JPH0790783A - Surface modification of polymer and dying - Google Patents

Abstract

PURPOSE:To impart excellent surface properties and dyability by subjecting a polyolefin material, etc., at first to ozone treatment, then graft- copolymerization with a vinyl compound under UV irradiation and further optionally to Hofmann rearrangement. CONSTITUTION:The surface of a polymer material or a fiber product composed of polyolefin, e.g. polypropylene or polyethylene is consecutively and continuously subjected to ozone treatment to induce functional groups, e.g OH groups on the surface, then to graft-copolymerization with a vinyl compound, e.g acrylic acid, (meth)acrylic acid ester or (meth)acrylamide under ultraviolet irradiation and further to Hofmann rearrangement to transform the acid amide group to an amine group. After these treatments the material is dyed. These processes modify the surface of the material to enable to perform dying in relatively deep color and in excellent solidity on a material hitherto being difficult to be dyed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for modifying the surface of a polymer material such as a synthetic polymer, a natural polymer, a mixture or modified product thereof. In particular, it relates to improvement in dyeability, hydrophilicity, hydrophobicity, adhesiveness and the like. In particular, it is effective for surface modification and improvement of dyeability of a polyolefin material that cannot be dyed by an ordinary dyeing method.

[0002]

2. Description of the Related Art Polyolefin materials such as polypropylene and polyethylene, phenol resin-based fibers, polyaramid-based materials and the like have low polarity in terms of chemical structure and high crystallinity, so plating, adhesion, painting, printing on the surface thereof, Difficult to dye. Therefore, surface modification treatment is often required.

In particular, polypropylene materials are light, strong,
It has excellent chemical resistance, and when used as a fiber at the beginning of the invention, it was said to be a "dream fiber". However, due to their chemical inertness, non-polarity, and high crystallinity, surface processing is difficult and there is no practical dyeing method. Therefore, the use as a fiber is limited to futon cotton and sewing thread. At present, polypropylene materials can be manufactured at low cost and are mainly used as molded products.

Coloring of polypropylene materials is generally carried out by kneading a pigment into a polymer raw material. Like other fibers (natural fibers, rayon, acetate, nylon, acrylics, polyesters, etc.) free dyeing is not possible. Several attempts have been made to improve the dyeability. For example, (1) a method of blending polypropylene with another polymer (for example, JP-B-53-221).
09, JP-A-63-182480, JP-A-1-11886.
83), (2) A method of copolymerizing propylene and another monomer having a functional group (Japanese Patent Publication No. 3-68149), (3).
Method of introducing metal compound into polypropylene
8-99472), (5) Improvement of dyeing method itself (Japanese Patent Publication No. 56-52152, JP-A-1-16890).

Several attempts have been made to modify polypropylene moldings by surface treatment. For example, a method for improving plating characteristics, paintability, and adhesiveness by ozone-oxidizing a polypropylene molded product (Japanese Patent Publication No. 3-103448).
Is being considered. However, according to the inventor's study, ozone oxidation is not as thin (or thin) as fiber or film.
When applied to the processing of materials, the surface properties are modified,
It can be said that it cannot be put to practical use because the strength is significantly reduced. Further, general dyeing is not possible only by ozone oxidation treatment.

In addition to this, although the surface modification of the polyolefin molded product by plasma treatment has been carried out and the results have been obtained, the general dyeing property using water as a medium has not been improved yet.

A method of graft-copolymerizing polypropylene with a molecular chain of another monomer has also been attempted.

In this case, polypropylene is often melted or made into a solution and then reacted. However, it is uneconomical because the product needs to be newly molded. In addition, the material itself is a modified polypropylene molecular structure.

[0009] Grafting of acrylamide by irradiation of ultraviolet rays on polypropylene or polyethylene moldings has also been studied. However, the reaction rate is extremely poor due to the inertness of the material surface and the additives contained,
It was observed that the wetting properties of the surface changed, but no measurable weight gain was observed.

A method of grafting methyl methacrylate to polyethylene and then acrylamide by irradiation of ultraviolet rays has also been studied.

In any case, if the reaction conditions are made severe in order to promote the grafting, there is a problem that the material strength is significantly lowered. It can be said that an easy method under which the reaction conditions are relatively mild and a high graft ratio (several% to several tens%) is obtained has not been established.

