JPS6198748A - Production of sheet matereial having surface and back with different function - Google Patents

Abstract

PURPOSE:To obtain the titled sheet material, by subjecting one surface of a high polymer sheet material treated with a resin to low-temperature plasma treatment, bringing further the sheet material into contacet with a dispersion of a radically polymerizable monomer and a dispersion of a transition metal salt and forming an apparent graft polymerization layer. CONSTITUTION:A high polymer sheet material is treated with a resin. The treated one surface, or only one surface is treated with a resin, and the other surface is subjected to low-temperature plasma treatment at 0.01-200 mmHg gas pressure of a radically polymerizable gas containing no oxygen gas or gas pressure containing the oxygen gas at 1-2,000 watt sec/cm<2> electric energy, and the surface is brought into contact with oxygen when the oxygen gas is not contained to form active points. The sheet material is brought into contact with 0.1-90 wt.% radically polymerizable monomer dispersion and 0.0001-l1 wt.% transition metal salt dispersion or mixed dispersion of them, and an appar ent graft polymerization layer is formed at room temperature or under heating.

Description

[Detailed description of the invention] Industrial application field> The present invention provides a method for treating one surface of a resin-processed polymer sheet,
The present invention relates to a method for producing a sheet material having different functions on both sides, which is characterized by forming an apparent graft polymerized layer after low-temperature plasma treatment.

<Prior art> Many methods have been used to produce sheet-like materials with durable properties by subjecting polymeric sheet-like materials, such as paper, film, non-woven fabrics, and woven and knitted materials, to high-voltage discharge treatment. ing. For example, published patent publications No. 52-98011, No. 53-61789, No. 54-56671, 5B-5
It has been proposed in No. 4851, etc.

However, with these methods, the functionality is the same, but the durability is only improved over the conventional processing method, and the high voltage discharge treatment increases the complexity and cost.

At present, it has not been put to practical use because it has not yet been fully covered.

In addition, we use low-temperature plasma processing to process different functions on the front and back.
What is conventionally known is:

(1) A method of imparting hydrophilicity by subjecting one side of a textile product containing at least 50 strands of synthetic fibers to low-temperature plasma treatment.

(2) A method of imparting hydrophilicity by subjecting one side of a water-repellent textile product to low-temperature plasma treatment.

It is.

However, it is well known that these methods cause loss of hydrophilicity over time.

As a textile product, it cannot be said to be durable and is not practical.

<Problems to be Solved by the Invention> As a result of further studies on low-temperature plasma discharge technology and low-temperature plasma discharge graft polymerization technology, the present inventors have developed a durable polymer having two or more different functions on the front and back sides. This invention was based on the invention of sheet-like materials.

<Means for Solving the Problems> In other words, the present invention involves processing a polymer sheet-like material with a resin, and then subjecting one surface thereof to low-temperature plasma treatment to form a sheet-like material capable of radical polymerization. , by contacting a radically polymerizable monomer dispersion and a transition metal salt dispersion, or a mixed dispersion of the monomer and the transition metal salt at room temperature or by heating, a resin-processed polymer sheet is produced. This is a method for producing a sheet-like article having different functions on both sides, characterized by forming an apparent graft polymerized layer of the monomer on one surface of the article.

The polymer sheet material referred to in the present invention is paper, film, nonwoven fabric, woven or knitted fabric, etc. made of natural polymers, synthetic polymers, etc.

The resin processing referred to in the present invention refers to permanent, press processing, shrink-proofing, water-repellent finishing, fire-proofing finishing, shrink-proofing finishing, mold-proofing finishing, insect-proofing finishing, waterproofing finishing, flame-retardant finishing, antistatic finishing, laminating finishing, and flocking finishing. , anti-pilling treatment, antifouling treatment, coating treatment, hydrophilic treatment, moisture absorption treatment, sweat absorption treatment, moisture permeability treatment, etc.

