JPH06329822A - Production of synthetic resin molding - Google Patents

Abstract

PURPOSE:To easily obtain the subject surface-modified molding imparted with excellent water and oil repellency, hydrophilic and lipophilic properties, chemical resistance, heat-resistance, etc., under mild conditions by containing the surface of a synthetic resin molding with a fluorine-containing gas and contacting with a polymerizable monomer. CONSTITUTION:The objective molding having a freshly formed polymer layer on the surface can be produced by containing the surface of a synthetic resin molding with (A) a fluorine-containing gas having a fluorine content of 0.1-50wt.% preferably at a contacting temperature of 0-80 deg.C and then contacting with (B) a radically polymerizable monomer preferably having an Alfrey-Price e-value of -1.0 to 1.7.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a surface-modified synthetic resin molded article and a synthetic resin molded article obtained thereby. More specifically, the present invention relates to a method for modifying the surface of a synthetic resin molded product by forming a polymer layer having a functional group on the surface of the synthetic resin molded product. According to the present invention, by introducing a fluorine-containing, oxygen-containing or nitrogen-containing functional group or various functional groups obtained via them to the surface of a synthetic resin molded article, water and oil repellency, sliding Performance, hydrophilic / lipophilic performance, chemical resistance,
New functions such as heat resistance, electrical conductivity, and electrical insulation can be imparted to the surface of the synthetic resin molded product.

[0002]

2. Description of the Related Art As a method for forming a polymer on the surface of a synthetic resin molded article, a coating method by coating or
A physical reforming method using physical energy such as plasma treatment, or a high-concentration gas such as fluorine is allowed to act,
Known is a chemical modification method in which radicals are formed by irradiation with radiation such as γ-rays or light to form graft chains.

[0003]

However, since the plasma processing method requires vacuum conditions, it is difficult to continuously process a large-sized material, and further, it is unsuitable as a general-purpose processing method which requires high equipment cost and is simple. . In the coating method by coating, it is difficult to obtain sufficient adhesiveness, it is difficult to form a thin film, and cleaning and drying steps are required due to wet processing, and the process is complicated.

In the method of using a high concentration gas such as fluorine, the synthetic resin is destroyed due to the high heat of reaction, and local heating is inevitable, so that the formation of a reproducible and uniform polymer layer cannot be achieved. . Furthermore, it is difficult to uniformly irradiate the surface of the resin base material having various shapes with the method using radiation or light, and it is also a problem that the apparatus cost is high.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a wide variety of synthetic resin materials by a simple process without the need for a special device and by the action of mild conditions. It is an object of the present invention to provide a method for modifying the surface of a synthetic resin molded article, which enables the formation of an arbitrary polymer layer having various functional groups with a uniform film thickness on the surface.

[0006]

Means for Solving the Problems That is, the gist of the present invention is to bring a fluorine-containing gas into contact with the surface of a synthetic resin molded article, and then bring a polymerizable monomer into contact therewith, so that a new polymer is added to the surface of the molded article. A method for producing a surface-modified synthetic resin molded product, which comprises forming a layer, and a synthetic resin molded product obtained thereby.

The present invention will be described in detail below. As the synthetic resin to which the present invention can be applied, those having a hydrocarbon moiety capable of reacting with a fluorine-containing gas are preferable. Examples of the synthetic resin include the synthetic resins described in (1) to (3) below. (1) Thermoplastic resin having a polymer main chain formed by C—C bonds Polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyacrylate, polymethacrylate, polyacrylonitrile, polyvinyl ketone, polyvinyl Various polyolefins such as ether and polybutene-1 (2) Thermoplastic resin containing oxygen or nitrogen atom in the polymer main chain Polyester represented by polyethylene terephthalate, polyurethane, polycarbonate, polyimide, polyamide represented by nylon resin, poly Thermoplastic resin such as ether, polyketone, polyanhydride, etc. (3) Thermosetting resin Thermosetting resin such as epoxy resin, phenol resin, furan resin, urea resin, unsaturated polyester resin Synthetic resin is in the form of film Plate, powder, fiber or molded article (tubing, and containers) may be selected such arbitrarily.

