JPS6189236A - Surface modification - Google Patents

Abstract

PURPOSE:To perform modification of polymer base surface by plasma treatment of the surface under a specific gas pressure with specified electric energy followed be forming graft polymer layer using radically polymerizable monomer and transition metal salt. CONSTITUTION:Either or both surfaces of a polymer base (e.g., polyethylene terephthalate) is exposed, under a pressure 0.01-20mmHg, to either O2-contg. gas or O2-free gas capable of forming radically polymerizable activation point, being subjected to a low-temperature plasma treatment at an electric energy level 1-2,000 watt.sec/cm<2>. In case of O2-free gas, contact of said surface(s) with O2-gas or O2-contg. mixed gas follows to form radically polymerizable activation points at a level of 10<-11>-10<-8>mol/cm<2> on said surface(s). Further more, the surface(s) is brought into contact with 0.1-90% radically polymeriza ble monomer dispersion and 0.0001-1% transition metal salt dispersion or mixed liquid thereof followed by treatment either at room temperature or ele vated temperatures, thus forming the objective graft polymer layer with its graft level controlled.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a surface modification method characterized by forming a graft polymerization layer on a base material made of a polymeric substance.

Substrates made of polymeric materials are widely used as extremely demanding substrates. However, at present, there are many defects caused by the surfaces of these base materials. For example, generation of static electricity, adhesion.

The drawbacks are poor printability, moisture absorption, sweat absorption, and water repellency. In order to solve these drawbacks, active research on surface modification is being conducted in various fields.

One of the methods for modifying a base material made of a polymeric substance is to form a graft polymerization layer. Conventionally, radiation grafting methods, ultraviolet graft polymerization methods, and the like have been studied as methods of this type.

The radiation graft polymerization method is a surface modification method in which radicals are generated in a polymeric substrate by irradiating the substrate with radiation, and various monomers are graft-polymerized using the radicals as a starting point. The graft polymerized layer produced by the radiation A method has excellent durability, but since the energy of the radiation is extremely high, the radiation penetrates not only the surface of the polymer base material but also the inside, impairing the functionality of the base material. will be damaged. Furthermore, it has the drawbacks of being more expensive and dangerous than generating low-temperature plasma.

Obtained by the ultraviolet graft polymerization method: (50) The removal is similar to the low-temperature plasma craft polymerization method, but in order to obtain the same young fruit, it requires 10 to 100 times more energy than a (warm plasma), However, this method has the disadvantage that it is limited to materials that absorb UV radiation sufficiently.

As a method of modifying the surface of a polymer base material, there is a -C low temperature plasma discharge graph) & method. What is Jin's method?

This is a method in which the surface of a polymer substrate is activated by low-temperature plasma discharge, and a polymerizable monomer is graft-polymerized from the active site to form an extremely thin t' polymeric molecular layer on the surface of the polymer substrate. Conventionally known grafting methods of this type include (a method in which the surface of a polymer base material is activated by 1 L of plasma radiation, and then graft polymerized by immediately bringing it into contact with Tosuke monoluteum. (2) A method in which madder molecular powder is subjected to plasma discharge treatment under a gas pressure of 0.1 rtm Hy, exposed to 1 M elementary gas, and then graft polymerized in an acrylonitrile bath liquid.
If you release high voltage below! , fW e is exposed to oxygen gas, and then subjected to ML polymerization in a monomer solution capable of radical polymerization. (4) Polymer base material at 0 gas pressure
．． 01gHy or more and 0.1 rag Hy or less, output 0.
Ol watts / Ca or more 5 watts) / cl After plasma discharge treatment under Ja, exposed to oxygen and then!
I (There is a method of graft polymerizing a merizable monomer.

Method (1) requires that the plasma discharge treatment of the polymer base material and the subsequent polymerization (graph) be carried out in a system in which oxygen, which acts as a radical sleeve) (!), has been removed first.

Developing such a device would be difficult and extremely expensive, making it impractical.

Method (2) is published in Polymer 1961, Vol. 2, 277.
However, there is no detailed description of the conditions for plasma discharge treatment of polymer powder.

