, butyl acrylamide, t-butyl acrylamide, etc. Cyclohexyl acrylamide, benzyl acrylamide, methoxyethyl acrylamide, dimethylaminoethyl acrylamide, phenyl acrylamide, dimethyl acrylamide, diethyl acrylamide, β-cyanoethyl acrylamide, diacetone acrylamide, etc .; Methacrylamides such as propyl methacrylamide, butyl methacrylamide, t-butyl Methacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, methoxyethyl Takuriruamido, dimethylaminoethyl methacrylamide, phenyl methacrylamide,
Dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide, etc .; Styrenes such as styrene, methylstyrene, dimethylstyrene, trimethylenestyrene, ethylstyrene, i-propylstyrene, chlorostyrene, methoxystyrene, acetoxystyrene, chlorostyrene. , Methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromstyrene; acrylonitrile, vinylidene chloride, phenyl vinyl ketone and the like as other monomers.

Further, a crosslinkable ethylenically unsaturated monomer may be used, and examples thereof include hydroquinone diacrylate, hydroquinone dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, and triethylene glycol dimethacrylate. Ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, 1,
4-butanediol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol dimethacrylate, glycerol diacrylate, glycerol dimethacrylate, glycerol triacrylate,
Glycerol tridimethacrylate, 1,1,1-trishydroxymethylethane diacrylate, 1,1,1
-Trishydroxymethylethane triacrylate,
1,1,1-Trishydroxymethylethane dimethacrylate, 1,1,1-Trishydroxymethylethane trimethacrylate, 1,1,1-Trishydroxymethylpropane diacrylate, 1,1,1-Trishydroxymethylpropane trimethacrylate Methacrylate, triallyl cyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate, divinylbenzene and the like can be mentioned.

In the present invention, the preferable ratio of the ethylenically unsaturated monomer having a nonionic hydrophilic group is 3 to 30% by mass, and more preferably 5 to 2% by mass based on the total monomers.
0% by mass, or plural kinds of the above monomers may be combined.

The binder in the hydrophilic binder layer preferably used in the present invention is a hydrophilic protective colloid,
An aqueous dispersion of resin may be mentioned.

Although gelatin is preferably used as the binder of the hydrophilic colloid layer, other hydrophilic colloids can be used in combination.

For example, gelatin derivatives, graft polymers of gelatin and other polymers; proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate, sodium alginate, cellulose sulfate, dextrin, dextran. , Sugar derivatives such as dextran sulfate; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. Can be used. As the gelatin, besides lime-processed gelatin, acid-processed gelatin may be used in combination, and further, a hydrolyzed product of gelatin or an enzymatically decomposed product of gelatin may be used.

Next, the polymer fine particle (hereinafter, also simply referred to as matting agent) dispersion liquid of the present invention will be described.

The polymer particle dispersion of the present invention contains the above-mentioned ethylenically unsaturated monomer having a nonionic hydrophilic group and the hydrophobic ethylenically unsaturated monomer, for example,
It can be obtained by polymerizing by the suspension polymerization method shown below to prepare copolymer fine particles, and adding an inorganic electrolytic substance described later to the copolymer fine particles.

The polymer fine particle dispersion of the present invention preferably contains polyvinylpyrrolidone (hereinafter abbreviated as PVP) from the viewpoint of more exerting the effect of the present invention.

The glass transition temperature (T
g) can be appropriately selected depending on the application, but is preferably 40
C. or higher, more preferably 70.degree. C. or higher.

The average particle size of the matting agent of the present invention can be appropriately selected depending on the application, but a diameter not less than the thickness of the hydrophilic binder layer is preferable, and 1.5 to 4 times is more preferable.

As the method for producing the matting agent of the present invention, a polymer which has been polymerized may be dispersed, or a monomer may be obtained by suspension polymerization in which the monomer is polymerized in an aqueous medium or after being dispersed. Good. The production method is not particularly limited as long as the polymer fine particles of the present invention can be formed, but a suspension polymerization method in which a suspension of an ethylenically unsaturated monomer in which an oil-soluble polymerization initiator is dissolved is polymerized in an aqueous medium is preferable.

In the present invention, when carrying out suspension polymerization,
You may use a surfactant as a dispersion stabilizer of a monomer.

