JPH01111A - Surface modification method for polymer materials - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (&) Object of the Invention (Industrial Field of Application) The present invention relates to a method for surface modification of polymeric materials, particularly to improve the hydrophilicity, antistatic property, protective property, etc. of various polymeric materials. This invention relates to a method for modifying surface properties such as adhesion to objects.

Note that the term "r surface of polymeric material" in this specification also includes "interface of polymeric material."

(Prior art) Many polymer materials have poor hydrophilicity and high electrical resistance, and are easily charged by slight mechanical action (for example, friction) and have #1 particles attached to them. It has drawbacks such as being easy to get dirty. Furthermore, due to its poor hydrophilicity, it has the disadvantage of poor interfacial adhesion when laminated with metals such as aluminum.

Conventionally, there have been methods to remove the drawbacks of polymeric materials, such as discontinuing the surfactant or incorporating the surfactant, but in the former method, the surfactant is attached to the surface of the polymeric material. Because it is only a small amount of friction,
Alternatively, by exposing the surfactant to a high humidity atmosphere, the surfactant may be washed away by water droplets adhering to the surface of the scraped di-polymer material, and its modifying effect may be lost within a short period of time. It had some serious drawbacks. Also, the latter method
The surfactant bleeds onto the surface and becomes sticky,
There are drawbacks such as blocking, or conversely, the surfactant remains inside and does not exhibit any surface modification effect.

In addition, a modification in which a monomer formed by randomly copolymerizing a monomer that forms a polymer chain that is compatible with the polymer material with a monomer having a hydrophilic group such as acrylic acid is kneaded into the polymer material. The law is also known. However, this method has the disadvantage that a sufficient surface modification effect cannot be obtained unless the amount of random copolymer added is relatively large, and when the amount added is increased, the properties of the polymer material itself are lost. I was disappointed.

In addition, in recent years, methods have been developed for modifying polymeric materials by adding pro-copolymers or graft copolymers consisting of a hydrophilic polymer portion and a hydrophobic polymer portion to the polymeric material. Various proposals have been made regarding this.

For example, "Atopansis in Chemistry" Part 1
42, p. 320 (1975), AB type has a hydrophobic poly(N-lauroylethyleneimine) moiety that is compatible with nylon fibers and a hydrophilic poly(N-probionylethyleneimine) moiety. It has been proposed to produce block copolymers by cationic ring-opening polymerization and add them to fibers to make their surfaces hydrophilic.

Also, "Journal of Macromolecular Science Chemistry Part A" Volume 13, No. 401
(1979), AB type consisting of a hydrophobic polystyrene part and a hydrophilic polytetrahydrofuran part,
Alternatively, it is described that an ABA type pro-copolymer is synthesized by both anionic and cationic living polymerization, and the surface is made hydrophilic by adding this to polystyrene.

However, since the production method of each of the above-mentioned polymeric copolymers is an ionic polymerization method, the polymerization does not proceed smoothly due to the presence of moisture and metal ion shadows, which are easily observed during the polymerization process. The disadvantage was that the polymerization process was complicated and unsuitable for industrial use.

Furthermore, in the Journal of the Japan Adhesive Association Vol. 17, No. 9, pages 371 et seq. (1981), a vinyl polymerizable double bond is added to one end of polymethyl methacrylate to make a macromonomer, and this macromonomer and By copolymerizing with hydroxyethyl methacrylate, a graft copolymer consisting of hydrophobic polymethyl methacrylate portions as branches and hydrophilic polyhydroxyethyl methacrylate portion as the trunk is synthesized.
It is described that this graft copolymer is added to premethyl methacrylate to make the surface of polymethyl methacrylate hydrophilic. However, the grafted polymer consisting of a hydrophilic polymer part and a hydrophobic polymer part obtained by the above synthesis method is not only complex in its synthesis method, but also requires copolymerization of macromonomers. To maintain sex,
It is necessary to maintain the molecular weight of the macromonomer at a certain level (number average molecular weight of 1000 to 10,000), and the polymethyl methacrylate portion, which is a branch portion, becomes an oligomer with a number average molecular weight of 10,000 or less. for that,
When this graft copolymer is added to polymethyl methacrylate, which is the target of modification, due to its low molecular weight, it is not always sufficiently captured in the polymer material, and the surface remains for a long time. The modification effect cannot be expected to last.

Furthermore, JP-A No. 59-202261 discloses a product composed of a hydrophobic polymer portion and a hydrophilic polymer portion that are compatible with polymeric forest materials, synthesized using I limerick peroxide or a polyazo compound as a polymerization initiator. A method of modifying a polymeric material by adding a copolymer to the polymeric material is described. However, in the block copolymer obtained by this synthesis method, it is not easy to control the molecular weight of the pro- and copolymers, and polyelectrolytic homopolymers are produced as by-products and are mixed in. Even if it is added to the material, it will not work well and the modification effect cannot be reliably exerted.