Methods (8) and (4) are respectively
3132° JP-A-59-80443 K has been described. The method of Nire et al. was considered to be the most widely used method among the above (1) to (4). Therefore, as a result of detailed experimental studies, the present inventors developed method (8). In many cases, the amount of grafting is relatively low, and furthermore, it has been found that it is difficult to control the amount of grafting. In addition, in method (4), the degree of pressure reduction is large during plasma discharge treatment of polymer substrates, and a large amount of energy and strict equipment are required to maintain this degree of vacuum when processing large polymer substrates. There are drawbacks to doing so. After conducting a more detailed follow-up test, the first
As shown in the figure, it was found that the amount of active sites capable of radical polymerization depends on the electrical energy of the process. 1st
tiDPE in the figure is high-density polyethylene with a film thickness of 60 μm. These film pieces were processed using an ungrounded plasma processing device at a frequency of 5 KHz and an Ar gas pressure of 0.04 H. In order to put the low-temperature plasma discharge graft polymerization method into practical use, the present inventors As a result of intense research into stable plasma processing conditions for
43 has 1.2 watts of electrical energy, which is said to have not been grafted.

Plasma treatment conditions have been found under which the graft assembly of fcjIJ: can be stably formed in 4 seconds or more. Namely.

Electrical energy 5 watts / 50 watts over Ca
Stable graft polymerization is possible when plasma treatment is performed at a speed of 4 seconds or less. When a higher amount of graft polymer is required, it is preferably 50 watts/cm2 or more.

The present inventors have discovered plasma treatment conditions that can stabilize the amount of graft polymer, and have completed the present invention by making it possible to put into practical use a method for surface modification of polymeric substrates by low-temperature plasma discharge graft polymerization.

The most characteristic feature of the present invention is the above-mentioned Japanese Patent Application Publication No. 59-804.
The amount of grafting is controlled by delicate adjustment of the plasma treatment time as described in detail in 43.It is not an attempt to pearl, but a stable amount of pearl.
,) A method in which low-temperature plasma treatment is performed to generate active sites capable of radical polymerization, and the apparent amount of graft aggregates is controlled by the transition metal salt used in combination with the monomer and the graft ff polymerization reaction conditions. It is.

The present invention will be explained below.

The polymer base material referred to in the present invention is 1. Natural C such as silk and wood; molecules, as well as polycoastyl, polyether, polyamide, and polyacrylonitrile.

Polyethylene, polypropylene, polyethylene, polycarbonate, vinylidene compound.

Cellulose acetate, cellophane, A B S j, Bl
, 7 p-lyl resin, methacrylic resin, phthanol resin (
fat, area resin, melamine resin, epoxy 4ji JI
Threat polymers such as # are introduced.

Furthermore, the composition Fi of these polymeric base materials does not necessarily have to be unique, and may be a mixture of two or more types or a block copolymer of two or more types.

In terms of shape, it is 41i fiber-like, plate-like, sheet-like, and cylindrical.

Any shape, such as a block shape, is fine.

The present invention is particularly directed to films and fiber molded articles. In particular, the fiber molded product may be filament yarn, spun yarn, knitted fabric, or woven fabric, and these molded products may be dyed or processed with 11 fat J:J! , there is no harm in ignoring it. Dyeing, processing and low-temperature plasma discharge grafting can be combined with 9 to 6 yuzu 1) 1j pi.

Front and back Ni1 function base material with medium function and super durable resin I-, excellent durability 1 and high original color base 44. Ten battles (Tsuku H)
It is possible to generate active points on one side of the substrate by treating at least one side with low-temperature plasma. . Furthermore, if both sides are subjected to low-temperature plasma treatment, it is possible to provide active sites on both sides of the base material. These processing planes t, LI'J, and KL6 should be selected at the appropriate time (l>I), and are not limited to Ql.

In Kienyu J, Kotori's polyechishi, ndeshi, and flute are at least phantom 75chi, which is repeated in the early position of the case, o.
-G-ooc-@-co (however, -G- contains 2 to 18 carbon atoms and has 1 o 11 carbon atoms!j) The unit of 4 is 4 times the divalent fuhii which is bonded to the oxygen baby of M. It means a glycol dicarboxylate rim-shaped unit such as h'j. Terephthalate & may be the only dicarboxylate component of the repeating structural unit, with I"'i y" repeated once, and adipate, sebacate, inophthalate, pi, etc. It is acceptable even if it contains other dicarboxylates such as benzoate, hexahytrotylephrate, diphenoxyethane-4,4'-dicarboxolate, and 5-sulfo-isophthalate groups. As the glycols, polymethylene glycols such as ethylene glycol, tetramethylene glycol and hexamethylene glycol, branched chain glycols such as 2,2-dimethyl-1.3-globandiol, diethylene glycol, or mixtures thereof can also be used. If desired, up to about 15% higher glycols such as high molecular weight polyethylene glycols can also be used. Various other substances such as matting agents, gloss improvers, anti-tarnish agents, inorganic particulates, etc. may also be added to the polymerization mixture if desired.