In the present invention, first, a fluorine-containing gas is brought into contact with the surface of the synthetic resin molded product. The effect of bringing the fluorine-containing gas into contact with the surface of the synthetic resin in advance is that the reaction between the synthetic resin and fluorine forms a radical-like reaction active site for initiating the polymerization reaction of the monomer described later. Therefore, the condition for contacting the fluorine-containing gas may be a condition that is significantly relaxed as compared with the case of the direct fluorination reaction treatment. Particularly, in the case of synthetic resin having a reaction site (side chain alkyl group, aromatic ring, unsaturated group, etc.) that easily reacts with fluorine, the conditions for contacting the fluorine-containing gas may be milder, and the formed film and substrate High adhesion to resin.

As the fluorine-containing gas in the present invention,
A fluorine gas diluted with an inert gas such as nitrogen or helium is preferably used. The dilution concentration is not particularly limited, but is selected from the range of 0.1 to 50% by weight, preferably 1 to 20% by weight. By setting such a fluorine gas concentration, it is possible to prevent the direct fluorination reaction from proceeding preferentially, and it is also safe to handle. Hereinafter, the contact pressure of the fluorine gas, which is simply referred to as fluorine gas, may be any condition from reduced pressure to increased pressure. The pressure is usually selected from the range of 1 torr to 2 atm, though it depends on the concentration of the fluorine gas used.

The contact temperature of the fluorine gas is selected such that the direct fluorination reaction does not proceed preferentially, but the range is usually -70 to 200 ° C, preferably -70 to 90.
C., most preferably 0 to 80.degree. The contact time of the fluorine gas is appropriately selected from a wide range and is usually
It is carried out for 1 second to 10 days, preferably 1 minute to 3 hours.

[0011] It should be noted that the conditions can be appropriately selected even if it is considered to be practicable outside the above ranges according to the judgment of those skilled in the art. Then, the polymerizable monomer is brought into contact with the surface of the synthetic resin molded article which is brought into contact with the fluorine gas. Due to the action of such a monomer, a polymerization reaction occurs on the surface of the synthetic resin to form a polymer film.

As the monomer, either a gas state or a liquid state can be used, but a monomer which can be handled in a gas state is preferable from the viewpoint of easy post-treatment after forming the polymer layer. As such a monomer, a radical-polymerizable monomer whose Alfrey-price e value, which is a measure of the reactivity of the monomer, is defined as 1.7>e> -1.0 is preferably used. Examples of the monomer having an e value defined as 1.7>e> −1.0 are shown in, for example, “Polymer Data Handbook” (Baifukan, 1986), and the following monomers are listed. To be

(1) Olefins Acenaphthylene, sodium ethylenesulfonate, butyl ethylenesulfonate, p-oxathiene, N- (2-
(Chloroethyl) ethylenesulfonamide, chlorotrifluoroethylene, 2-chloro-1-propylene, 3-chloro-1-propylene, cyclopentene-1,3-dione, 2-vinylnaphthalene, 1,3-butadiene-1-
Carboxylic acid, 1,3-butadiene-1-carboxylic acid 2,
3-epoxypropyl, tert-butyl isopropenyl ketone, propylene, hexachloro-1,3-butadiene, 1-hexene, etc.

(2) Fluorine-containing olefin tetrafluoroethylene, hexafluoropropylene,
Vinylidene fluoride, vinyl fluoride, 3,3,3-trifluoropropylene, 1,3,3,3-tetrafluoropropylene, octafluoroisobutylene, hexafluoro-1,3-butadiene, chlorotrifluoroethylene, etc.

(3) Styrene and its derivatives p-acetoxystyrene, p-acetyl-α-methylstyrene, α-acetoxystyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-chloromethylstyrene, p-cyanostyrene, β, β-difluorostyrene, α- (difluoromethyl) styrene, 2,4-dibromostyrene, butyl styrenesulfonate, cis-stilbene, trans-stilbene, p-
Nitrostyrene, p-phenylstyrene, p-fluorostyrene, β-fluorostyrene, p-tert-butylstyrene, p-bromostyrene, p-benzoylstyrene, 2,3,4,6-chlorostyrene, 2,3,3. 4,
5,6-pentafluorostyrene, p-iodostyrene, etc.