[0012]

SUMMARY OF THE INVENTION The object of the present invention is not to use materials that are inconvenient to handle, and to apply pressure, pressure reduction,
It is to find a way to improve the surface properties of many polymeric materials by economical processing methods that do not require capital investment such as heating and energy consumption. In particular, emphasis is placed on achieving modification of the dyeability, adhesiveness, hydrophilicity, antistatic property, etc. of polyolefin materials. Surface modification methods for polyolefin materials are considered applicable to many other polymeric materials.

[0013]

In order to improve the surface characteristics of a polyolefin molded article to the extent that it can be dyed by an ordinary dyeing method, the present inventor has conducted ozone treatment and under irradiation of ultraviolet rays of a specific wavelength. It was found to be effective to combine the two steps of grafting the vinyl compound in.

Further, it has been found that it is effective to carry out Hoffman rearrangement (Hoffman reaction) after grafting a vinyl compound having an amide group in order to further improve surface properties such as dyeability.

That is, according to the present invention, the surface of the polyolefin molded article is treated with (1) ozone, (2)
A method for modifying the surface of a polyolefin molded article, which comprises performing a step of grafting a vinyl compound while irradiating ultraviolet rays;

Alternatively, in step (2), a vinyl compound having an amide group is grafted, and then in step (3)
And a method for modifying the surface of a polyolefin molded article, wherein the amide group is converted to an amino group by Huffman rearrangement.

The present invention relates to a method for dyeing a polyolefin fiber product, which is characterized in that the polyolefin fiber product is modified as described above and then dyed.

Further, for many polymer materials other than polyolefin, (1) a step of treating with ozone,
(2) a surface modification method characterized by treatment in two steps, i.e., a step of grafting a vinyl compound while irradiating with ultraviolet rays;

Alternatively, a vinyl compound having an amide group is grafted in the step (2), and then the step (3) is performed.
And a method for modifying the surface of a polyolefin molded article, wherein the amide group is converted to an amino group by Huffman rearrangement.

After modifying the fiber products of many polymeric materials other than polyolefin in the steps (1), (2) and (3),
The present invention relates to a method of dyeing a polymer material / fiber product, which is characterized by dyeing.

The present invention will be described in more detail below.

"Polymer material" The polymer material as referred to in the present invention includes many of commonly used polymer substances such as synthetic polymers, natural polymers, and mixtures and modified products thereof. (I) Synthetic polymer includes both thermoplastic polymer and thermosetting polymer. Depending on the synthesis method, (1) addition polymers, that is, homopolymers or copolymers of vinyl compounds (olefins, vinyl chloride, styrene, acrylic acid or methacrylic acid derivatives, vinyl acetate, acrylonitrile, etc.), isoprene, chloroprene, butadiene, etc. Polymers, mixtures or modified products thereof, (2) polycondensates, that is, homopolymers or copolymers of polyester, polyamide, polyaramid, etc., or mixtures or modified products thereof, (3) addition condensation products, ie, Phenolic resin (including Kynol), urea resin, melamine resin,
Homopolymer or copolymer such as xylene resin, or mixture or modified product thereof, (4) polyaddition product, that is, homopolymer or copolymer such as polyurethane or polyurea, or mixture or modified product thereof. (5) ring-opening polymer, that is, homopolymer or copolymer of cyclopropane, ethylene oxide, propylene oxide, lactone, lactam, etc., or a mixture or modified product thereof,
(6) Cyclic polymer, that is, divinyl compound (Example: 1,
4-pentadiene) and diyne compounds (eg: 1,6-heptadiyne), homopolymers or copolymers, or mixtures or modified products thereof, (7) isomerized polymers, for example,
Alternating copolymer of ethylene and isobutene, (7) electrolytic polymer, that is, homopolymer or copolymer of pyrrole, aniline, acetylene, etc., or a mixture or modified product thereof, (8) polymer of aldehyde or ketone, (9) Materials such as polypeptides are included. Further, (II) natural polymers, that is, celluloses, proteins, polysaccharides and the like alone or as a mixture or modified product are included.

"Polyolefin" In the present invention, the polyolefin is not particularly limited, and includes ethylene, propylene, butene-1, pentene-2, hexene-1, 4-methyl-pentene-1, octene-1 and the like. A homopolymer of any α-olefin, a copolymer of two or more kinds of these, or a mixture of these homopolymers and / or copolymers can be appropriately used. Particularly preferred are polyethylene, homopolymers of ethylene and other α-olefins, polypropylene, copolymers of propylene and other α-olefins such as ethylene, or random copolymers.