The low-temperature plasma discharge 11i referred to in the present invention is a gas discharge different from a 17-corona discharge or a corona discharge.
, N (J2.02. Air, fluorocarbon, halogenated carbon, etc.

Alternatively, using a gas mixture of these, direct current, alternating current 1
In this case, a counter current high frequency power source is used to generate plasma in the gas atmosphere directly below the plasma.
It is preferable to generate plasma between electrodes having an inter-electrode spacing of cIn or more and 1Ocrn or less, but when the true degree is high, the distance between the strokes is increased by '1', and when the true degree is low, the distance between the strokes is widened. 1! ! It is better to narrow the distance between A.

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 with one electrode grounded to the can body or an ungrounded electrode with both electrodes insulated from the can body, but it is not possible to use an ungrounded electrode. , which has the advantage of being able to perform the same treatment with a grounded type electric power of about 172. In the present invention, gases that can form radically polymerizable active sites that do not contain oxygen include Ar, He, N2,
N2, NO2, NO, C (J2, CO, halogen,
It is a gas such as halogenated carbon, fluorinated carbon, or a mixture of these. Next, oxygen and fertility are representative gases containing 4T. The corners of the oxygen-containing dregs are not particularly rounded, and a mixture of the above gases may be used.

The low temperature plasma processing conditions related to the present invention V are the gas pressure of τ during discharge! It can be determined by electrical energy.

The gas pressure applied to the low-temperature plasma treatment must be 0.01 N2 or more and 20 rrrra My or less.

That is, practical use at 0.01 w Hf or less is not preferable because it requires a precise device. At 20 kiy or more, the discharge becomes unstable and a local discharge 1) 1 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 in the range of 0.05rmH2 or more and 10w)iy or less. More preferably 0.
1 question is Hp or more and 0.2 tan ki or less. It was found that within this range, the largest number of active sites capable of radical polymerization is generated in the axial rotation that was intensively investigated by Shishi et al., without causing damage to the base material. That is.

When a high amount of graft 1 is required, plasma treatment at 0.1 to H7 or more and 0.2 tn or less to K11 is recommended.
It's an elegant method. Usually 0.05 trrm Hf
A range of 10 rrra kb or more is sufficient.

When the base material is a sheet-like material, using a drum type or plate-shaped electrode, while contacting the drum type or plate-shaped mb,
By fixing or moving it, you can create a sheet-like material that has uniform radically polymerizable active sites on only one side! It is possible to do so. A sheet-like material having active points on one side is processed in the same manner as one of the two, to obtain a sheet-like material having active points on both sides.

In addition, by fixing or moving the active points between the electrodes without touching the electrodes, it is possible to generate radicals in both blood. can be generated.

The processing electrical energy in low temperature plasma processing is 1
It is necessary to set the value between watts/min and 2000 watts/tri. It can be expressed as the treatment time (seconds), S: electrode area Cc, ). If the processing electrician energy is less than 1 watt-second/-, 4? It is described in Examples of 1984-80443 that a relatively high graft polymer sensitivity can be obtained and that the amount of graft polymer can be freely controlled within this range by changing the plasma treatment time. Certainly l
Such a tendency was confirmed below Watts/d.

However, as a way to freely control the craft polymer award.

Unfortunately, the adjustment range for plasma treatment time is narrow, and detailed control is difficult in practice. However, if the processing electrical energy exceeds 2,000 watts/sec/crti, there is a risk of damage to the can body and the base material, making it unsuitable for practical use. In the present invention, the particularly preferable processing electric energy is 5 watts/m or more and 1000 watts/sec/cr.
A or below. In particular, the treatment of the base material used for normal grafting is 5 watts / crA or more 50 watts / seconds /
Practically and from the viewpoint of production control, it is preferable to perform the plasma treatment in a stable range of the amount of radically polymerizable r-occupied points of 6A or less. However, the apparent amount of graft polymer can be controlled by the transition metal salt used in combination with the monomer and the graft polymerization reaction conditions. Moreover, if a graft polymer with high appearance is required, it is possible to appropriately select the processing electrical energy from 50 watts/- to 2000 watts/-.