(4) Vinyl halides Vinylidene chloride, vinyl chloride, vinyl bromide, vinyl iodide, etc. (5) Vinyl esters Vinyl benzoate, vinyl isocyanate, p-isocyanate
-Vinylphenyl, vinyl isothiocyanate, vinyl formate, vinyl p-chlorobenzoate, vinyl chloroacetate, vinyl cinnamate, vinyl acetate, vinyl p-cyanobenzoate, ethyl vinyl oxalate, vinyl dichloroacetate, divinyl carbonate, vinyl trichloroacetate. , Trifluorovinyl acetate, p-vinylbenzoic acid, p-vinylbenzoic acid chloride, vinyl propionate, vinyl pentafluoroacetate,
α-Methoxybenzoate etc.

(6) Vinyl pyridines 2-isopropenyl pyridine, 2-vinyl pyridine, 4
-Vinyl pyridine, 2-vinyl pyridine oxide, etc.

(7) Acrylic acid derivative Acrylamide, isopropyl acrylate, ethyl acrylate, 2,3-epoxypropyl acrylate, octadecyl acrylate, p-cresyl acrylate, chloride acrylate, 2-chloroethyl acrylate, acrylic acid p-chlorophenyl, cyclododecyl acrylate, 6,8-dimethyl-4-oxochromanimethyl acrylate,
2,4,6-Trichlorophenyl acrylate, sodium acrylate, 2-nitrobutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, phenyl acrylate, ferrocenylmethyl acrylate, butyl acrylate, P-Bromophenyl acrylate, propyl acrylate, benzyl acrylate, methyl acrylate, 1-acryloylaziridine, N-acryloylpyrrolidone, 1-acryloyl-2-benzoylhydrazine, acrylonitrile, acrolein, α-
Ethyl acetoxy acrylate, α-acetoxy acrylonitrile, α-ethyl methyl acrylate, β-ethoxy acrylate, N-octyl acrylamide, α-
Methyl chloroacrylate, α-chloroacrylonitrile, α-chloroacrolein, 3- (2-chloroethyl) -6-acroyloxypyridazinone, methyl α-cyanoacrylate, N, N-dibutylacrylamide,
N, N-dimethyl acrylamide, methyl thioacrylate, N- (hydroxymethyl) acrylamide, α-fluoromethyl acrylate, ethyl α-fluoromethyl acrylate, acrylic anhydride, α-methoxyacrylonitrile, etc.

(8) Methacrylic acid derivative 1,2-dimethacryloyloxyethane, N-phenylmethacrylamide, methacrylic anhydride, methacrylamide, methacrylic acid, zinc methacrylate, methacrylic acid 2
-Acetoxyethyl, isopropyl methacrylate, ethyl methacrylate, 2,3-epoxypropyl methacrylate, octafluoropentyl methacrylate, chloride chloride, 2-chloroethyl methacrylate, chloromethyl methacrylate, dodecyl methacrylate, 2-methacrylate Nitropropyl, cyclohexyl methacrylate,
Phenyl methacrylate, furfuryl methacrylate, fluoride fluoride, propyl methacrylate, benzyl methacrylate, methyl methacrylate, methacrylonitrile, methacrolein, N-methylmethacrylamide, etc.

(9) Dienes 2-acetoxy-3-methyl-1,3-butadiene, butadiene, isoprene, chloroprene, etc.

(10) Others Methyl atropate, atroponitrile, N-allylacetamide, allyl alcohol, 2-allylpyrrole, allylphenyl ether, allylbenzene, N-allylbenzamide, isopropyl vinyl ketone, isopropenyl phenyl ketone, Isopropenyl methyl ketone, itaconic acid, diethyl itaconate, ethyl isopropenyl ketone, ethyl vinyl ketone, ethyl vinyl sulfide,
Ethyl vinyl sulfoxide, octadecyl vinyl ether, crotonaldehyde, methyl crotonate, crotonnitrile, N- (2-chloroethyl) itaconimide,
p-Methyl chlorocinnamate, allyl chloroacetate, chloroprene, chloromethyl vinyl ketone, phenyl cinnamate, tert-butyl cinnamate, benzyl cinnamate, methyl arsenate, isopropenyl acetate, cinnamonitrile, diphenylvinylphosphine, diphenylvinylphosphine. Oxide, methyl sorbate, sorbonitrile, vinylene carbonate, triethoxyvinylsilane, tributylvinyltin, trimethylvinylgermane, trimethylvinylsilane, trimethyl (p-vinylphenyl) silane, 5-vinylisoxazole, 1-vinylimidazole, 2-vinyl Thiophene, 2-vinylphenanthrene, m-vinylphenol, p-vinylbenzenesulfonamide, p-vinylbenzamide, diethyl vinylphosphate, phenylvinyl Ton, phenyl vinyl sulfone, α-phenyl vinyl phosphoric acid, diallyl phthalate, diethyl fumarate, diisopropyl fumarate, pentafluorophenyl vinyl sulfide, muconic acid, diethyl muconate, dicyclohexyl mesaconate, diphenyl mesaconate, dimethyl mesaconate, Methyl vinyl sulfone,
2-methylene glutarate diethyl etc.