Within the range that does not significantly impair the effects of the present invention,
A stabilizer, a nucleating agent, a flame retardant, a filler, a foaming agent and the like and various additives usually added to polymer materials may be contained. It is also possible to blend a plurality of polymers. In order to increase the grafting efficiency under UV irradiation, a substance such as benzophenone or hydrogen peroxide that improves the sensitivity to UV rays can be added in advance.

"Molded Product of Polyolefin and Other Polymeric Material" In the present invention, the shape of the molded product of polyolefin and other polymeric material subjected to the surface modification treatment is not limited. Any of fibrous, woven, non-woven, cloth-like, film-like, sheet-like, tubular, rod-like, hollow container-like, box-like, foamed and laminated bodies can be preferably used. In particular, a fibrous molded product such as polypropylene is preferable from the viewpoint of improving the dyeing performance.

"Ozone treatment step" The treatment of the surface of a molded article of a polymer material with ozone is intended to bring the surface of the molded article into contact with ozone molecules to carry out a reforming reaction mainly consisting of an oxidation reaction. There is.

The ozone treatment is carried out by exposing the molded polymer material to ozone. As an exposure method, an appropriate method such as a method of holding in an atmosphere in which ozone is present for a predetermined time or a method of exposing in an ozone gas stream for a predetermined time can be used.

Ozone can be generated by supplying an oxygen-containing gas such as air, oxygen gas, or oxygen-added air to the ozone generator. The ozone-containing gas thus obtained is introduced into a container, a tank, or the like holding the polymer material molded product to perform ozone treatment. Various conditions such as the ozone concentration in the ozone-containing gas, the exposure time, and the exposure temperature can be appropriately determined depending on the types of polyolefin and other polymer materials and the purpose of surface modification.

For example, in the case of polypropylene fiber, an oxygen stream having an ozone concentration of 5 to 10 g / m ³ is used and the temperature is 10
The treatment can be performed at -50 ° C for 30 minutes to 60 minutes.

Ozone treatment introduces a percarbonate group (--C--O--OH) into the surface of polyolefin and other polymer materials by a reaction mainly involving oxidation, which is a hydroxyl group (--OH) or a carbonyl group (--OH). It is presumed that it changes to a functional group such as C = O).

“Grafting or graft copolymerization step”
The ozone-treated polyolefin and other polymer materials are then subjected to a treatment of grafting a vinyl compound while being irradiated with ultraviolet rays. The compound used for grafting preferably has 3 to 20 carbon atoms. In addition to the vinyl group, it may have an amide group, an ester group, a phenyl group, an ether group, or the like. Specific examples of preferable compounds include acrylic acid ester.
Methacrylic acid ester or its derivative (eg, α-hydroxyethyl methacrylate), acrylic acid, methacrylic acid, styrene and its derivative, vinyl acetate, acrylonitrile, vinyl ether and the like. Specific examples of the vinyl compound having an amide group include acrylamide and methacrylamide. N-vinyl compounds, divinyl compounds, etc. are also applicable.

In the present invention, the ultraviolet ray is 180 nm to
Light having a wavelength of 600 nm or light containing these is effective, but it is preferable to use light having a wavelength of 300 nm to 500 nm, or light having a range centered on 365 or 366 nm. However, irradiation with light of a shorter wavelength is disadvantageous because it tends to cause a decrease in material strength, and irradiation of light with a longer wavelength is disadvantageous because a reaction is less likely to occur.

The ultraviolet rays in this wavelength range may be those generated by a known low or high pressure mercury lamp, fluorescent lamp, xenon lamp, carbon arc lamp or ultraviolet laser generator. An appropriate filter can be used to cut unnecessary wavelength regions.

Grafting is carried out by diluting or dissolving a vinyl compound, alone or in combination, with another inert gas or liquid, and using it in the gas phase or in the liquid phase to form a vinyl compound on the surface of polyolefin and other polymer materials. It is performed by irradiating with ultraviolet rays in the presence of the compound. A water-insoluble vinyl compound such as methyl methacrylate or styrene can be used in an alcohol solution, and acrylic acid or acrylamide can be used in an aqueous solution.

The temperature at the time of grafting is suitably 25 to 60 ° C., but depending on the purpose, the higher the temperature, the better the reactivity.

In order to increase the reaction efficiency, a reaction initiator such as peroxide or a reaction catalyst can be present in the system during grafting.