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.
High waves 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. . , 1. Eh)
It may be a capacitive coupling type such as an internal electrode type or an external electrode coil type, or an inductive coupling type.

[1] The surface of the sintered surface has been plasma-treated, and then oxygen gas or a mixed gas containing oxygen gas (e.g.,
Alternatively, it is taken out into the atmosphere and reacted with oxygen and active sites generated on the surface of the base material by plasma treatment. It is not necessary to carry out this operation if the specimen is plasma-treated in a filtration gas, or a mixed gas containing oxygen gas.

The radical 5 on the base phase treated in this way (the generation of viscous points that can be combined is 10 mol A (below) from lOmorph'c+4 to 10 mol/cr).
When it is less than 1, the apparent value of j= of the graft polymer is small.

Also, according to detailed experimental studies conducted by the present inventors, the generation of active points M,'! A large amount of energy is required to increase ilO mol/cA, and the cost becomes too high for practical use. In particular, children with l divination points that are favorable for graft sessions are l
Omol/7 or more 1.0mo17'c++! The thus treated sheep antibody dispersant containing at least 0.1 and not more than 90% of one or more radically polymerizable sheep antibody dispersants and not less than 0.0001% O1 % or less, or touch the mixed fraction of the transition metal salt with the single body.

When converting the crystal phase into monokL-dispersed particles and toxic transfer metals, the combination and sequence of the process cannot be overstated.

There are no particular methods for applying the base material to each dispersion, such as dipping, coating, or spreading. All a woman has to do is touch a base material that has active sites capable of radical polymerization.

Before bringing the core material having active sites capable of radical polymerization into contact with the monomer or the transition metal salt, the surface of the base material is heated to 0. l trayr Hf or more 100 rt
The digraft polymerization reaction 6 progresses more easily by washing away oxygen gas and impurities contained in the base material by vacuum degassing or blowing with high pressure inert gas at a pressure of less than rm liy. There is no problem even if the monomer is brought into contact with the monomer, etc. and then subjected to vacuum degassing.In addition, before or after contacting the monomer, etc. with the monomer and the monomer, or during the reaction, The graft reaction proceeds more easily by introducing an inert gas into each dispersed ill to remove tea.

The monomer fraction tli, (I!La'LLIri o, t
%[Upper 90% or less. Preferably o, i'>50% or more.

Within this range, it is easy to suppress the homo-moped reaction and increase or control the amount r of grafted vehicles combined by using the transition makuri salt.

The amount of salinity involved in the transfer is not less than 0.0001 and not more than 1. If it is 0.0001% or more, the effect of suppressing the homozygous reaction is extremely low and cannot be used in practical use (+=4-L).Furthermore, if it is 1% or more, the flies will become too colored to be practical. The monomer ?M, the reaction temperature.

It is possible to increase or control the apparent graft polymerization by changing the concentration of transition gold scraps depending on the reaction time.

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 degree of reactivity of the monoconjugate, the degree of distant metal salinity, and the reaction time, and cannot be particularly limited.

The reaction time is in the range of 10 seconds or more and 10 hours or less.

Reaction time: 1 reaction method 1 reaction temperature ut, trtit body? I
! It is not something that can be particularly limited, as it is difficult to make a choice due to the II wave, II transfer money Kaede Shiose suction, etc.

The grafting reaction method involves simultaneously exposing the substrate to a mixture of monomers and transition metal salts.

There is a method of heating the mixed solution, a method of heating the mixed solution by squeezing the mixture appropriately, and a method of heating the substrate by squeezing it moderately. Alternatively, the heating may be carried out by a separate heating method. Furthermore, as described above, there is nothing wrong with carrying out the above-mentioned graft polymerization reaction by contacting the monomer and the transition base salt separately with the base material.

It is preferable to exclude oxygen from the inside of the graft polymerization reactor (1) For example, in the atmosphere in the reactor, the monomer transition metal salt mixture, the monomer charge, and the dissolved oxygen in the transition metal salt bath solution, nitrogen gas or Either replace the bath medium with an inert gas in the bath, or in the case of this number of baths, boil and deaerate the bath medium in advance and replace it with an inert gas, or contact the substrate with the monomer and transition metal in the bath. After this, it is preferable to introduce the base material into the base material and remove as much of the #1 element as possible.