Usually, when the Alfrey-price e value showing the polymerization reactivity of the monomer is 1.7>e> -1.0,
It is said that radical polymerization is easy, while e> 1.7.
It is considered that the monomer (1) is easily anionically polymerized.
Therefore, it is considered that the above-mentioned monomer has a high reactivity with the activated site formed by the action of the fluorine gas, and a polymerized film is satisfactorily formed. Among these monomers, fluorine-containing olefins such as tetrafluoroethylene, which have a relatively positive e value, and acrylic acid derivatives such as acrylic acid, methyl acrylate, and acrylonitrile are particularly preferable.

These monomers may be used alone or in a combination of two or more. The contact pressure of the monomer having various functional units can be any condition from reduced pressure to increased pressure, and normally, the range of 1 torr to 10 atm is selected. In order to industrially advantageously carry out the method of the present invention in consideration of the reactor, productivity, etc., and to avoid the risk of explosion, the range of 0.5 to 2 atm is preferable.

The contact temperature of the monomer varies depending on the monomer used, but is usually 0 to 200 ° C., preferably 2
It is selected from the range of 0 to 90 ° C. The contact time of the monomer is appropriately selected from a wide range and is usually 1 second to 10 days,
It is preferably in the range of 1 minute to 5 hours. Even outside these ranges, the conditions can be appropriately selected when it is considered practicable by those skilled in the art.

In the present invention, after the polymerization reaction, the polymerization can be terminated by bringing the polymerization terminals into contact with various gases. The reaction conditions at that time can be the same as the above-mentioned fluorine gas action conditions, and it is also possible to form different polymer layers by using other monomer gas. The film thickness of the polymer having a functional unit to be formed can be controlled by factors such as the pressure of the monomer to be acted, the temperature, and the action time, but it is usually several Å to several 100 μm, specifically, 1 Å to 500 μm Can be formed.

The surface-modified synthetic resin molded article according to the present invention exhibits extremely excellent water repellency, especially when a fluorinated olefin is used as the polymerizable monomer.
Specifically, the contact angle with water (water droplet contact angle) is 110 °,
The surface performance that is preferably 140 ° or more can be maintained. As described above, the method for modifying a synthetic resin according to the present invention is carried out under mild conditions, and this advantage will be described by comparison with the prior art.

For example, although it is a method of modifying a metal surface,
US Pat. No. 3,567,521 discloses a method of contacting a fluorine gas with a metal surface and then contacting a fluorine-containing olefin (tetrafluoroethylene) to form Teflon on the metal surface. . According to this example, in order to form a metal fluoride on a metal surface, it is necessary to use a high-concentration fluorine gas near 100% and to adopt a high temperature condition of 100 to 300 ° C. as a contact condition of the fluorine gas. In addition, the contact condition of the fluorine-containing olefin also requires the condition of 3 to 4 atmospheres and 100 ° C.

On the other hand, in the case of the present invention, it is sufficient that the contact conditions of the fluorine gas are mild conditions in which the concentration, temperature and time are greatly relaxed, and the contact conditions of the fluorinated olefin are intentionally added. Does not require pressure. Then, according to the present invention, by adopting mild conditions, the following (1)-
There is an advantage of (3).

(1) Since it is not necessary to use highly dangerous fluorine gas of high concentration, operational safety can be obtained. (2) Since the surface can be modified even at a low temperature of 100 ° C or less,
It can also be applied to thermoplastic resins that require low-temperature treatment. (3) Since it is possible to adopt a pressure condition at room temperature or lower, it is possible to use tetrafluoroethylene gas or the like, which may explode under pressure, under safe conditions. Avoiding pressurization conditions is also advantageous from the viewpoint of reactor and productivity.