Prior to the grafting treatment, the surfaces of the polyolefin and other polymeric materials are preferably washed with a suitable liquid. For example, it is preferable to wash the polyolefin with toluene and then with alcohol or the like. Nylon, polyester, polystyrene, acrylic resin, polyvinyl acetate, polycarbonate, polyurethane, etc. can be washed with alcohol. Cellulosic products, namely cotton,
It is preferable to wash hemp, rayon and the like with a detergent and then with alcohol.

The ultraviolet irradiation is carried out by appropriately setting the irradiation time and intensity in consideration of the desired degree of surface modification, type of vinyl compound and temperature.

For example, in the case of polypropylene fiber, a vinyl compound solution and ozone-treated polypropylene fiber are placed in a hard glass container having a thickness of 1 to 2 mm,
A nitrogen atmosphere is created in the container. Next, ultraviolet rays centering around 360 to 400 nm are taken out from a 400 w ultraviolet lamp with a filter, and irradiation is performed with the distance from the lamp surface to the bottom of the reaction vessel being 15.5 cm. A reaction temperature of 40 to 50 ° C. and a reaction time of 2 to 4 hours are suitable. Air cool between the lamp and the vessel to prevent overheating of the reaction vessel.

"Hoffman Rearrangement (Hoffman Reaction)" In the present invention, the Hoffmann rearrangement of the grafted vinyl compound-derived amide group (-CONH ₂ ) is caused by the amino group (-NH ₂ ) produced thereby. This is to further improve the dyeability. The Hoffman rearrangement can be performed by a usual method. That is, it can be easily carried out by immersing the grafted polyolefin and other polymer materials in an aqueous solution of sodium hydroxide and adding an aqueous solution of sodium hypochlorite (or sodium hypobromite). Alternatively, the amide group may be hydrolyzed by the action of bromine or chlorine in the presence of alkali.
The reaction temperature and time can be appropriately selected.

Chemical formula 1 shows an outline of the reaction in each step of ozone treatment, graft treatment and Hoffman rearrangement when a polypropylene molded product and acrylamide are used.

[0042]

[Chemical 1]

"Dye" After ozone treatment, polypropylene fibers grafted with hydrophobic vinyl compounds such as methyl methacrylate, styrene and vinyl acetate are dyed intensively with disperse dyes. The disperse dye is a dye developed for dyeing acetate / polyester, and is mainly composed of aminoazo type and aminoanthraquinone type due to its chemical structure.
Since the heat resistant temperature of polypropylene is not as high as that of polyester, a carrier as an auxiliary agent is used during dyeing.
As the carrier, o-phenyl phenol, dimethyl terephthalate, methylnaphthalene compound, chlorobenzene compound, and diphenyl compound can be used.

The polypropylene fibers which have undergone the Hoffmann rearrangement after grafting acrylamide are (1) acid dye,
Dyeing with (2) cationic dye, (3) vat dye, and (4) vegetable dye is possible. It is difficult to obtain practical dyeing with general-purpose direct dyes and reactive dyes. It is also possible to dye with a sulfur dye or a naphthol dye.

The acid dyes are dyes mainly used for dyeing protein fibers such as silk and wool and nylon fibers, and include azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes and the like in terms of chemical structure. It has an anionic group such as sodium sulfonate group and forms an ionic bond with the fiber.

The cationic dye is a dye mainly used for dyeing acrylic fibers. Due to its chemical structure, it has a cation in the molecule. Auramine O (C.I. Basic
Yellow2), Malachite Green (C.I.
Basic Green 4), Rhodamine B (C.I.
Typical examples are Basic Violet 10), Crystal Violet (CI Basic Violet 3), and Methylene Blue (CI Basic Blue 9).

The vat dye is also called vat dye, and indigo is typical. There are indigo type and anthraquinone type in terms of chemical structure, and a reducing agent is used for dyeing.

The plant dye is a dye whose main component is a pigment extracted from various plants such as roots, trunks, bark, leaves, flowers and fruits. Many materials such as Akane, Kariyasu, Kuchinashi, Suou, Murasaki, Onion, Yasha, and chestnut are useful. Upon dyeing, a metal compound having a valence of 2 or more (a salt of iron, copper, aluminum, chromium or the like) is used as a mordant.

[0049]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 Reaction of Polypropylene Fiber with Methyl Methacrylate (MMA) Polypropylene Fiber (Product sold by Kansai Clothing Research Group 170
0.3 g (size 50 x 50 mm) of plain woven fabric of d (denier) yarn (one yarn consists of 20 single fibers) was put in a hard glass container with a thickness of 1.5 mm, and the ozone generator (Japan) was used. From ozone ON-1-2 type) ozone (9.2 g /
m ³ ) -containing oxygen at a flow rate of 2000 ml / hour 45
Blown for a minute. Next, oxygen containing no ozone was blown in for 10 minutes.