Methods for applying these resin treatments include dipping, dip nip, pad curing, foaming, spraying, coating, laminating, and the like.

The low-temperature plasma treatment referred to in the present invention is a gas discharge different from arc discharge or corona discharge, and the ion species constituting the plasma include Ar * He, H2+ N2 e
NO2+ 02, Air, Fluorocarbon, No.
Plasma is generated using rogenated hydrocarbons, etc., or a gas mixture thereof, using a direct current, alternating current, or high frequency power source. In this case, it is preferable to generate plasma between electrodes having an inter-electrode spacing of 11 or more and 100/cm2 or less using an AC high-frequency power supply in a gas atmosphere under vacuum. It is better to widen the distance, and narrow the distance between the electrodes when the degree of vacuum is low.

Both electrodes may be a pair of plate-shaped or rod-shaped electrodes, or a combination of a rod-shaped electrode and a drum-shaped or plate-shaped electrode, respectively. Furthermore, the electrode surface may be coated with glass, ceramics, or the like. Further, the electrode may be cooled or heated as necessary.

Low-temperature plasma processing equipment may use either an electrode in which one electrode is grounded for a grounded can, or an ungrounded electrode in which both electrodes are insulated for a grounded can. If you use a grounded electrode, the power will be about 1
It has the advantage that equivalent processing can be performed with /2. Using a drum type or plate-shaped electrode, a resin-treated sheet material is placed in contact with the drum type or plate-shaped electrode,
By fixing or moving, it is possible to obtain a sheet-like material having uniform radically polymerizable active sites on only one surface.

The low-temperature plasma processing conditions related to the present invention can be determined by the gas pressure and processing electrical energy during discharge.

The gas/pressure in low temperature plasma treatment is 0.01m
It is necessary that it is HQ or more and 20JffH9 or less.

That is, the practical application of 0.01 H9 or less is not preferable because it requires a precise device. 7 Q my
If it exceeds sHq, the discharge becomes unstable and localized discharge occurs, which tends to damage the base material and makes it difficult to generate active points. The gas pressure of the present invention is preferably 0.05M
The range is MH9 or higher↑OjlIIIHg or lower. More preferably, g is 1 tmHg or more and 0.2 flH9 or less. In this range, without damaging the base material,
The inventors of the present invention have found that this method generates the largest number of active sites capable of radical polymerization within the range of intensive investigation.

That is, when a high amount of graft polymer is required, 0. lmH
g or more 0. ．． 2 Plasma treatment at MMIH9 or less is an effective method. Usually 0.05 llHg
A range of 10 WjlHg or more is sufficient.

The gas used in the low-temperature plasma treatment in the present invention is a gas that does not contain oxygen and can form all active sites capable of radical polymerization, or a gas that contains oxygen gas.

In the present invention, the gases that do not contain oxygen and can form active sites capable of radical polymerization include Ar, He, H2? N2
+ NO2+ No v CO2+ It is a gas such as CO, halogen, halogenated carbon, fluorocarbon hydrocarbon, or a mixture thereof. Then, it contains oxygen gas. Oxygen and air are representative gases.

The oxygen-containing gas is not particularly limited, and a mixture of the above gases may be used. The processing electrical energy in the low temperature plasma processing is 1
It is necessary that the wattage is 1 or more and 2000 watts/cm2 or less. The processing electrical energy is E ==
W knee T (Watts'd) Wi discharge output (Watts) T; processing time (seconds) S; electrode area (d). The processing electrical energy is 17) [4'/
, /cm2 or less 7, the example of JP-A-59-80445 shows that a relatively high amount of graft polymer can be obtained, and that the amount of digraft polymer can be freely controlled by the plasma treatment time within this range. Are listed.

Indeed, such a tendency was confirmed below 1 Watsu''/i. However, as a method for freely controlling the amount of graft polymer, the adjustment range of plasma treatment time is too narrow, and detailed control is actually difficult. Furthermore, if the processing electric energy is 2000 watts/second or more, there is a risk of damage to the can body and the base material, and it is not practical in terms of cost.