Inorganic fine particles, such as 5iOz, that do not inhibit radical polymerization even when the monomer fraction consists of a non-water-bathable nail body and an aqueous medium containing an emulsifier.

As long as it contains k12<J3%, there is no problem with the temperature at °C.

The radical-binding OI-capable monomer used in the present invention is 7
It should be possible to select one depending on the intended use and is not particularly limited. The monomers that can combine with the radical are carbon-carbon compounds, and are monomers that combine with the radical as the propagating terminal. For example, acrylamide, N-n- Acrylamidation adducts with butoxymethylacrylamide, N-methylolacrylamide, etc.

Acrylic acid, methyl acrylate, enal acrylate, N-buna acrylate, glyc7dyl acrylate,
2-dimethylaminoethyl acrylate, 2-3-diglomoprohylacrylate.

Acrylated @ products such as diethylene glycol diacrylate, 2-hydroxyethyl acrylate, methoxypolyethylene glycol acrylate, methacrylic acid, methyl methacrylate, butyl methacrylate, isobutyl methacrylate, tertiary-butyl methacrylate, glycidyl methacrylate, ethylene glycol dimethacrylate, 2-dimethylamino Ether methacrylate.

Methacrylic compounds such as tetrahydrofurfuryl methacrylate, trimethylolpropane trimethacrylate, sodium methacrylprohylsulfonate, divinylbenzene, 2-vinylpyridine.

Examples include vinyl compounds such as N-vinyl-2-pyrrolidone and vinyl acetic acid, and styrene compounds such as styrene and sodium styrene sulfonate.

The transition metal salt used in the present invention is F'eα2° (NO
4) 2Fe(SO2)2, Cuα, Cu(NO3)2
, Cu5L)4, Cuα2, N1(NO3)2. C
o(NO3)2. Cr(Nus)2. Pb(NO3
)2. Examples include Liα, and it is possible to select a transition metal salt suitable for the purpose depending on the base material, monomer, and reaction conditions.

In the monolithic kraft polymerization reaction product formed on the surface of the base material, 1, a graft polymer, a homozygote with good durability, a homozygote with poor durability (coalescence, unreacted monopolymerization) The kraft polymerization reaction product is heated to 3°C from the boiling point of the kraft polymer by using the monomer and the 61 medium of the monomer.
The product obtained by removing unreacted AA bodies and homo-like bodies with poor durability by washing in a commercial medium at a temperature of 5℃ to 65"C or by ultrasonic cleaning. The apparent graft bonding layer is made of an apparent craft polymer containing a graft polymer and a homopolymer having good durability.

Furthermore, the apparent graft bonding layer can be washed with a hot solvent or ultrasonically cleaned using the solvent of the vehicle body at a temperature close to 0°C to 25°C above the boiling point of the solvent. The layer from which the polymer is also removed is used as a graft binding layer.

The graft polymer layer is made of a kraft polymer.

The process of removing by chemical and physical methods the homopolymer with poor durability and the unreacted single fjt form in the graft polymerization reaction product of the monomer formed on the surface of the base material (graph)
By carrying out the K-type reaction, it is possible to obtain a kraft A-type layer with good durability. Chemical and physical methods include washing with water, extraction with common solvents, and Bi-wave cleaning.

Through this process and the above-mentioned combination reaction conditions, it is possible to control the homopolymer content with good durability in the graft polymerization layer of the monomer. By containing 90% or less of a durable homopolymer, it is possible to form a main laminated layer according to each purpose.

Advantages of the present invention are (υ) According to the method of the present invention, it is possible to suppress or control the formation of homopolymers compared to conventional discharge grafting layers.

(2) The active sites generated by the method of the present invention remain active for a longer time than when they are brought into contact with oxygen.

It can be used when necessary. This is a great advantage for production and management. (8) The apparent graft layer formed according to the present invention has excellent durability because it is chemically bonded to the base material. (4) It is possible to suit various uses by arbitrarily changing the homo-carcass-containing shell in the apparent kraft polymerization polymer formed according to the present invention.

The following is a dud due to lol! Explain evening.