In summary, the unresolved issues in modifying the surface of polymeric materials are as follows:
There was no industrially satisfactory method.

(Problems to be Solved by the Invention) The present invention reliably and efficiently imparts long-lasting properties such as hydrophilicity, antistatic property, antifogging property, and adhesion to the surface of a polymeric material. The present invention aims to provide a method for surface modification of polymeric materials that can be used to modify the surface of polymeric materials.

(b) Structure of the Invention (Means for Solving the Problems) As a result of various studies conducted in order to solve the above problems, the present invention has developed a method for radical polymerization using an initiator having a dithiocarbamate group. This purpose can be achieved by using as a modifier a specific pro-copolymer having hydrophilic pro- and di-chains and pro- and di-chains that have an affinity for polymeric materials, obtained by polymerizing monomers. I was able to accomplish this.

That is, the method for surface modification of a polymeric material of the present invention involves the addition of - to at least the surface portion of a polymeric material (in the formula, R1 and R2 are each hydrogen or an alkyl group having 1 to 10 carbon atoms). A pro- and polycopolymer obtained by polymerizing a radically polymerizable monomer using an initiator having a dithiocar/sulfomate group represented by: a hydrophilic block chain A and the polymer material described above. This method is characterized in that a block copolymer having a block chain B having an affinity for is present.

The polymer materials to be subjected to the modification method of the present invention include various polymer molded products made of synthetic polymers and natural polymers, such as films, sheets, fibers, rubber molded products, etc. Not only various plastic molded products, but also paints, fibers, membranes, sheets, cloth, sealants, and various other materials obtained using various polymers can be opened. Further, specific examples of the polymers include pre-acrylic resin, polyvinyl chloride resin, divinylidene chloride resin, polystyrene resin, ABS resin, styrene chlorinated polypropylene resin, 4-lyamide resin, 4-lyester resin, epoxy resin, Polyphenylene oxide resin, polycarbonate resin, I-litz vinyliso/resin, noryl resin, polyurethane resin, nitrocellulose resin, cellulose acetate resin, ethyl cellulose resin, cellulose acetate butyrate resin, cellulose acetate propionate resin, ethylene- Vinyl acetate resin, urea resin, melamine resin, polyvinyl ether resin, petroleum resin, coumaron resin, indene resin, phenolic resin,
a7tar resin, acrylonitrilutazoene rubber,
Chloroprene rubber, acrylic rubber, buterpum, polybutadiene rubber, polyisogrene rubber, ethylene-propylene-diene rubber, polyacrylic fiber, polyester fiber, polyvinyl alcohol fiber, polyvinyl chloride fiber,
I-lyamide fiber, polyvinylidene chloride fiber, ? Examples include polyethylene fiber, polypropylene fiber, 4-urethane fiber, I-lipinylacetal fiber, and natural polymer materials such as rosin, natural rubber, cotton, linen, wool, and silk.

The pro- and poly-copolymers used in the modification method of the present invention are:
The dithiocarbamate group represented by -introduction (ri) is 1
It is obtained by polymerizing radically polymerizable monomers using one or more initiators, but the polymerization reaction to synthesize the pro-copolymer is usually a two-step method. It is done. That is, the polymerization reaction is carried out in the first step by using an initiator having a dithiocarbamate group to form a radically polymerizable monomer (hereinafter referred to as a "hydrophilic monomer") to form a hydrophilic block chain A. ), or a professional with affinity for polymer materials,
One of the radically polymerizable monomers (hereinafter sometimes referred to as "affinity monomers") that forms the chain B is polymerized. In the polymerization reaction of this first step, an initiator (hereinafter sometimes referred to as a "polymer initiator") having a dithiocarbamate group bonded to the end of the polymer chain formed by the polymerization is obtained. It will be done.

Next, in the second step, the polymeric initiator obtained in the first step is used as an initiator to polymerize the other monomer (i.e., affinity monomer or a hydrophilic monomer), the hydrophilic block chain A used in the present invention and the affinity pro-chain B
A block copolymer having the following is obtained.

In such a two-step polymerization reaction, when a monofunctional initiator having one dithiocarbamate group is used as an initiator, the pro-, di-chain A and block chain B are AH
A combination of AB type blocks bonded to the molecular structure of the type is obtained. Furthermore, if a bifunctional initiator having two dithiocarbamate groups is used, an ABA type or BAB type pro-copolymer can be obtained. In this case, the ABA type block copolymer is obtained in the first step by polymerizing the monomer that forms the affinity pro-chain B, that is, the affinity monomer, and the BAB type block copolymer is The copolymer is the first
It is obtained when the monomers that form the hydrophilic block chain A in the process, that is, the hydrophilic monomers, are combined. Furthermore, if a polyfunctional initiator having three or more dithiocarbamate groups is used for polymerization, the block chain (chain A or B) formed in the first step polymerization can be used in the second step polymerization. Pro, button (chain B or A) formed with
) is bonded in a star shape (radially) to form a block copolymer having a molecular structure, that is, an AB star block copolymer.