[0030]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist.

Example 1 A polypropylene sheet sample was placed in a reactor having resistance to fluorine, and after evacuation, fluorine gas diluted to 5% with nitrogen was introduced to 760 torr. 2 at room temperature
After standing for a time, the fluorine gas is evacuated and then tetrafluoroethylene gas (TFE) is introduced to obtain 760 to
rr. After standing still at room temperature for 1 hour, unreacted tetrafluoroethylene gas was replaced with nitrogen gas. After evacuation of the nitrogen gas again, in order to replace the polymerization terminal with fluorine, fluorine gas diluted to 5% with nitrogen was introduced and 36
The pressure was set to 0 torr and left for 15 minutes. Finally, after replacing the fluorine gas with nitrogen, the sample was taken out and the film formed on the surface was analyzed.

The contact angle θ with water was 118 °, and it was confirmed that a water-repellent film was formed on the sample surface (θ = 97 °). As a result of XPS analysis, a peak (292 eV) attributed to (CF ₂ ) _n was observed,
It was confirmed that the formed water-repellent film had a polytetrafluoroethylene structure and the film thickness was 50 Å or more.

Examples 2 to 5 Various synthetic resin samples shown in Table 1 were subjected to surface treatment by the same treatment operation as in Example 1. In each case, a water repellent polytetrafluoroethylene film was formed. Table 1 shows the measurement results of the contact angle θ with water.

Example 6 A polypropylene sheet sample was placed in a reactor having resistance to fluorine, and after evacuation, fluorine gas diluted to 10% with nitrogen was introduced to adjust the pressure to 760 torr. After standing at room temperature for 1 hour, the fluorine gas was evacuated and then tetrafluoroethylene gas was introduced to adjust the pressure to 760 torr. After leaving still at 70 ° C. for 1 hour, the temperature was returned to room temperature, and unreacted tetrafluoroethylene gas was replaced with nitrogen gas. After evacuation of the nitrogen gas again, a fluorine gas diluted with nitrogen to 10% in order to replace the polymerization terminal with fluorine was introduced to 360 torr, and the mixture was left standing for 15 minutes. Finally, after replacing the fluorine gas with nitrogen, the sample was taken out and the film formed on the surface was analyzed.

The contact angle θ with water was 118 °, and it was confirmed that a water-repellent film was formed on the sample surface (θ = 97 °). As a result of XPS analysis, a peak (292 eV) attributed to (CF ₂ ) _n was observed,
It was confirmed that the formed water-repellent film had a polytetrafluoroethylene structure and the film thickness was 50 Å or more.

Examples 7 and 8 The surface treatment of the synthetic resin samples shown in Table 1 was carried out by the same treatment operation as in Example 6. In any case, a water repellent polytetrafluoroethylene film was formed. Table 1 shows the measurement results of the contact angle θ with water.

Example 9 A polypropylene sheet sample was placed in a reactor having resistance to fluorine, and after evacuation, a fluorine gas diluted with nitrogen to 10% was introduced to 760 torr. After standing at room temperature for 1 hour, the fluorine gas was evacuated and then a mixed gas of tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) (TFE / HFP = 360 /
400 torr) was introduced to make 760 torr. 90
The mixture was left standing for 1 hour at 0 ° C., then returned to room temperature, and the unreacted mixed gas was replaced with nitrogen gas. After evacuation of the nitrogen gas again, a fluorine gas diluted with nitrogen to 10% in order to replace the polymerization terminal with fluorine was introduced to 360 torr, and the mixture was left standing for 15 minutes. Finally, after replacing the fluorine gas with nitrogen, the sample was taken out and the film formed on the surface was analyzed.

The contact angle θ with water was 118 °, and it was confirmed that the water-repellent film was formed on the sample surface (θ = 97 °). As a result of XPS analysis, a peak (292 eV) attributed to (CF ₂ ) _n and a peak (293 eV) attributed to CF ₃ were observed, and HFP was determined from the intensity ratio.
It was confirmed that a copolymer film of /TFE=0.16 was formed.