In the present invention, the particularly preferable processing electric energy is 5 watts or more and 10,007 watts or less. In particular, the treatment of substrates used in normal graft polymerization is
Practically and from the viewpoint of production control, it is preferable to perform plasma treatment in a stable range of the amount of radically polymerizable active sites generated in the range of 5 watts/sec to 50 watts/cm 2 .

However, the apparent amount of graft polymer can be controlled by
This can be achieved depending on the transition metal salt used in combination with the monomer and the graft polymerization reaction conditions. Further, if a high apparent amount of graft polymer is required, it is possible to appropriately select the processing electric energy from 5 Q7t I'/d to 2000'7t I'/d or less.

The low-temperature plasma is generated between the counter discharge electrodes at a frequency of 5 KHz to 100 MH under the above gas pressure and processing electric energy.
A high frequency such as z can be used.

Furthermore, as the discharge frequency band, in addition to the above-mentioned high frequency, low frequency, microwave, direct current, etc. can also be used. The low-temperature plasma generator may be a capacitively coupled type such as an external electrode type or a coil type, or an inductively coupled type.

The sheet-like material whose one surface has been treated with low-temperature plasma is then exposed to oxygen gas or a mixed gas containing oxygen gas, or taken out into the atmosphere, and the radicals generated on one surface of the sheet-like material by the plasma treatment are removed. React the polymerizable active site with oxygen.

In oxygen gas or a mixed gas containing oxygen gas,
This operation is not necessary for plasma treated items. By these operations, the radically polymerizable active site becomes a stable active site for a long period of time.

The amount of radically polymerizable active sites generated on one surface of the sheet-like material treated in this way is 10-11 or more.
−8−v−x/, which is the following. The amount of active points generated is 10-
When it is less than "mo"/d, the apparent amount of graft polymer is small. Further, according to detailed experimental studies conducted by the present inventors, a large amount of energy is required to increase the amount of active sites generated to io-1'%□ or more, which makes the cost too high for practical use. The amount of active sites u particularly preferred for graft polymerization,
It is 10-10 m''/d or more and 1 g-8 mol/cd or less.

The sheet material treated in this way was then heated to 0.
A dispersion of one or more radically polymerizable monomers of 1% or more and 90% or less, and a dispersion of a transition metal salt of 0.0001% or more and 1% or less, or the monomer and the transition metal salt. and the mixed dispersion.

When the sheet-like material is brought into contact with the monomer dispersion and the transition metal salt, the combination and order are not particularly determined.

The method of bringing the sheet-like material into contact with each dispersion is not particularly defined, such as dipping or coating.

In short, it is sufficient to touch one surface of the sheet-like material that has active sites capable of radical polymerization.

When bringing the sheet-like material having active sites capable of radical polymerization into contact with the monomer or the transition metal salt, the surface of the sheet-like material is heated at a temperature of 0.1 urHti or more to 10
The digraft polymerization reaction proceeds more easily by removing oxygen gas, impurities, etc. contained in the sheet-like material by vacuum degassing at 0 MMkh or less or blowing with high-pressure inert gas.

There is also nothing wrong with carrying out vacuum deaeration or the like after contacting with the monomer, etc.

In addition, the digraft polymerization reaction can be improved by introducing an inert gas into each dispersion liquid to deoxidize it before or after bringing the sheet material into contact with the monomer and transition metal salt, or during the reaction. Proceeds easily.

The concentration of the monomer dispersion is 0.1% or more and 90% or less. Preferably it is 0.1% or more and 50% or less.

Within this range, it is easy to suppress the homopolymerization reaction and increase or control the apparent amount of graft polymer by using the transition metal salt.