These AB-type, ABA-type, BAB-type and AB star-type block copolymers can all be used as the pro- and polycopolymers of the present invention. It has already been announced and known that by using a plurality of initiators, block copolymers having various molecular structures can be obtained ["Polymer Pregreen, Shirt Back" Vol. 31, Vol. No. 6 (1982), p. 1289 et seq., and Vol. It is something that will be done.

The dithiocarbamate group represented by the general formula (1) used in the production of the pro- and poly-copolymers of the present invention is
There are various types of initiators having one or more initiators.

The monofunctional initiator having one dithiocarbamate group (functional group) has the general formula (wherein, X is an organic group, and R1 and R2 are the same as R1 and R2 in the general formula (1), respectively) is 0
), and a compound represented by the general formula (wherein R1 and R2 are R in the above general formula (1)
1 and R2, respectively. ) can be mentioned. The organic group X in general formula (n) may be a saturated or unsaturated hydrocarbon group,
There is no problem even if it is a hydrocarbon group including /I/, y-nyl group, ester group, ether group, etc.

Specific examples of the monofunctional initiator represented by the general formula (II) include the following compounds.

(n-butyl N,N-nomethyldithiocaranomate
) S (benzyldithiocarbamate) (benzyl N-methyldithiocarbamate) δ (benzyl N, N-dimethyldithiocarbamate) (benzyl N-ethyldithiocarbamate) (pe/zyl N,
N-diethyldithiocarbamate) Also, the above-mentioned formula (
Specific examples of the monofunctional initiator represented by III) include:
Examples include the following compounds.

S (thiuram monosulfite) S (N,N-dimethylthiuram monosulfide) (N,
N,N',N'-tetramethylthiuram monosulfide)S (NeN'-yethelthiuram monos, 11/fip
) (N, N, N', N'-tetraethylthiuram monosulfide) In addition, as a polyfunctional initiator that can be used, -
A compound represented by the formula (wherein R1 and R2 are the same as R and R in the formula (1) above), and a compound represented by the formula (wherein R1 and R2 are the same as R in the formula (1) above), and R are respectively the same, and 17.!l is 1 or 2.) and a compound represented by the formula (wherein 2 is an organic group υ 11 and R2 are R and and m is an integer of 2 to 40).

Specific examples of the compound represented by formula (IV) include the following compounds.

S (thiuram disulfide) S (N,N'-dimethylthiuram disulfide) (N,N
,N%N'-tetramethylthiuram disulfide)SS (N,N'-diethylthiuram disulfide)(N,N
, N',N'-tetraethylthiuram disulfide) Specific examples of the compound represented by the general formula (V) include the following compounds.

SS (thiuram trisulfide) SS (N,N'-dimethylthiuram trisulfide) (N,
N'-tetraethylthiuram trisulfide)S
S (thiuram tetrasulfide) SS (N,N'-dimethylthiuram tetrasulfide) (N
, N, N', N'-tetraethylthiuram tetrasulfide) Further, specific examples of the compound represented by the general formula (V1) include the following compounds.

Cp-xylene bis(diteocarbamate)]]Cp-
xylene bis N-methyldithiocarbamate)][]p
-xylenebisN,N-dimethyldithiocarbamate)
](]p-xylenebisN,N-diethyldithiocarbamate)](]1.2-bisN,N-diethylsothiocarpamyl)ethane](: 1.2-ni's(N,N- dimethyldithiocarpamyl)ethane][1,2,3-)lis(N,N-nomethyldithiocarpamyl)pro[1,2
,4,5-tetrakis(N,N-diethyldithiocarpamylmethyl)benzene] The initiator having such a dithiocarbamate group used in the present invention generally reacts sodium dithiocarbamate with the corresponding organohalodanide. It can be synthesized with good yield by doing this. For example, if p-xylene dibromide and sodium N,N-diethylzothiocarpamate are reacted, p-xylene bis(N,N
-diethyldithiocarbamate) is obtained. In addition, since various compounds having such dithiocarbamate groups have already been industrially produced and commercially available, such commercially available compounds having dithiocarbamate groups may be used to manufacture the block copolymer used in the present invention. can do.