In suspension polymerization, gelatin, gelatin derivatives, graft polymers of gelatin and other polymers; proteins such as albumin and casein; hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, as dispersion stabilizers for monomers; Cellulose, polyvinylpyrrolidone, polyvinyl alcohol,
Polyethylene glycol, polyethylene oxide, polyether, polysaccharide, hydrophilic polyurethane,
Polyhydroxyacrylate, polymethacrylate, dextran, xanthane, methylcellulose, N-vinylpyrrolidone, N-vinyllactam, N-vinylbutyrolactam, N-vinylcaprolactam, other vinyl compounds having polar pendant groups, hydrophilic esterification groups A hydrophilic colloid such as a homopolymer or copolymer of acrylate, methacrylate, hydroxy acrylate acrylic acid having ## STR4 ## or starch may be used, and the dispersion stabilizer may be added during the polymerization.

As the polymerization initiator of the suspension polymerization for obtaining the fine particles of the copolymer of the present invention (arithmetic mean particle size: 3 to 10 μm), for example, organic solvent-soluble peroxides, azobis compounds and the like can be used.

Specific examples include 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile), lauryl peroxide and benzoyl peroxide. .

If necessary, a chain transfer agent can be added to the monomer. Other suspension stabilizers include anionic fine particle suspension stabilizers (silica, clay, talc, etc.), anionic, cationic and nonionic surfactants such as ((sulfonated) alkylaryl polyethers and ethylene of polyhydric alcohols. Glycol ether, carboxyalkyl-substituted polyglycol ether and ester, sodium salt of condensation product of naphthalene sulfonic acid and formaldehyde, glycidol polyether phosphate ester, higher alcohol sulfate ester, fatty acid ester derivative of sulfosuccinic acid, α-of fatty acid Sulfo lower alkyl esters and sulfuric acid ester products of glycidol polyethers, etc.) can be used.

As a polymerization method and conditions for obtaining the copolymer fine particles of the present invention, the reaction temperature is preferably 50 to 90 ° C., more preferably 55 to 85 ° C., and the polymerization reaction is continuously stirred for 1 to 5 hours while continuously stirring the reaction solution. It is preferable to carry out the polymerization reaction for 2 to 3 hours, and then the reaction solution is left standing or intermittently stirred until the reaction is stopped.

Specific examples of the inorganic electrolytic substance include sodium chloride, calcium chloride, potassium chloride, potassium iodide, sodium sulfate, sodium nitrate, sodium citrate, sodium acetate, ammonium acetate, magnesium sulfate and the like. Of these, sodium chloride, sodium sulfate, magnesium sulfate and calcium chloride are preferable.

In the present invention, the content of the inorganic electrolytic substance is 0.1 to the total mass of the fine polymer particle dispersion.
It is preferably 10% by mass from the viewpoint that the effect of the present invention can be further exhibited.

[0048]

EXAMPLES The present invention will now be described in detail with reference to examples, but the embodiments of the present invention are not limited thereto.

<Manufacture of Matting Agent> MA-1 methyl methacrylate (75 g) and hydroxyethyl methacrylate (25 g) are mixed and the polymerization initiator lauryl peroxide (4 g) is dissolved in the mixed monomer.

On the other hand, 0.6 g of sodium dioctylsuccinate and 10 g of polyvinylpyrrolidone are dissolved in 400 g of water, the above-mentioned monomer and polymerization initiator are added while stirring the solution, and the mixture is dispersed at 2,000 rpm for 30 minutes. This suspension was placed in a 1 liter round bottom flask and stirred at 70
After heating at ℃ for 5 hours, it was cooled. The produced polymer particle dispersion was designated as MA-1. The arithmetic mean particle size measured by Multisizer was 6.5 μm.

The arithmetic mean particle size was measured with a Coulter Multisizer (manufactured by Coulter). (Hereinafter, measured in the same manner.) MA-2 75 g of methyl methacrylate, 20 g of hydroxyethyl methacrylate and 5 g of lauryl methacrylate are mixed, and 2 g of lauryl peroxide, a polymerization initiator, is dissolved in this mixed monomer.

On the other hand, 400 ml of water was added to a 1 liter round bottom flask.
g, 0.6 g of sodium dioctylsuccinate is dissolved,
The solution is warmed to 70 ° C. with stirring. 3,000 solution
While dispersing at 0 rpm, the monomer and the polymerization initiator are added, and the dispersion is continued for 120 minutes. After that, the dispersion was stopped, and the mixture was heated at 70 ° C. for 3 hours and then cooled. The produced polymer particle dispersion was designated as MA-2. The arithmetic mean particle size measured by Multisizer was 8.7 μm.