Next, 15 ml of methanol and 1 g of MMA were added, the reaction vessel was made a nitrogen atmosphere, and then a high pressure mercury lamp (Toshiba high pressure mercury lamp H400P) was irradiated from a distance of 15.5 cm for 3 hours. The temperature is 45 ° C. The contents of the reaction vessel were poured into a large amount of methanol. The polypropylene fiber with MMA polymer attached was taken out and washed with 100 ml of toluene three times (at room temperature, washing time 2
Homopolymer (a homopolymer of MMA) was removed after 1 hour. The treated material was dried. Graft ratio (ratio of graft polymer to the total weight of material) is 16%
Met.

FIG. 1 shows untreated polypropylene fibers (1)
And the Fourier transform infrared absorption spectrum (KBr tablet method) of the obtained MMA graft polypropylene fiber (2) are shown. Comparing the spectra of (1) and (2),
In the spectrum of (2), strong absorption based on the carboxyl group of MMA is observed near 1738 cm ⁻¹ , which indicates that the grafting has occurred.

Example 2 Reaction of Polypropylene Plate with Acrylamide Two polypropylene plates having a length of 50 mm, a width of 10 mm and a thickness of 1 mm (weight: 0.986 g) were placed in a hard glass Erlenmeyer flask, and ozone (9.2 g / Oxygen containing m ³ ) was blown in for 45 minutes at a flow rate of 2000 ml / hour. Then oxygen was bubbled in for 10 minutes.

In an Erlenmeyer flask, add 0.98 acrylamide.
6 g, 3% hydrogen peroxide aqueous solution 1 ml, and water 15 ml were added. The reaction vessel was placed in a nitrogen atmosphere, and a high pressure mercury lamp (Toshiba high pressure mercury lamp H400P) was operated from a distance of 15.5 cm for 3 hours.
Irradiated for an hour. The temperature was 45 ° C. Next, the contents of the container were put into a large amount of water. The polypropylene plate to which the acrylamide polymer was attached was taken out, and washed by boiling with 100 ml of water three times. The treated polypropylene plate obtained was dried. The graft ratio was 1.12%.

(Example 3) Adhesive strength test Regarding the grafted polypropylene plate obtained in Example 2, the polypropylene plate only subjected to ozone treatment, and the untreated polypropylene plate, a commercially available two-component mixed epoxy adhesive (Konishi Co., Ltd.) Bonding was performed using Bond Quick 5), and a tensile shear adhesive strength test was performed. 25m long test piece
Adhesive area 25 mm ² , adhesive amount 100 mg, adhesive drying time 5 for 2 sheets of m, width 5 mm, thickness 1 mm
It was glued in time.

Test conditions: Tensile testing machine Imada Seisakusho SV
-55-0-20-M, tensile speed 30 mm / min, test piece size width 5 mm, length 50 mm, grip portion length 8.
5 mm, tensile part length 28 mm.

The adhesive strength is as follows: untreated polypropylene plate:
0.4 kg / cm ² , ozone-treated polypropylene plate: 1
6.0 kg / cm ^2, acrylamide grafted polypropylene plate: was 30.4 kg / cm ^2.

Although the adhesiveness of the polypropylene molded article was improved only by the ozone treatment, it was found that the polypropylene grafted according to the present invention further increases the adhesive strength. It was interpreted that the grafting of acrylamide increased the surface polarity of polypropylene and increased its affinity with polar adhesives.

Example 4 Reaction of Polyvinyl Chloride Fiber with Methyl Methacrylate (MMA) Polyvinyl Chloride Fiber (Sold by Kansai Clothing Research Group 75d
(Denier) thread (one thread consists of 25 single fibers)
0.15 g (size 50 × 50 mm) of plain woven fabric of No. 1 is put into a hard glass container having a thickness of 1.5 mm, and ozone (9.2 g / oz) is supplied from an ozone generator (Japan Ozone ON-1-2 type).
Oxygen containing m ³ ) was blown in for 45 minutes at a flow rate of 1500 ml / hour. Next, oxygen containing no ozone was blown in for 10 minutes.