Next, as the hydrophilic monomer used for forming the hydrophilic pro-chain A for producing the block copolymer in the present invention, for example, (meth)acrylic acid [Note: This is not acrylic acid. It is a general term for methacrylic acid. Same below. ),
Radically polymerizable unsaturated carboxylic acids such as itaconic acid and crotonic acid, alkali metal salts of these unsaturated cargenic acids, ammonium ffl, organic amine salts, and radically polymerizable compounds with sulfonic acid groups such as styrene sulfonic acid. Unsaturated monomers, alkali metal salts, ammonium salts, organic amine salts of radically polymerizable unsaturated monomers having sulfonic acid groups, (meth)acrylics such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride Quaternary ammonium salts derived from acids, (meth)
(meth)acrylic acid esters of alcohols having a tertiary amine group such as acrylic acid diethylamino ester, their quaternary ammonium salts, and radically polymerizable substances containing an amide group such as (meth)acrylic acid amide. Unsaturated monomers, quaternary ammonium salts derived from amidoamines obtained from (meth)acrylic acid and diamines, (
meth)acrylic acid hydroxyethyl ester, (meth)
Hydroxyalkyl esters of (meth)acrylic acid, such as acrylic acid hydroxypropyl ester, (meth)
Polyethylene glycol or polypropylene glycol ester of (meth)acrylic acid, such as acrylic acid diethylene glycol ester, (meth)acrylic acid triethylene glycol ester, (meth)acrylic acid dipropylene glycol ester, and (meth)acrylic acid monoglyceride. Polyhydric alcohol esters of (meth)acrylic acid, phosphates of (meth)acrylic acid such as mono(2-hydroxyethyl acrylate) acid phosphate, vinylpyridine, vinylpyridine salts,
Examples include vinylpyrrolidone. These hydrophilic vinyl monomers include 1a [or hydrophilic monomers using two or more],
Furthermore, the hydrophilic pro-chains formed in these hydrophilic monomers can be combined with other monomers to form hydrophilic chains at a level that does not impair the hydrophilicity of the chain A. A block chain A can be formed.

In addition, the affinity monomers used to form the affinity monomers and chains B for producing the block copolymer of the present invention vary depending on the type of polymeric material to be modified. , a monomer that forms a polymer with good miscibility with a certain polymeric material (note 2: ordinary monomer) is
Even if a block chain is formed, it will give a block chain that has affinity for the polymer material. This can be easily determined by forming the film into a film and visually inspecting the resulting film.

That is, if the film obtained in that case is transparent, or even if it is not transparent, if the polymer is uniformly dispersed in the polymer material, it is determined that the film has good miscibility. On the other hand, if a heterogeneous film in which polymer particles are dispersed as particles large enough to be visually observed is obtained, the miscibility is determined to be poor. Therefore, by using such a visual judgment method based on preliminary experiments, it is possible to easily select a monomer that provides a pro- and di-chain with good affinity for a certain polymeric material.

Polymers with good miscibility with many polymeric materials are also described in ``Journal of Macromolecules, Laer Science / 4'-To CJ, Vol. 7, p. 251 (1972) and ``Japan Contact. It is well known as it is described in "Ken Kyokai Zasshi", Vol. 11, No. 1, page 2 et seq. (1975). Based on the descriptions of these known documents, combinations of polymeric materials and polymers with good miscibility therein are summarized as shown in Table 1.

From this Table 1, it is easy to select monomers (including monomer mixtures) that provide block chains with affinity for many polymeric materials.

Furthermore, representative monomers that can be selected as monomers used to form the affinity chain B of the pro- and poly-copolymers used in the present invention include, for example: (meth)methyl acrylate, (meth)ethyl acrylate, (meth)
n-propyl acrylate, isopropyl (meth)acrylate, glycidyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, (meth)acrylate n-hexyl acid, cyclohexyl (meth)acrylate,
(Meth)acrylic #R2-Ethylhexyl, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and other (meth)acrylic acid esters, styrene, vinyltoluene, α-methylstyrene, and other aromas. Group vinyl type monomers, vinyl cargenate esters such as vinyl formate, vinyl acetate, vinyl propionate, and vinyl stearate, trifluoroethylene, vinylidene fluoride, etc., vinyl monomers, butadiene,
Examples include vinyl chloride, vinylidene chloride, (meth)acrylonitrile, and (meth)allyl glycysol ether. Among these monomers, depending on the type of polymeric material to be modified, 1 is selected from among these monomers for the formation of 1 and 2 chains B, depending on the type of polymer material to be modified, etc., by visual judgment in the preliminary experiment described above and by taking into account known facts. Monomers of various types may be used, or two or more types of monomers may be used in combination as appropriate. Furthermore, as the monomer for forming the affinity block chain B, a monomer having a functional group reactive with the functional group contained in the polymeric material can be used. In addition, Affinity Pro.

As for the monomer that forms the chain B, it is also possible to use other monomers with no affinity in combination with the affinity monomer in an amount that does not impair the affinity of the pro- and chain B. It is.

In order to produce the block copolymer used in the present invention using the initiator having a dithiocarbamate group, the hydrophilic monomer, and the affinity monomer detailed above, the first step is usually carried out as described above. AB type, ABA type, BAB type, or ABM type block copolymer is synthesized using a two-stage polymerization reaction method consisting of a second step and a second step.