The concentration of the transition metal salt dispersion is 0.0001% or more and 1% or less. If it is 0.0001% or less, the effect of suppressing the homopolymerization reaction is extremely low and is not of practical use. Furthermore, if the number of sheets is more than 1 inch, the sheet-like material will be significantly colored, which is not practical. Further, by changing the transition metal salt concentration depending on the monomer concentration, reaction temperature, and reaction time, it is possible to increase or control the apparent amount of graft polymer.

The reaction temperature is preferably room temperature or 20°C or more and 80°C or less. The optimum temperature should be appropriately selected depending on the reactivity of the monomer, monomer concentration, transition metal salt concentration, and reaction time, and is not particularly limited.

The reaction time is in the range of 10 seconds or more and 10 hours or less. The reaction time should be selected depending on the reaction method, reaction temperature, monomer concentration, transition metal salt concentration, etc., and is not particularly limited.

The methods for the graft polymerization reaction include a method in which the sheet material is brought into contact with a mixed solution of a monomer and a transition metal salt and heated at the same time, a method in which the sheet material is brought into contact with the mixed solution and then moderately squeezed and heated; Furthermore, after the sheet-like material is heat-treated in the reaction apparatus, it may be brought into contact with the mixed solution immediately, and the heating may be carried out either in the same bath or by heating separately. Furthermore, as described above, there is no problem even if the monomer and the transition metal salt are brought into contact with the sheet-like material separately to carry out the above-mentioned graft polymerization reaction.

It is preferable to exclude oxygen from inside the graft polymerization reactor. For example, dissolved oxygen in the atmosphere in the reactor, monomer transition metal salt mixed solution, monomer solution, and transition metal salt concentration is removed by nitrogen gas or other After replacing with an inert gas, or in the case of the solution, the solvent is degassed by boiling beforehand and then replaced with an inert gas, or after contacting the sheet-like material with the monomer and transition metal salt solution, It is preferable to remove as much oxygen as possible by introducing a sheet-like material into high-pressure steam.

Even if the monomer dispersion consists of an aqueous medium containing a water-insoluble monomer and an emulsifier, or contains inorganic fine particles that do not inhibit radical polymerization, such as 51021AI205, etc. I have no reservations.

The radically polymerizable monomer used in the present invention should be appropriately selected depending on the intended use, and is not particularly limited. The radically polymerizable monomer is carbon-
It is a compound that has a carbon double bond and is a monomer that polymerizes with radicals as propagating terminals. Examples include acrylamide compounds, acrylic compounds, methacrylic compounds, vinyl compounds, and styrene compounds.

The transition metal salt used in the present invention is FeC7?2° (N
H4)2Fe(SO4)2* CuCn, Cu(N
O3)2. CuSO4゜CuCJh, Ni(NO
3)2. Co(NOs)+e Cr(NOs)2°Pb(NO3)2. LiCJl! It is possible to select a transition metal salt suitable for the purpose depending on the sheet material, monomer, reaction conditions, etc.

The Gunft polymerization reaction product of the monomers formed on the surface of the sheet-like material contains graft polymers, homopolymers with good durability, homopolymers with poor durability, unreacted monomers, etc. It will be done. The graft polymerization reaction product is heated at 65°C or higher than the boiling point of the good solvent using a good solvent for the monomer and the polymer.
By washing in a good solvent at a temperature lower than 65°C or by ultrasonic cleaning, or in the absence of a suitable good solvent,
An apparent graft polymer layer is obtained by removing unreacted monomers and homopolymers with poor durability by ultrasonic cleaning for 1 hour in water or a good solvent for the monomers.

That is, the apparent graft polymer layer is composed of an apparent graft polymer containing a graft polymer and a homopolymer having good durability. Furthermore, the apparent graft polymerization layer is formed using a good solvent for the polymer at a temperature of 0°C to 25°C below the boiling point of the solvent.
Even durable homopolymers can be removed by washing with a low-temperature solvent or by ultrasonic washing, or if a suitable good solvent is not available, by ultrasonic washing for 5 hours in water or a good monomer solvent. The resulting layer is used as a graft polymerization layer. The graft polymer layer is made of a graft polymer.