MA-3 98 g of methyl methacrylate and 2 g of lauryl methacrylate are mixed, and 2 g of the polymerization initiator lauryl peroxide is dissolved in this mixed monomer.

On the other hand, 8 g of polyvinylpyrrolidone was dissolved in 400 g of water, the monomer and the polymerization initiator were added while stirring the solution, and the mixture was dispersed at 3000 rpm for 1 hour. This suspension was placed in a 1-liter round bottom flask, heated with stirring at 70 ° C. for 5 hours, and then cooled. The produced polymer particle dispersion was designated as MA-3. The arithmetic average particle diameter measured by Multisizer was 9.0 μm.

MA-4 88 g of methyl methacrylate, 10 g of hydroxyethyl methacrylate and 2 g of lauryl methacrylate were mixed, and 5 g of lauryl peroxide, a polymerization initiator, was dissolved in this mixed monomer.

On the other hand, in 400 g of water, 0.6 g of sodium dioctylsuccinate, 1 g of polyvinylpyrrolidone and 1.5 g of sodium chloride were dissolved, the above-mentioned monomer and polymerization initiator were added while stirring the solution, and the mixture was added at 30 rpm at 2500 rpm.
Disperse in time. This suspension was placed in a 1-liter round bottom flask, heated at 70 ° C. for 3 hours with stirring, and then cooled. The produced polymer particle dispersion was designated as MA-4. The arithmetic mean particle size measured by Multisizer was 7.9 μm.

Example Preparation of Matting Agent The matting agent M described above.
The types and amounts of additives shown in Table 1 were added to -1 to M-4 to prepare matting agents of Examples 1 to 6 and 8.

In Example 7, the types and amounts of the inorganic electrolytic substances shown in Table 1 were added in the step of synthesizing the copolymer fine particles.

<Evaluation of Handling Property> Examples 1 to 8 and Comparative Example 9
After thoroughly stirring the matting agents of ~ 13, the state after standing for 24 hours was visually observed and evaluated by a feel of a spatula in three grades.

Evaluation Criteria ◯: There is no precipitate having a feel on the spatula, and it can be easily and uniformly stirred. Δ: There is a feel of a soft precipitate, but it can be uniformly stirred. ×: There is a hard precipitate. Difficult to stir evenly.

The evaluation results are shown in Table 1. <Preparation of coating sample> Pure water was added to 2 g of the solid content of the matting agent and 0.04 g of sodium di-N-hexylsulfonate as a surfactant to adjust to 100 g.
After stirring for 5 minutes, ultrasonic dispersion is performed for 3 minutes to prepare a matting agent dispersion liquid.

On the other hand, pure water was added to 3.5 g of gelatin to obtain 5
Adjust to 0 g, swell gelatin and heat to 40 ° C.

6.7 g of the matting agent dispersion liquid and 50 g of a gelatin solution are mixed at 40 ° C. or lower to prepare a coating liquid.

The coating solution is heated to a predetermined temperature and coated on a 100 μm polyethylene terephthalate support with a wire bar so that the dry film thickness becomes 3.9 μm. Application temperature setting is 40 ℃, 45 ℃,
The five points are 50 ° C, 55 ° C, and 60 ° C.

<Evaluation of Cohesion of Coating Liquid> Coating sample 5 cm × 5
cm is piled up 3 sheets, and the degree of cloudiness of the sample is 40 ° C, 45 ° C, 50 ° C, 55 ° C with a Tokyo Denshoku haze meter.
It was evaluated at 5 points of 60 ° C. The significantly worse the coagulation of the coating solution,
The particles are aggregated, the particles are unevenly distributed, and the change in the haze value (%) (values at 40 ° C, 45 ° C, 50 ° C, 55 ° C, and 60 ° C) is large with respect to the value at 40 ° C. The smaller the change with respect to the value of 40 ° C., the less the coating liquid aggregates. Table 1 shows the evaluation results
Shown in.

<Evaluation of Sticking> 3.5 cm × 10 cm for a guide coating sample coated at a coating liquid temperature of 45 ° C.
Were cut into 6 pieces each and were left for 1 day in an atmosphere of 30 ° C. and 80% RH so as not to contact each other. After that, the six samples were stacked, and left under the same atmosphere for one day with a load of 800 g being applied.

Thereafter, with the load still applied, the temperature is 50 ° C. at 23 ° C.
The sample was peeled off after standing for 1 day in an atmosphere of% RH. The state of sticking when peeled off was evaluated by 5 levels according to the following evaluation criteria.