Note that the pro- and poly-copolymers obtained by the second-stage polymerization reaction still have the ability as a polymer initiator, so in some cases, they may be used as initiators for polymerization. A multi-block copolymer can be produced by carrying out multi-stage polymerization of three or more stages. Such multi-block copolymers also include hydrophilic block chains A,
! : i-compatible block chain B can be used as a pro- or poly-copolymer in the present invention.

The ability to initiate one polymerization in the first stage (first step) in the pro-copolymer production reaction using an initiator containing a dithiocarbamate group is determined by light, preferably at a wavelength of 300 to 400 nm.
However, in the case of the initiators represented by the general formulas (IV) and (V), the 1-coin initiation ability can be further expressed by thermal energy (heating). . The heating temperature in that case is preferably 50 to 120°C. On the other hand, in the initiators represented by the above general formulas (It), (III) and (M), the bond that requires one solution kt is the S-C bond, and the bond energy is large, so the light (ultraviolet arm) Polymerization initiation ability cannot be expressed without energy.

In addition, in the case of the second stage (second step) polymerization reaction that uses the polymer initiator produced in the first stage polymerization reaction, the polymer initiator should dissociate according to the general formula % formula %. Since the bond is a C-8 bond, light (ultraviolet light) is used to develop its ability to initiate polymerization. The temperature of the polymerization system when photopolymerization (ultraviolet light) is carried out through the first and second stages is preferably 150° C. or lower from the viewpoint of protecting the diteocarbamate group.

In the polymerization reaction using a dithiocarbamate initiator and light energy to produce the pro- and polycopolymers used in the present invention, as long as the light energy necessary for dissociation of the dithiocarbamate group can sufficiently reach the initiator, Both homogeneous and heterogeneous reaction systems can be used. However, in general, bulk polymerization or solution polymerization is used for the first stage polymerization reaction, and solution polymerization is used for the second stage polymerization reaction, or a polymer initiator is used in a single cap for the second stage polymerization. Dissolved solution polymerization is used.

As the solvent for solution polymerization, it is preferable to use a solvent that has no characteristic absorption of ultraviolet light in the wavelength range of 300 to 400 nm, has a small chain transfer constant, and can dissolve the monomer and the polymer well. Preferred solvents include, for example, benzene,
Toluene, xylene, ethylbenzene, acetone, methyl ethyl ketone, ethyl acetate, dimethylformamide,
Improvil alcohol, butanol, hexane, pentane, etc. are rejected.

In the polymerization reaction for producing the block copolymer of the present invention, the molecular weight of each block can be controlled by adjusting the molar ratio of the initiator to the monomer. For example, 1 N,N-noethylpendylthiocarpamate is added to methyl methacrylate in the molecule jtloO.
When molti is added and reacted, a polymer having a number average molecular weight of about 10,000 and a weight average molecular weight of about 20,000 is obtained.

Similarly, if the amount added is changed to 0.1 mole, the number average molecular weight is 100,000, and the weight average molecular weight is 200.
000 polymer is obtained. Similarly, in the second stage polymerization reaction, the molecular weight of the produced pro-chains can be controlled by adjusting the molar ratio of the polymer initiator and the second stage single cap.

The block copolymer used in the present invention preferably has a weight average molecular weight of 500 to 1,000,000 and a content of hydrophilic pro-chains A of 5 to 75% by weight. 1M average molecular weight of the same block co-merger is 5000
Less than professional from polymeric materials.

The copolymer tends to bleed out, and sufficient sustainability of the modification effect cannot be obtained, and i, o o o, o o
.

If it exceeds this, the diffusion rate of the pro-copolymer to the surface will be low and it will not necessarily migrate to the surface, making it impossible to fully exhibit the surface-modifying effect.

Furthermore, if the content of block chain A is less than 5%, the hydrophilic chains will not be able to sufficiently loosen the entire surface, resulting in insufficient modification effect, and if the content exceeds 75Mjlk%. Since the content of affinity pro-chains is relatively small, the affinity with the polymeric material becomes insufficient, resulting in poor dispersion.

In order to make the pro-copolymer exist in at least the surface portion of the polymer material in the modification method of the present invention, the pro-copolymer is present (mixed) in the entire polymer material.
The block copolymer may be present only on the surface of the polymeric material, and there are various ways in which the pro-copolymer can be present. First, as a typical embodiment, a block copolymer is added to the polymer material to be modified and mixed, for example, when the polymer material is molded, the block copolymer is added to the polymer and the child material.

Examples include an embodiment in which the polycopolymer is mixed and kneaded and then molded, or a solution in which the polymeric material and the polypropylene copolymer are dissolved is formed into a film and molded. In this embodiment, the entire polymer material is modified, not just the optical surface portion. Other embodiments include applying a solvent bath solution or dispersion of the block copolymer to the surface of the polymeric material, or coating the surface of the polymeric material with a pre-sheet-formed pro, copolymer, or pro-copolymer. A mode in which a sheet of resin containing a copolymer is bonded under heat or using an adhesive, and a mode in which a copolymer is welded as a powder to the surface of a polymer material, etc. In these latter embodiments, usually only the surface portion of the polymeric material will be modified by the pro-copolymer.