Sharpening 111 Hatamitsu Tomo Holie Telelen film (thickness: 60 μm) was subjected to Soxhlet extraction with methanol and then dried and used as a sample.These film pieces were subjected to non-grounded plasma processing
Mk IL7V 1 frequency d 5 kliz, argon gas pressure 0.04 ma My 1 various outputs,
After processing both sides for
)2 F'e (S04)2 was immersed in a mixed water bath and the system was sealed with N2 water.

Graft polymerization was carried out at 50° C. for 2 hours in a sealed tube, and after the completion of the combination, unreacted 1 cone and homopolymer were removed with 800℃ hot water and then dried under reduced pressure.

After the plasma treatment, the active points -t+, which were generated by being exposed to nitrogen gas and capable of attaching radicals, were treated as follows.

A film with one active point was immersed in benzene i Tanikin of 2,2-diphenyl-1-picrylhydrazyl, which is a radical scavenger, and heated at 60°C. The amount of ruhydrazyl fleas was determined by a colorimetric method and used as the amount of active sites capable of radical attachment.

Also, the constant tI/'i of the grafted acrylamide.

I went to the following DK. First, a grafted polyethylene film was immersed in 2.5 liters of hydrochloric acid and heated at 110°C. After hydrolyzing the kraft polyacrylamide, ninhydrin was added to develop a color, and the NHs group in the decomposed solution was measured using a colorimetric method using a calibration curve. Quantitated by comparing with

Comparative Example 1 A high density polyethylene film treated according to Example 1 was prepared at 10% in the absence of (NH4)2Fe(SO4)2O.
The sample was soaked in an aqueous acrylamide solution and subjected to the same post-treatment as in Example 1.

As is clear from Example 1, the amount of active points due to the plasma treatment electrical energy is 5 watts/second or more.
It was stable at watts/second/d or less. When the electrical energy was further increased, the number of active sites increased. Furthermore, if the active site world was stable, the amount of gelabut polymer was also stable at a relatively high level. Furthermore, as the amount of active sites increased, the amount of graft polymer increased.Due to the presence of the transition metal salt, the solution viscosity in the graft polymerization reaction system did not change, and the homopolymerization reaction was suppressed. The amount of graft polymer also increased somewhat under these conditions.

Example 2 Polyester cloth (JIS attached attachment 110KHz
(Using a D high frequency power supply, with an output of 0.64 w/-,
1. 40 seconds on one side only. The treatment was carried out under the Ar gas pressure shown in the table below. This fabric was taken out into the air and immersed in a mixed aqueous solution of monomers and transition metal salts shown in the table below, and the system was vacuum degassed and reacted for 30 minutes under N2 at the reaction temperature shown in the table below. The monopolymer and homopolymer f were removed by extraction with hot water at 80°C.

As in Example 2, the amount of graft polymer was clearly increased by increasing the monomer concentration and the polymerization reaction temperature. In addition, if the concentration of transition metal salt (NHS2Fe(5O4)2 is 1% or more, the base material will be obviously colored brown and it is not practical.) The effect of suppressing the reaction was insufficient, and the viscosity of the reaction system increased extremely, making it difficult to remove the homopolymer.

Furthermore, after low-temperature plasma treatment under various Ar gas pressures, a graft polymerization reaction was attempted.
．． At 1 msHg or more and 0.2 mHg or less, the grave of the graft polymer was the highest.

Example 3 100% polyester georgette (DiankxB
rack BG-FS 10% (o, w, f,)
dyed fabric) using a 13.56 MHz high frequency power source, Ar gas pressure of 0.2 to Hg, and 1.24 watts/
-, the best 1 non-grounded type insulated against the can body.
Only one side was subjected to low temperature plasma treatment for 40 seconds and exposed to oxygen gas.

Before bringing the treated fabric into contact with the reaction solution, the degree of vacuum is 5ffJ.
HgF was degassed for 10 seconds, and 20% sodium sulfone rohil methacrylate and 0.001 g of (N.L.
After immersion in a mixed water bath solution of OO2, it was heated at 60C for 20 minutes under N2.
I reacted for a minute. Intermittent treated cloth served in this way% 40
The fabric was thoroughly washed with hot running water at 80°C to remove unreacted monoh(h) and homopolymer with poor durability, and a fabric with an apparent graft polymer layer was obtained. , Cloth 7fJ having a graft polymerization layer with good durability was obtained by removing the homogeneous coalescence.

Apparent graft polymerization layer and graph) The +ft polymerization layer was determined by M Sei 6I determination.