After the graft polymerization reaction, a step of removing the homopolymer with poor durability and unreacted monomers from the graft polymerization reaction product of the monomers formed on the surface of the sheet-like article is carried out by a chemical or physical method. In particular, it is possible to obtain graft polymerized layers with good durability and appearance. Chemical and physical methods include water washing, solvent extraction, ultrasonic cleaning, etc.

By this step and the polymerization reaction conditions, it is possible to control the homopolymer content with good durability in the apparent graft polymerization layer of the monomer.

By containing 90% or less of a homopolymer with good durability in the apparent graft polymerization layer, it is possible to form a polymerization layer suitable for various purposes.

By subjecting the resin-processed surface (A side) and/or one surface (B side) on which an apparent graft polymerization layer has been formed of the sheet-like material having different functions on the front and back sides obtained by the method according to the present invention to low-temperature plasma treatment. It is possible for the resin and/or apparent graft polymer to be crosslinked to form a stronger resin treated layer and/or apparent graft polymer layer.

In the case of double-sided treatment, it is possible to obtain a sheet-like material having uniform radically polymerizable active sites by performing the treatment twice on the front and back sides while touching each other on a drum-type or plate-shaped electrode, or by floating, fixing or moving the material. .

<Effects of the present invention> The advantages of the present invention are as follows: (1) After processing a polymer sheet with resin, one surface thereof is subjected to low-temperature plasma treatment, and then an apparent graft polymerization layer is formed, resulting in improved durability. It is possible to produce a sheet-like product that has excellent front and back functions.

(2) Processing only one surface of the polymer sheet with resin,
By directly forming an apparent graft polymerization layer on the other surface of the sheet after low-temperature plasma treatment, it is possible to produce a sheet that is even more durable and has different functions on both sides. .

(3) At least one surface of these highly durable sheet-like materials having different functions on both sides is further subjected to low-temperature plasma treatment to form a resin processed layer and/or an apparent graft polymerized layer with high crosslinking density. However, it is possible to further improve durability.

<Example> The present invention will be explained below with reference to Examples.

Example 1 After dyeing a stretchable fabric made of double knit polyester processed yarn, it was thoroughly dried in a pin tenter (120°C).
Antistatic agent whose main component is polyethylene glycol,
Dip nipping was performed in a 5% aqueous emulsion solution containing polyethylene glycol dimethacrylate having a molecular weight of 100 G, and then curing was performed at 170°C. Only one surface of this hydrophilized fabric was subjected to low-temperature plasma for 20 seconds by introducing Ar gas in an internal electrode type plasma device at a frequency of 13.56 MHz and an output of 0.64 Watts at a vacuum level of 0.2 MTIHg. The treatment was carried out to form active points capable of graft polymerization, and when the active points were taken out into the air and quantified, it was found that there were 5.2 x 10-''/d of active points. % hexafluorodimethyl methacrylate 1% sodium polystyrene sulfonate and 0.05% (NH4)2 Fe
After reacting for 1 hour at 40°C in an aqueous dispersion containing (5Oa)2, the mixture was ultrasonically cleaned in acetone at room temperature. As a result of weight measurement, the apparent amount of the graft polymerized layer was 97 μm. There was almost no viscosity change in the jigger dyeing machine during this graft polymerization reaction. The water pressure resistance of 8 surfaces of the obtained surface treated product is I G OO mm or more, and it can withstand 50
There was no change even after the test. Furthermore, the water repellency was 100 points, and even after washing it was 90 points. It also had excellent oil repellency. Also, the frictional charging field on the A surface after washing 50 times is 73
It exhibited a good power training performance of 0V, and when water droplets were dropped on it, the water droplets instantly dispersed, indicating hydrophilicity.