Example 10 A sample of a polyethylene sheet was placed in a reactor having resistance to fluorine, evacuated, and then fluorine gas diluted to 10% with nitrogen was introduced to adjust the pressure to 760 torr. 1 at room temperature
After standing for a while, the fluorine gas was evacuated, then acrylonitrile gas was introduced at 140 torr, and nitrogen gas was added to bring the pressure to 1 atm. After standing at room temperature for 1 hour, unreacted acrylonitrile gas was replaced with nitrogen gas, a sample was taken out, and the film formed on the surface was analyzed. The contact angle θ with water was 75 °, and an acrylonitrile film was formed on the sample surface (θ = 96 °). As a result of XPS analysis,
Since the peak attributed to —CN (401 eV) was observed, it was confirmed that the formed film had an acrylonitrile structure and the film thickness was 50 Å or more.

Example 11 The surface treatment of PET was carried out by the same treatment operation as in Example 10. Also in this case, as a result of XPS analysis, a peak attributed to the —CN group was observed, which confirmed that the formed film had an acrylonitrile structure and the film thickness was 50 Å or more. Table 1 shows the measurement results of the contact angle θ with water.

Example 12 A sample of polycarbonate was placed in a reactor having resistance to fluorine, and after evacuation, a 10% diluted fluorine gas was introduced at room temperature to 120 torr. 20 at room temperature
After standing for a minute, the fluorine gas was evacuated and then tetrafluoroethylene gas was introduced to adjust the pressure to 760 torr. After standing still at 100 ° C. for 15 minutes, the temperature was returned to room temperature, and unreacted tetrafluoroethylene gas was replaced with nitrogen gas.
After evacuating the nitrogen gas again, a fluorine gas diluted with nitrogen to 10% was introduced to replace the polymerization terminal with fluorine.
The pressure was set to 0 torr and left for 5 minutes. Finally, after replacing the fluorine gas with nitrogen, the sample was taken out and the film formed on the surface was analyzed.

The contact angle θ with water was 159 °, and it was confirmed that a water-repellent film was formed on the sample surface (θ = 80 °). As a result of XPS analysis, a peak (292 eV) attributed to (CF ₂ ) _n was observed, and thus the formed water-repellent film has a polytetrafluoroethylene structure and its film thickness is 50 Å or more. Was confirmed.

Example 13 The surface treatment of a polyethylene sheet was carried out by the same treatment operation as in Example 12. The contact angle θ with water was 1
It was 62 °, and it was confirmed that the water-repellent film was formed on the sample surface (θ = 93 °).

Example 14 A polyethylene sheet sample was placed in a glass container,
After evacuation, the system was filled with nitrogen, and fluorine gas diluted with nitrogen to 10% was introduced for 30 minutes at 50 cc / min in a flow system. After the reaction, the fluorine gas was evacuated and replaced with nitrogen, and then the styrene monomer liquid was introduced into the container until the sheet was substantially immersed. After standing at room temperature for 30 minutes, the sample was taken out, washed with chloroform and deaerated under vacuum, and then the film formed on the surface was analyzed. Contact angle to water is 84
It was confirmed by FT-IR measurement that a peak derived from the C—H bond of the benzene ring was observed at around 3026 cm ⁻¹ , confirming that the formed film had a polystyrene structure.

Example 15 A polyethylene sheet was surface-treated by the same treatment operation as in Example 1 except that methyl acrylate was used as a monomer. The contact angle with water is 73 °, and F
From the T-IR measurement, a peak derived from a carbonyl group was observed around 1700 cm ⁻¹ , which confirmed that the formed film had a methyl acrylate structure.

Example 16 Compounds shown in Table 1 as monomers (CH ₂ ═CHCO ₂ C
The surface treatment of the polyethylene sheet was performed by the same treatment operation as in Example 14 except that ₂ H ₄ (CF ₂ ) ₆ F) was used. The contact angle with water was 112 °, and as a result of XPS analysis, a peak (292 eV) attributed to (CF ₂ ) _n was observed. Therefore, the formed water-repellent film had a fluoroalkyl chain, It was confirmed that the film thickness was 50 Å or more.