No increase in the viscosity of the graft polymerization reaction system was observed, and both the fabric with the apparent graft polymerization layer and the fabric with graft polymerization l- had a single-sided hydrophilic 11 mesh that could withstand a durability test of 50 washes. Was.

Implementation 1! 7IJ4 100% nylon tack (JIS attached cloth)
A high frequency 'rt source of 10 KHz was used and an air pressure of 0.
Immediately after applying low-temperature plasma treatment on both sides for 10 seconds at an output of 0.64 watts/C10 under 15+xmHg,
20% hegisafluoroptyl methacrylate, 1% polystyrene sulfonate and 0.05% hexafluoroptyl methacrylate.
8 in water dispersion and rinsing containing Le Mr. Salt! After soaking and mangling at a squeezing rate of 80 inches, the pieces were left in superheated steam at 120°C for 10 minutes, and then washed with methanol.

The amount of graft polymer was 140μ2/- as a result of two weight measurements.
Met. No increase in viscosity in the graft polymerization reaction system was observed, and the resulting fabric with the graft polymerization layer had excellent water-repellent properties on both sides that withstood a durability test of 50 washes. ))

[Brief explanation of the drawing]

Figure 1 is a diagram showing the relationship between i of the active point capable of radical polymerization and the treatment energy jet in a plasma-treated intestinal tray made of crystal-tight polyethylene film.

Claims (1)

[Claims] 1) At least one side of a base material made of a polymeric substance is coated with 0.
Under a gas pressure of 01 mmHg or more and 20 mmHg or less that does not contain oxygen gas and can form active sites capable of radical polymerization,
After performing low-temperature plasma treatment with electrical energy of 1 watt/sec/cm^2 to 2000 watts/cm^2 or less, expose to oxygen gas or a mixed gas containing oxygen gas, or 0.01 mmHg to 20 mmHg. Under gas pressure containing the following oxygen gas, electrical energy of 1 watt/sec/cm^2 or more 2000 watt/sec/cm^2
The following low-temperature plasma treatment is applied to the base material for 10^-^1^
1 mol/cm^2 or more and 10^-^8 mol/cm^2 or less of active points capable of radical polymerization are formed, and the base material on which the active points have been formed is treated with 0.1% or more and 90% or less of 1 A dispersion of radically polymerizable monomers of 0.0001% or more and 1% or less of a transition metal salt, or a mixed dispersion of the monomer and the transition metal salt are brought into contact with each other, and the mixture is heated to room temperature. Alternatively, a surface modification method comprising forming an apparent graft polymerized layer of the monomer on the surface of the substrate by heating. 2) The surface modification method according to claim 1, wherein the base material made of a polymeric substance is in the form of a sheet or fiber. 3) The surface modification method according to claim 1 or 2, wherein the base material made of a polymeric substance is polyethylene terephthalate. 4) Surface modification according to any one of claims 1, 2, and 3, wherein the base material made of a polymeric substance is a base material that has been subjected to dyeing processing, resin processing, etc. Law. 5) Claim 1, characterized in that the low-temperature plasma treatment is performed with a non-grounded electrode insulated from the can body.
The surface modification method according to any one of Items 1 to 4. 6) The surface according to any one of claims 1 to 5, wherein the apparent graft polymerization layer of the monomer contains 90% or less of a homopolymer with good durability. Modification method. 7) The surface according to any one of claims 1 to 6, wherein the radically polymerizable monomer dispersion consists of an aqueous medium containing a water-insoluble monomer and an emulsifier. Modification method. 8) A feature of deoxidizing the dispersion by introducing an inert gas into the dispersion before or after contacting the base material with a radically polymerizable monomer dispersion or a transition metal salt dispersion, or during the reaction. A surface modification method according to any one of claims 1 to 7. 9) Before contacting the base material on which radically polymerizable active sites are formed with a radically polymerizable monomer dispersion or transition metal salt dispersion, the surface of the base material is degassed in vacuum or with a high-pressure inert gas in advance. 9. The method for surface modification according to any one of claims 1 to 8, characterized in that cleaning is carried out by wiping the surface with water. 10) Homopolymers with poor durability and unreacted monomers are removed from the graft polymerization reaction product of the monomers formed on the surface of the substrate by chemical or physical methods. A surface modification method according to any one of claims 1 to 9.