Next, 10 ml of methanol and 2.3 of MMA.
After adding g, the reaction vessel was placed in a nitrogen atmosphere and irradiated with a high pressure mercury lamp (Toshiba high pressure mercury lamp H400P) from a distance of 15.5 cm for 3 hours. The temperature is 45 ° C. The contents of the reaction vessel were poured into a large amount of methanol. The polypropylene fiber to which the MMA polymer was attached was taken out and washed with 100 ml of toluene three times (at room temperature, washing time 2 hours / once) to remove the homopolymer (MMA homopolymer). The treated material was dried. The graft ratio (ratio of the graft polymer to the total weight of the material) was 35%.

FIG. 2 shows Fourier transform infrared absorption spectra (diffuse reflection method) of untreated polyvinyl chloride fiber (1), vinyl chloride fiber (2) treated with ozone for 1 hour, and MMA graft polypropylene fiber (3) obtained. Indicates. Comparing the spectra of (1) and (2) with that of (3), in the spectrum of (3), strong absorption based on the carboxyl group of MMA is observed near 1736 cm ^-1 . In addition, absorption based on MMA is 1150, 148
It is also found near 0,750 m ^-1 . The positions of these absorptions are indicated by arrows and numerical values in the figure. From these, it was considered that MMA was grafted to polyvinyl chloride. In the spectrum of (1), 1730
The untreated polyvinyl chloride appeared to be somewhat oxidized, as a small absorption peak was seen near cm ⁻¹ .
The absorption intensity near 1730 cm ⁻¹ in the ozone-treated polyvinyl chloride spectrum of (2) is similar to the absorption observed in the untreated polyvinyl chloride spectrum, so under the experimental conditions , It was considered that the change of polyvinyl chloride fiber due to ozone oxidation was small.

(Example 5) Reaction of Polypropylene Fiber with Acrylamide Polypropylene fiber (Sold by Kansai Life Research Association 170
A plain woven fabric 0.3 g (size 50 × 50 mm) of d (denier) yarn (one yarn is composed of 20 single fibers) was put in a hard glass container having a thickness of 1.5 mm, and an ozone generator (for example, Ozone (9.
Oxygen containing 2 g / m ³ ) was bubbled in for 45 minutes at a flow rate of 2000 ml / hour. Next, add 1
Blow for 0 minutes.

Next, 0.4 g of acrylamide, 1 ml of a 3% aqueous solution of hydrogen peroxide, and 15 ml of water were added, and the reaction vessel was placed in a nitrogen atmosphere. High-pressure mercury lamp (Toshiba high-pressure mercury lamp H
400P) was irradiated to the reaction vessel from a distance of 15.5 cm for 3 hours. The temperature was 45 ° C. Next, the contents of the container were put into a large amount of water. The polypropylene fiber to which the acrylamide polymer was attached was taken out and washed by boiling with 100 ml of water three times. The graft ratio was 6%.

Example 6 Treatment by Hoffman Rearrangement The acrylamide-grafted polypropylene obtained in Example 4 was put in water, made alkaline with sodium hydroxide, and sodium hypochlorite was added to carry out the Hoffman rearrangement. . Charge of reactant: grafted polypropylene 0.
3 g, water 20 ml, sodium hydroxide 0.2 g, sodium hypochlorite (5% aqueous solution) 1 ml. The reaction time and temperature are 1 hour and 50 ° C., respectively.

It is known that the amide group of acrylamide is changed to an amino group by Hoffman rearrangement.
The treated polypropylene obtained by this operation is referred to below as AMH
Abbreviated as PP.

FIG. 3 shows untreated polypropylene fibers, ozone-treated polypropylene fibers (obtained by the ozone treatment of Example 5), acrylamide graft polypropylene fibers (obtained in Example 5), and AMHPP fibers (Example). The Fourier transform infrared absorption spectrum (diffuse reflection method) of each of those obtained in No. 6) is shown. Compared with the untreated polypropylene (1), the ozone-treated polypropylene (2) shows absorption of carbonyl groups produced by oxidation at around 1710 cm ^-1 . 1610 cm ^-1 , 16 for acrylamide graft polypropylene (3)
Absorption due to an amide group is seen near 70 cm ^-1 . It is 1630 cm ^-1 for the Hoffmann rearrangement (4).
And an absorption peak is seen at 1670 cm ^-1 , but the absorbance is greatly reduced. That is, it was found that the amount of the amide group was decreased, which seems to suggest the change from the amide group to the amino group by the Hoffman rearrangement.