Comparative Example 1 A polypropylene sheet sample was placed in a reactor having resistance to fluorine, evacuated and then tetrafluoroethylene gas was introduced to 760 torr. After standing still at 70 ° C. for 1 hour, the temperature was returned to room temperature and the unreacted tetrafluoroethylene gas was replaced with nitrogen gas. After evacuation of the nitrogen gas again, nitrogen was replaced with nitrogen to replace the polymerization end with fluorine.
Fluorine gas diluted to 100% was introduced to 360 torr, and the mixture was left standing for 15 minutes. Finally, after replacing the fluorine gas with nitrogen, a sample was taken out and the polypropylene sheet surface was analyzed. The contact angle θ with water was 80 °, and it was confirmed that the water-repellent film was not formed on the sample surface (θ = 97 °).

Comparative Example 2 A polyethylene sheet sample was placed in a reactor, and after evacuation, acrylonitrile gas was introduced at 140 torr.
Further, nitrogen gas was added to adjust the pressure to 760 torr, and the mixture was allowed to stand at room temperature for 1 hour. After replacing the unreacted acrylonitrile gas with nitrogen, a sample was taken out and the surface of the polyethylene sheet was analyzed. The contact angle θ with water was 96 °, and as a result of XPS analysis, a peak derived from nitrogen was not observed. Therefore, it was confirmed that an acrylonitrile film was not formed on the sample surface.

[0049]

[Table 1] ──────────────────────────────────── Contact angle θ (degree) Example Synthetic resin Sample Monomer ─────────── Film formation Untreated Surface treatment ─────────────────────────────── ───── Example 1 PP TFE 97 118 ○ 2 PE TFE 96 118 ○ 3 PET TFE 72 117 ○ 4 PEEK TFE 90 118 ○ 5 PI TFE 73 118 ○ 6 PP TFE 97 118 ○ 7 PE TF ○ Epoxy resin TFE 70 116 ○ 9 PP TFE / HFP 97 118 ○ 10 PE acrylonitrile 96 75 ○ 11 PET acrylonitrile 72 75 ○ 12 PC TFE 80 159 ○ 13 PE TFE 93 162 ○ 14 PE styrene 93 84 ○ 15 PE methyl acrylate _{93 73 ○ 16 PE CH 2 =} CHCO 2 C 2 H 4 (CF 2) 6 F 93 112 ○ ─────────────────── Comparative Example 1 PP TFE 97 80 × 2 PE acrylonitrile 96 96 × ───────────────────────────────────── ───────────────── The abbreviations in the table have the following meanings.

PP: Polypropylene PE: Polyethylene PET: Polyethylene terephthalate PEEK: Polyetheretherketone PI: Polyimide (Dupont, USA, trade name "Kapton") PC: Polycarbonate TFE: Tetrafluoroethylene HFP: Hexafluoropropylene

[0051]

EFFECTS OF THE INVENTION According to the present invention, a uniform functional-containing polymer film having an arbitrary thickness can be formed on the surface of a wide variety of synthetic resin materials by a simple process without requiring a special apparatus and a large amount of energy. It can be coated or can have a multi-layer structure by using several kinds of monomers, and its industrial significance is great.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nao Imaki 1000, Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd.

Claims (7)

[Claims] 1. A method of contacting a surface of a synthetic resin molded article with a fluorine-containing gas, and then bringing a polymerizable monomer into contact therewith to form a new polymer layer on the surface of the molded article. A method for producing a modified synthetic resin molded product. 2. The fluorine-containing gas contains 0.1 to 5 fluorine.
The method for producing a synthetic resin molded article according to claim 1, wherein the content is 0% by weight. 3. The contact temperature of the fluorine-containing gas is 0 to 80 ° C.
The method for producing a synthetic resin molded article according to claim 1 or 2. 4. A polymerizable monomer having an Alfrey-price e value of 1.7> which is a measure of the reactivity of the monomer.
The method for producing a synthetic resin molded article according to claim 1, wherein a radically polymerizable monomer having e> -1.0 is used. 5. A surface-modified synthetic resin molded product obtained by bringing a fluorine-containing gas into contact with the surface of the synthetic resin molded product, and then bringing a polymerizable monomer into contact therewith. 6. The synthetic resin molded article according to claim 5, wherein the polymerizable monomer is a fluorinated olefin. 7. The synthetic resin molded article according to claim 6, wherein the water droplet contact angle on the surface is 110 ° or more.