Example 2 One surface (side A) of nylon taffeta was subjected to dry breathable and moisture-permeable waterproofing using a urethane resin processing compound liquid using a floating knife coater.Subsequently, the other surface (side B)
The sample was subjected to low-temperature plasma treatment for 40 seconds in air at a frequency of 110 KHz, an output of 1.24 Watts, and a degree of vacuum of 0.15111 HiF on an ungrounded electrode insulated with respect to the grounded can. This was followed by 10 g of 3-(p-octadecylfluorononioxypenzoyloxy)2-hydroxypropyl methacrylate, 1 g of sodium polystyrene sulfonate, and 0.005% (NH4)2Fe(SO4
) 2 at room temperature, immediately left under heated N2 without exposure to oxygen for 10 minutes, and then ultrasonically cleaned in water at room temperature for 1 hour. The resulting processed fabric had water-repellent functions on the front, breathable and moisture-permeable waterproof functions on the back. The water repellency of side B was 100 points in the shower method, and 90 points after 50 home washings, indicating sufficient durability. Also, the water pressure resistance of side A is 13
00 tm N20 or higher, moisture permeability 5500'Art-2
4h rs-Breathability 0.1CC, cH: 7' (
.

Example 3 One surface of polyester taffeta (A side, thickness 25μ,
A 47-ethylene chloride film having micropores of about 0.2 to 5 μm was laminated, and then only the other surface (B side) was heated at a frequency of 110 KHz, an output of 0.82 watts, and a degree of vacuum of 0: 211 RHg in oxygen. , low temperature plasma treatment was performed for 60 seconds. Next, heated N2 at 80°C was blown onto the B side in a reaction tank purged with N2, and immediately 20% hexamethylolmelamine and 0.01% (NH4)2
After dip-nipping into the mixed dispersion of Fe (S Oa and 2), it was immediately reacted in superheated steam for 15 minutes, and heated at 40°
Washed with warm water of C. As a result, the A side of the fabric was treated to be moisture-permeable and waterproof, and the B side was treated to be heat-proof. On the A side, moisture permeability is 6000'/7F! '-24 hrs, water pressure 1
000 ml (2Q). On the B side, the Burn Index was 50 according to the heating pellet method, and the MP property was 550°C according to the glass bulb test method, making it possible to manufacture a material that has sufficient front and back melting, moisture permeable and waterproof functions. It became possible.

As a result of a durability test of 60 home washings and 10 dry cleanings, these functions did not deteriorate at all. Washing with warm water at 40°C yielded an apparent graft polymer layer (21°0 μQ/d ). 80 more
Graft polymerization layer (130 μg removed) after washing with hot water at °C.
I got it. That is, the apparent graft polymerization layer according to the present invention is made of a homopolymer with good durability (B0/'9//cd,
38).

Example 4 A cotton cloth was immersed in a mixed solution of 20 g of 2-methacryloyloxyethyl acid phosphate triethylamine salt, 5 g of N-methylolacrylamide, and 1% potassium persulfate, and after pre-drying, it was heated at 150°C. Cure ring, washed and dried. One surface of this processed cloth (B
As a result of low-temperature plasma treatment using the method shown in Example 2, and then the grafting reaction shown in Example 2, the B side achieved a water repellency of 100 points using the shower method and was washed 50 times at home. After irrigation, the oil repellency was 90 points, and the oil repellency was 6th grade according to the AATC-TM 118 method, and after 50 home washes, it was 5th grade.

The limiting oxygen index (LOI) is a measure of the flame retardancy of this processed fabric.
) was 0.26. It had sufficient flame retardancy even after 50 washes.

Example 5 A cotton fabric was subjected to sanitary treatment using 6-methoxylizuglobil octadecyl-dimethylammonium chloride. Only one surface (Side B) of the processed cloth was subjected to the same low-temperature plasma treatment and graft reaction as in Example 2. As a result of the culture test, the A side of the obtained processed fabric showed high antibacterial and mold resistant properties, and the B side showed sufficient water repellency and oil repellency. After a durability test of 20 washes, the performance was almost the same as the initial performance.