(Example 7) Tensile strength test
The tensile strengths of the treated fibers and the untreated fibers obtained in Examples 1, 4, and 6 were measured. One polypropylene yarn and two polyvinyl chloride yarns were measured. Tensile test conditions: Tensile tester
Imada SV-55-0-20-M, tensile speed 30
mm / min, test piece Length 50mm One thread (Thickness 170
d), grip part length 11 mm, tension part length 28 m
m, temperature 25 ° C. The results are shown in Table 1.

[0068]

[Table 1]

(Example 7) Wetting test Each of the untreated polypropylene (1), the ozone-treated polypropylene (2), the acrylamide graft polypropylene (3) and the AMHPP (4) was tested for "wetting" with water. . The contact angle of water was determined with a homemade device. That is, a drop of water having a diameter of about 1 mm was dropped from the syringe on the surface of the test cloth, and the size was calculated from the size of the image magnified and projected by the lens.

The contact angles were as follows: Untreated polypropylene 129 °, ozone treated (1 hour) polypropylene 123 °, ozone treated (4 hours) polypropylene 105 °.

For acrylamide-grafted polypropylene (3) and AMHPP (4), the contact angle is 140-
It was considered to be less than 150 °.

When each sample is put in water, "(1) repels water, (2) partially wets gently, (3)
And (4) get wet well with water. "

Qualitatively, it was observed that static electricity was less likely to occur in (3) and (4).

Example 8 Dyeing Untreated polypropylene cloth, ozone-treated polypropylene cloth, grafted polypropylene cloth or AMHPP cloth, untreated polyvinyl chloride cloth, ozone-treated polyvinyl chloride cloth and MMA grafted polyvinyl chloride cloth are the same respectively. A dyeing experiment was performed under the conditions. Examples of each dyeing will be shown below.

(1) Dyeing of MMA-grafted polypropylene cloth 0.3 g of cloth was used as a disperse dye for polyester (manufactured by Mitsubishi Kasei Co., Ltd., Dianex Red AC-E, Blue AC).
-E, each of Turkish Blue AC-E) 40 mg
Was dispersed in 75 ml of water. Separately, 5 ml of carrier agent (sodium salt of orthophenylphenol) in 25 ml of water
0 mg was mixed, 2 mg of anionic surfactant was added, and the mixture was well emulsified. Both solutions were mixed, and acetic acid was added to adjust the pH to around 5. Cloth was added and boiled for 30 minutes. The cloth was washed with a detergent solution by boiling, washed with water and dried. A fairly thick dyed polypropylene fabric was obtained.

By the same dyeing method, the untreated polypropylene cloth and the ozone-treated polypropylene cloth were hardly dyed.

(2) Dyeing of MMA-grafted polyvinyl chloride cloth 0.3 g of cloth was used as a disperse dye for polyester (manufactured by Mitsubishi Kasei Co., Ltd., Dianex Red AC-E, Blue AC).
40 mg each of -E and Turkish Blue AC-E) was dispersed in 75 ml of water. Separately, 50 ml of carrier agent (sodium salt of orthophenylphenol) in 25 ml of water
mg was mixed, 2 mg of anionic surfactant was added, and the mixture was well emulsified. Both solutions were mixed, and acetic acid was added to adjust the pH to around 5. Cloth was added and boiled for 30 minutes. The cloth was washed with a detergent solution by boiling, washed with water and dried. A fairly thick dyed fabric was obtained.

By the same dyeing method, untreated polyvinyl chloride cloth and ozone-treated polyvinyl chloride cloth were also dyed, but MMA-grafted polyvinyl chloride was dyed most densely.

(2) Dyeing of AMHPP cloth

(2-1) Dyeing with Acid Dye Acid dye (each of Kayanol Yellow N5G and Kayanol Red NB manufactured by Nippon Kayaku Co., Ltd.) was added to 50 ml of 2% aqueous solution, and AMH was added.
0.3 g of PP cloth was put and heated for 30 minutes. The cloth was taken out, washed by boiling with an aqueous detergent solution, washed with water and dried to obtain a dyed polypropylene cloth.

By the same method, the untreated polypropylene cloth and the ozone-treated polypropylene cloth were hardly dyed. The acrylamide grafted polypropylene fabric was slightly dyed.

(2-2) Dyeing with Cationic Dye 0.1 g of AMHPP cloth was placed in 50 ml of a 1% aqueous solution of a cationic dye (each of malachite green, rose and magenta) and heated for 25 minutes. The cloth was taken out, washed by boiling with an aqueous detergent solution, washed with water and dried to obtain a dyed polypropylene cloth. In this case, a fairly thick dyeing was achieved.