5: Peel without resistance, no adhesion mark 4: Peel without resistance, but adhesion mark is less than 20% of the total area 3: Peel without resistance, but adhesion mark is 20% to 6% of the total area
Less than 0% can be seen 2: Resistance to peeling is felt, and 60% or more of adhesion area is observed 1: There is resistance to peeling, and peeling of the hydrophilic binder is recognized.

<Evaluation of Detachability> A coating sample coated at a coating liquid temperature of 45 ° C. was fixed on a flat test stand made of metal, and a felt cloth was applied to the surface to form a flat surface having a thickness of 5 mm and a square of 1 cm. The stainless plate was brought into contact with the surface of the sample such that the felt surface of the sample was contacted, a load of 1000 g was applied to the plate, and the sample was rubbed 20 times in the plane direction of the sample with a length of 5 cm. The surface after rubbing was observed, and the level of exfoliation of the matting agent was evaluated on a scale of 5 according to the following evaluation criteria.

5: No peeling is observed 4: Slight peeling is observed 3: Stripping is clearly recognized 2: Almost exfoliated 1: Completely stripped.

[0071]

[Table 1]

The unit of haze value in the table is%. As is clear from the results in Table 1, the sample of the present invention has no sticking and no deterioration in peeling property, has good handleability, and has good coating solution stability.

[0073]

As demonstrated in the examples, the sheet-like material and the method for producing the same according to the present invention have good handleability, no agglomeration of polymer fine particles occurs in the coating liquid, and the sheet-like materials are superposed. It has an excellent effect that it does not stick to the surface and polymer particles do not come off.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 3/00 C08K 3/00 C08L 101/02 C08L 101/02 F term (reference) 4D075 BB24Z CA04 CA13 CA15 CA35 CA43 CA47 DA04 DB13 DB18 DB31 DC24 DC27 EA06 EA13 EB13 EB14 EB15 EB19 EB22 EB39 EB56 EB57 EC01 4F071 AA22 AA28 A02 33 DE01A EH46A EJ86A GB90 JB05A JB06A JL11 YY00A 4J002 AD012 BC041 BG051 BG131 BJ003 DD056 DG046 FD206 GS00 HA06

Claims (10)

[Claims] 1. A polymer obtained by adding an inorganic electrolytic substance to a copolymer fine particle dispersion containing an ethylenically unsaturated monomer having a nonionic hydrophilic group and a hydrophobic ethylenically unsaturated monomer. Coating the fine particle dispersion on a support,
A sheet material characterized by being dried. 2. A polymer obtained by adding an inorganic electrolytic substance to a copolymer fine particle dispersion containing an ethylenically unsaturated monomer having a nonionic hydrophilic group and a hydrophobic ethylenically unsaturated monomer. A method for producing a sheet-like material, which comprises producing a dispersion of fine particles by coating on a support and drying. 3. A copolymer fine particle dispersion obtained by polymerizing an ethylenically unsaturated monomer having a nonionic hydrophilic group and a hydrophobic ethylenically unsaturated monomer in the presence of an inorganic electrolytic substance is supported. A method for producing a sheet-shaped material, which comprises applying the composition on a body and drying the composition. 4. The sheet material according to claim 1, wherein the polymer fine particle dispersion contains polyvinylpyrrolidone. 5. The sheet-shaped material according to claim 1, wherein the content of the inorganic electrolytic substance is 0.1 to 10 mass% with respect to the total mass of the polymer fine particle dispersion. 6. The method for producing a sheet-like material according to claim 2, wherein the content of the inorganic electrolytic substance is 0.1 to 10 mass% with respect to the total mass of the polymer particle dispersion. 7. The sheet-like material according to claim 1, 4 or 5, wherein the inorganic electrolytic substance is at least one compound selected from sodium chloride, sodium sulfate, magnesium sulfate and calcium chloride. 8. The sheet-like material according to claim 2, 3 or 6, wherein the inorganic electrolytic substance is at least one compound selected from sodium chloride, sodium sulfate, magnesium sulfate and calcium chloride. Method. 9. The sheet-shaped material according to claim 1, wherein the polymer fine particles in the polymer fine particle dispersion have an arithmetic average particle diameter of 3 to 15 μm. 10. The method for producing a sheet material according to claim 2, wherein the polymer fine particles in the polymer fine particle dispersion have an arithmetic average particle diameter of 3 to 15 μm.