Claims (1)

[Scope of Claims] 1. After processing a polymer sheet with a resin, one surface thereof is subjected to low temperature plasma treatment to form active sites capable of radical polymerization. By contacting the body dispersion and the transition metal salt dispersion or the mixed dispersion of the monomer and the transition metal salt at room temperature or by heating, one surface of the resin-treated polymer sheet is A method for producing a sheet-like article having different functions on both sides, the method comprising forming an apparent graft polymerization layer of the monomer. 2. The resin processing is applied to only one surface (side A) of the polymer sheet, and the other surface (side B) is treated with low-temperature plasma to form an apparent graft polymerization layer. A method for producing a sheet-like article having different functions on both sides as claimed in claim 1. 3. Low temperature plasma treatment is 0.01mmHg or more 20m
Under a gas pressure that can form radically polymerizable active sites that do not contain oxygen gas of mHg or less, the electric energy is 1 watts/cm^2 or more and 2000 watts/cm^2 or less, and then oxygen gas or , exposure to a mixed gas containing oxygen gas, or low-temperature plasma treatment in advance under a gas pressure containing oxygen gas of 0.01 mmHg or more and 20 mmHg or less, electrical energy of 1 watt-second/cm^2 or more and 2000 watt-seconds/ cm^2 or less, and 10^-^1^1 mol/cm^2 or more 10^-
2. A method for producing a sheet material having different functions on the front and back sides as claimed in claim 1, which is capable of forming active sites capable of radical polymerization of ^8 mol/cm^2 or less. 4. A polymer sheet having radically polymerizable active sites formed therein is mixed with a dispersion of one or more radically polymerizable monomers of 0.1% or more and 90% or less and 0.0001% or more and 1% or less. A sheet-like material having different functions on both sides according to claim 1, which is brought into contact with a transition metal salt dispersion or a mixed dispersion of the monomer and the transition metal salt and heated at room temperature. manufacturing method. 5. A method for manufacturing a sheet-like article having different functions on both sides as claimed in claim 1, wherein the low-temperature plasma treatment is performed using a non-grounded electrode insulated from the can body. 6. Production of a sheet-like article having different functions on both sides as set forth in claim 1, wherein the apparent graft polymerization layer of monomers contains 90% or less of a homopolymer with good durability. Method. 7. A sheet-like article having different functions on both sides as claimed in claim 1, wherein the radically polymerizable monomer dispersion comprises an aqueous medium containing a water-insoluble monomer and an emulsifier. Production method. 8. Before or after contacting the sheet material with a radically polymerizable monomer dispersion or transition metal salt dispersion, or during the reaction, an inert gas may be introduced into the dispersion to remove oxygen. A method for producing a sheet-like article having different functions on both sides as claimed in claim 1. 9. Before bringing the sheet-like material on which radically polymerizable active sites have been formed into contact with a radically-polymerizable monomer dispersion or transition metal salt dispersion, the surface of the sheet-like material is degassed in vacuum or under high pressure. 2. A method for producing a sheet material having different functions on both sides as claimed in claim 1, wherein deoxidation is carried out by blowing an active gas. 10. It is characterized by including a step of removing by chemical and physical methods homopolymers with poor durability and unreacted monomers from the graft polymerization reaction product of the monomers formed on the surface of the sheet-like article. A method for producing a sheet-like article having different functions on both sides as claimed in claim 1. 11. After processing a polymer sheet with a resin, one surface of the sheet is subjected to low temperature plasma treatment to form active sites capable of radical polymerization, and then treated with a monomer dispersion capable of radical polymerization and a transition metal. By contacting a salt dispersion liquid or a mixed dispersion liquid of the monomer and the transition metal salt, and heating at room temperature or heating, the appearance of the monomer is formed on one surface of the resin-treated polymer sheet. 1. A method for producing a sheet-like article having different functions on both sides, the method comprising: forming a graft polymerization layer of the above, and further subjecting at least one surface of the obtained sheet-like article to low-temperature plasma treatment.