The untreated polypropylene fabric was hardly dyed by this method. The ozone-treated polypropylene fabric was dyed to a light density. The acrylamide grafted polypropylene fabric was slightly dyed.

(2-3) Dyeing with vat dye Vat dye (Kiriyama Ushio dye (product of Kiriyama dye store) blue (color index number CI Vat Blue1),
Each of purple, mustard, iron and olive green) 0.02g
A small amount of alcohol was added to and kneaded, 50 ml of water, 0.01 g of sodium hydroxide and 0.06 g of sodium hydrosulfite were added, and the mixture was heated at 80 ° C. for 10 minutes to prepare a leuco aqueous solution of the dye. To this, the AMHPP cloth 0.
1 g was put and left for 60 minutes (heated to about 40 ° C.). The dyed cloth thus obtained was washed with an aqueous detergent solution by boiling several times. Further, excess dye was washed off with alcohol. A fairly thick dyed fabric was obtained.

By the same dyeing method, ozone treated polypropylene cloth and acrylamide graft polypropylene cloth were
Although not as dark as the MHPP fabric, it dyed relatively well. The untreated polypropylene fabric was dyed to a light density.

(2-4) Dyeing with vegetable dye 50 ml of a boiling aqueous solution of a vegetable dyeing material (dried suou, chinashi, kariyasu, onion rind) is added to 0.2 ml of AMHPP cloth.
g, and boiled for 30 minutes. The cloth was taken out, washed by boiling with an aqueous detergent solution, and then dried to obtain a dyed cloth.

By the same method, untreated polypropylene fabrics, ozone treated polypropylene fabrics and acrylamide grafted polypropylene fabrics were not dyed.

(3) Dye fastness

The light fastness was according to the original fastness of the respective dye. That is, disperse dyes and cationic dyes are grades 5 to 7, acid dyes are grades 4 to 5, and vat dyes are grades 7 to 9.
Grade and vegetable dyes were about grade 2.

The washing fastness was about 4 to 5 for disperse dyes and cationic dyes, 3 to 5 for acid dyes, 5 for vat dyes, and 2 to 4 for vegetable dyes.

[Brief description of drawings]

FIG. 1 shows Fourier transform infrared absorption spectra of untreated polypropylene (1) and MMA-grafted polypropylene (2) by a KBr tablet method.

FIG. 2 shows Fourier transform infrared absorption spectra of untreated polyvinyl chloride (1), ozone-treated polyvinyl chloride (2), and MMA-grafted polyvinyl chloride (3) by the diffuse reflection method.

FIG. 3 shows Fourier transform infrared absorption spectra of untreated polypropylene (1), ozone-treated polypropylene (2), acrylamide-grafted polypropylene (3), and AMHPP (acrylamide-grafted-Hoffmann rearranged polypropylene) (4) by the diffuse reflection method. .

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location C08F 8/06 MGC C08J 3/00 D06M 11/32 14/18 D06P 5/00 DBA DBE DBG 104

Claims (4)

[Claims] 1. A surface treatment of a molded article or a fiber product made of a polymer material, comprising the steps of (1) a step of treating with ozone, and (2) a step of grafting a vinyl compound while irradiating ultraviolet rays. A method for modifying the surface of a molded article or a fiber product of a polymer material, which comprises successively treating in order. 2. A surface of a molded article / fiber product of a polymer material is treated with (1) ozone, (2) a step of grafting a vinyl compound having an amide group while irradiating with ultraviolet rays, and (3). A molded article of a polymer material characterized by being continuously treated in this order in three steps of a step of Hoffman rearrangement of the amide group grafted in step 2.
Surface modification method for textiles. 3. The surface of a molded article or fiber product of a polymeric material is treated in two steps, (1) a step of treating with ozone, and (2) a step of grafting a vinyl compound while irradiating ultraviolet rays. A method for dyeing a molded article or a fiber product of a polymer material, which comprises sequentially and successively treating and then dyeing. 4. The surface of a molded article or fiber product of a polymer material is treated with (1) ozone, (2) a step of grafting a vinyl compound having an amide group while irradiating with ultraviolet rays, and (3). A method for dyeing a molded article / fiber product of a polymer material, which comprises successively treating in this order in three steps of a step of Hoffman rearrangement of the amide group grafted in step 2, and then dyeing.