In the modification method of the present invention, the proportion of the pro-copolymer used is as follows: The block copolymer is 0.01 for every 100 heavy plate parts.
~30:i parts, preferably 0.1 to 20 parts by weight. If the proportion of the pro-copolymer used is too small, a sufficient modifying effect cannot be obtained, and if it is too large, the original properties of the polymeric material will be impaired.

In the modification method of the present invention, an anionic surfactant such as an alkyl phosphate ester; a cationic surfactant such as laurylbenzylammonium chloride, trimethyldodecyl ammonium chloride, or polyoxyethylene alkylamine; and a betaine type surfactant are added to the block copolymer. Alternatively, various surfactants including imidacillin type amphoteric surfactants can be used in combination. In this case, the proportion of the surfactant used in combination is desirably 50% by weight or less based on the pro-copolymer, since the effect of the block copolymer will be impaired if the quantity is too large.

(Examples, etc.) The following is a more detailed explanation of pro- and poly-copolymer synthesis examples and examples. Part 1” and “C” listed in these examples
means "jubinbu" and "juichi" respectively.

Block copolymer synthesis example 1 (1st step) In a constant temperature bath at 50°C, at a distance of 10 m from an ultraviolet lamp with an output of 400 W (H-40OL manufactured by Toshiba Corporation), a mother tube, a diameter 33 glass tube made of glass glass, Volume 20011
/ Place a container containing styrene 10019, benzyl-N,N-diethyldithiocarha 1 -) in this container.
After 39 g of the container was charged and the gas in the container was replaced with nitrogen, the container was sealed and irradiated with ultraviolet rays using the above-mentioned ultraviolet lamp for 10 hours to effect photopolymerization.

The obtained polymer was a pale yellow transparent solid, and the residual monomer value was 1.6%. In addition, the number average molecule sr in terms of polystyrene measured by GPC (GPC) was as follows: It's called "Mn". ) is 9800
The weight average molecular weight in terms of polystyrene (hereinafter referred to as “M
It's called WJ. ) is 22,000. This polymer is a polymeric initiator.

(Second process) 4ON of pulverized powder of fc, 8 compound obtained in the first step.

2-Hydroxyethyl methacrylate 4ON and 160 g of methyl ethyl ketone were thoroughly mixed and dissolved, and the resulting mixture was charged into a container of the same device as used in the first step, and after replacing the slip, the yarn was heated for 10 hours. Photopolymerization was carried out by irradiating with external radiation.

The resulting translucent white monomer dispersion was reprecipitated using hexane and dried to obtain a block copolymer. This block copolymer was determined by GPC to have Mn=22.000, M
When w was 45,000, it was stale, and the remaining monomer* contained less than 1 t in total.

Block copolymer synthesis example 2 (first step) Using the same equipment as in synthesis example IK, 2.39 g of methyl methacrylate 100F, benzyl N, N-diethyldithiocarpa) were charged into the container, and synthesis example Photopolymerization was carried out in the same manner as in 1. The obtained compound 1 was a pale yellow transparent solid, and the residual monomer content was 1.0%. Mn = 9.900 by GPC), Mw = 2
It was 3,000.

(Second process) Pulverized powder of polymer obtained in the first step 40. F.

2-Hydroxyethyl methacrylate 40! ! , and 160 g of methyl ethyl ketone, otherwise photopolymerization was carried out in the same manner as in Synthesis Example 1, and the same post-treatment was carried out to obtain a block copolymer. Mn by GPC of the copolymer
= 23,000, MW = 4 s, o OO, and the total remaining monomer was less than 1 h.

Block copolymer synthesis example 3 40 g of crushed powder of the polymer obtained in the first step of synthesis example 2
, acrylic acid 4011 and methyl ethyl ketone 160y
was used, and photopolymerization was carried out in the same manner as in the second step of Synthesis Example 1 except for the above, and a block copolymer was obtained by post-treatment in the same manner. Mn=22 by GPC of this copolymer,
000, Mw = 46,000, and the total residual monomer was less than 1%.

Proac copolymer synthesis example 4 40f crushed powder of polymer obtained in the first step of synthesis example 2
Photopolymerization was carried out in the same manner as in the second step of Synthesis Example 1 except for using I, 40 g of sodium styrene sulfonate, 80 g of methanol, and 8011 acetone, and post-treatment was carried out in the same manner to obtain a block copolymer. This co-merger is GPC
Mn=21,000 and My=46,000, and the total residual monomer content was less than 1%.

Block copolymer synthesis example 5 (first step) Methyl methacrylate 100J1p-xylene bis(N,
Using 4.0 g of N-noethyldithiocarpamate, photopolymerization was carried out in the same manner as in the first step of Synthesis Example 1,
Post-processed in the same way, Mn = 9.800, MW = 2
2,000 polymers were obtained.

(Second step) 40 g of crushed powder of the polymer obtained in the first step, 40 g of 2-hydroxyethyl methacrylate. Using 160 g of li' and methyl ethyl ketone, photopolymerization was carried out in the same manner as in the second step of Synthesis Example 1, and post-treatment was carried out in the same manner to obtain a block copolymer.

This co-merger was determined by GPC with Mn=23. OOO1MW
= 49,000, and the total amount of residual monomers was less than 1.

Example 1 100 parts of polystyrene resin powder and 5 parts of the block copolymer obtained in Synthesis Example 1 above were kneaded into a sheet using an extrusion molding machine, and then press molded to obtain a sheet with a thickness of 0.5 gourd. Ta.

This sheet had no coloration, no bleeding was observed on the surface, and had good processability.

The surface resistivity and contact angle of pure water were measured for this sheet and a sheet made of polystyrene resin for all tests in the same manner. Ta.). The result is the second
It was as shown in the table.

Table 2 Notes to Table 2 (same for each table below): *1... Measured using a surface resistance measuring device manufactured by Sanko Seiki Co., Ltd.

*2...FACE contact angle needle C from Kyowa Interface Science Co., Ltd.
It was measured by A-D type.

As is clear from Table 2, the surface specific resistance value and contact angle of the products containing the Pro and Rikyo 1 combinations are much lower than those without the combinations, and the surface modification effect is clear. Further, after washing this surface with tap water at 25° C. for 1 hour at a flow rate of 217 minutes, similar characteristics were measured, and the results were no different from those before washing.

Example 2 100 parts of methacrylic acid resin powder and 5 parts of the block copolymer obtained in Synthesis Example 2 above were molded in the same manner as in Example 1, and the obtained sheet had no coloring and no bleeding. Workability was also good. Furthermore, the same characteristic values as in Example 1 were measured for the sheet, and the results were as shown in Table 3.

As is clear from Table 3, the surface properties were significantly modified by the addition of the pro- and poly-copolymers. Further, the sheet was washed with water under the same conditions as in Example 1, and the results were completely unchanged from before washing.

Example 3 A sheet was prepared in the same manner as in Example 1 except that 100 parts of polyvinyl chloride resin powder and 5 parts of the pro- and lyco-1 combination obtained in Synthesis Example 2 were used. The obtained sheet has no coloring,
There was no bleeding and the workability was good69, and the characteristic values measured in the same manner as in Example 1 were as shown in Table 4.

As is clear from Table 4, the surface properties were significantly modified by the addition of the pro- and poly-copolymers. Further, the sheet was washed with water under the same conditions as in Example 1, and the results were completely unchanged from before washing.

Example 4 A sheet was produced according to Example 1 except that 100 parts of polyvinylidene fluoride resin powder and 5 parts of the pro-polymer copolymer obtained in Synthesis Example 2 were used. The obtained sheet had no coloring, no bleeding, and had good processability.

Also, the sheet has the same characteristics as Example 1. The results of measuring W were as shown in Table 5.

As is clear from the results in Table 5, the surface properties were significantly modified by the addition of the pro- and poly-copolymers.

In addition, the sheet was washed with water under the same conditions as in Example 1, and the results were completely unchanged from before washing. A sheet having a thickness of 1 cm was prepared in the same manner as in Example 1 except for the above. This sheet had no coloration, no bleed, and had good workability. Also, the surface resistivity value and the surface resistivity value after friction were measured for this sheet and the pro-copolymer-free sheet. were as shown in Table 6.

Table 6 Notes to Table 6 (same for Table 7): *1...Measured using a rotary static tester manufactured by Koa Shokai at a rotation speed of 15 Or, p, m after rubbing for 3 minutes using cotton cloth. (The measurement environment was the same as in Example 1).

As is clear from Table 6, the specific resistance value of the product containing the pro-copolymer was low, and there was almost no change in the value even after rubbing. In contrast, the sheet made without block copolymer additives had a high specific resistance value, and the same value became even higher after friction. Furthermore, the results of washing with water under the same conditions as in Example 1 were no different from before washing.

Example 6, j? IJ 100 parts of methyl methacrylate resin and 5 parts of the block copolymer obtained in Synthesis Example 2 were dissolved in ethyl acetate and a film was prepared by a 1m agent film forming method.The obtained film was free of coloration and no bleeding. The surface resistivity value and the surface resistivity value after friction were measured for this film and a film formed in the same manner without using any block copolymer. The result is the 7th
It was as shown in the table.

In Table 7, the block copolymer compound showed very good antistatic effect, with almost no change in surface resistance even after surface friction. Further, even after washing the surface with water under the same conditions as in Example 1, there was no difference at all from before washing.

Example 7 A dispersion in which 30 parts of the block copolymer obtained in Synthesis Example 2 was dispersed in 100 parts of ethyl acetate was prepared so that the thickness after drying was 8 μm.
It was coated on an acrylic resin plate by bar coating so that the resultant composition was obtained, and then dried at room temperature for 2 hours, and then heated to 60° C. for 2 hours. The surface resistivity value and the contact angle with respect to pure water of the obtained coated acrylic resin plate were measured (the measurement environment was the same as in Example 1). The results were as shown in Table 8.

As is clear from the results in Table 8, the surface resistivity and contact angle of the samples coated with the pro-copolymer were significantly lower than those coated without the coating. In addition, the surface of Example 1
The same characteristics were measured after washing under the same conditions as in , and the results were no different from before washing.

Example 8 2 parts of the block copolymer obtained in Synthesis Example 2 were mixed with 100 parts of an acrylic resin face for paint (ethyl acetate bath liquid with a solid content of 30%), and polymethyl methacrylate was prepared by washing with ethanol in advance. The resin sheet was painted with Ford Kag Black 4 in gray at a viscosity of 19-20 seconds and dried at 60° C. for 1 hour. The obtained coated sheet and a sheet coated with an acrylic resin face to which no block copolymer was added in the same manner and dried were subjected to the same test as in Example 1, and the results are shown in Table 9.

As is clear from the results in Table 9, those coated with the block copolymer-added face have both extremely low surface resistivity and contact angle, compared to those coated with the non-additive face. Further, after washing the coated surface with water under the same conditions as in Example 1, the same characteristics were measured, and the results were no different from those before washing with water.

Example 9 A sheet was produced in the same manner as in Example 1 except that 10.0 parts of polymethyl methacrylate resin and 5 parts of the pro- and polycopolymer obtained in Synthesis Example 4 were used. Surface properties were tested. The results were as shown in Table 10. Furthermore, the obtained sheet had no coloring, no bleeding, and had good workability.

As is clear from Table 10, No. 10, the surface resistivity and contact angle of the block copolymer added are significantly lower than those without additives. Furthermore, the surface was washed with water under the same conditions as in Example 1, and the results were completely unchanged from before washing.

Example 10 Using 100 parts of methyl methacrylate bile powder and the pro- and polycopolymer obtained in Synthesis Example 4, the rest was as in Example 1.
A sheet was manufactured in the same manner as in, and tested in the same manner. The results were as shown in Table 11. Furthermore, the obtained sheet had no coloring, no bleeding, and had good processability.

Table 11 As is clear from Table 11, the surface resistivity and contact angle of the block copolymer added are significantly lower than those without additives. Further, the surface was washed with water in the same manner as in Example 1, and the results were no different from before washing.

Example 11 100 parts of polymethyl methacrylate resin and the block copolymer obtained in Synthesis Example 5 were used, and the rest was as in Example 1.
A sheet was produced in the same manner as in. The resulting sheet had no coloring, no bleeding, and had good workability. Further, the surface characteristics were measured in the same manner as in Example S, and the results were as shown in Table 12.

Table 12 As is clear from Table 12, the sample to which the block copolymer was added has a much lower optical surface specific resistance value and contact angle than the sample containing no additive. Furthermore, the sheet surface was washed with water under the same conditions as in Example 1, and the results were no different from before washing.

Example 12 100 parts of acrylic resin face for paint (ethyl acetate solution with a solid content of 30 parts) was mixed with 2 parts of the pro-recopolymer obtained in Synthesis Example 3, and a mixture was mixed with a mixture of 13. On the actual board shown in Table 1, 1 with Ford Cag A4.
It was coated with gray paint with a viscosity of 9 to 20 seconds and dried at 60°C for 1 hour. In addition, the same coating without the addition of the pro-copolymer was applied to various substrates in the same manner and dried in the same manner.

Coating film of each coated plate obtained (Aku IJ/l/resin coating film)
The adhesion with the substrate was tested. The result was as shown in Table 13.

13th light note) The test method is based on the cellophane tape peel test method.

As is clear from Table 13, the adhesion of acrylic resins to which a pro-copolymer is added significantly improves adhesion to various substrates compared to additive-free acrylic resins.
) A similar adhesion test was conducted after immersing each substrate coated with Wa 37 in tap water at 25°C for 24 hours. Both the additives and the additives did not change at all from before immersion.

(C) Effects of the Invention The method of the present invention can efficiently, stably and reliably modify the surface properties of various polymeric materials, such as hydrophilicity, antistatic property, antifogging property, and adhesion. can.

Claims (1)

[Claims] 1) At least the surface portion of the polymeric material has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (wherein R^1 and R^2 are each hydrogen or 1 carbon number)
~10 alkyl groups. ) A block copolymer obtained by polymerizing a radically polymerizable monomer using an initiator having a dithiocarbamate group represented by 1. A method for surface modification of a polymeric material, which comprises causing a block copolymer having a block chain B to exist.