JPH09176961A - Block copolymer oligomer, method for producing the same, antifouling agent and textile product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antisoil finishing agent containing a hydrophilic, hydro phobic and fiber-reactive multi-component block copolymeric oligomer as an essential component and applicable to a variety of fibers. SOLUTION: At least one of hydrophilic monomer selected from the group consisting of lower alkoxy-ethylene glycol (meth)acrylate, lower alkoxy-propylene glycol (meth)acrylate, (meth)acrylic acid or their salts, a hydrophobic monomer consisting of perfluoroalkyl methacrylates and a fiber-reactive monomer of N-methylol (meth)acrylamide are mixed with a polymerization initiator comprising tetraethylthiuram disulfide and they are polymerized under irradiation of light to form a hydrophilic, hydrophobic and fiber-reactive block-copolymeric oligomer. This oligomer is treated with light irradiation in the presence of a chain transfer agent or treated with heat in the presence of oxygen or treated with amine to eliminate the diethyl dithiocarbamate groups from the chain terminals, thus giving an oligomer with a number-average molecular weight of 600-10,000. This product is used as an essential component to prepare the objective antisoil finishing agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel hydrophilic-hydrophobic-fiber reactive block copolymer oligomer, a process for producing the same and an antifouling agent.

[0002]

2. Description of the Related Art Conventional methods for obtaining block copolymer oligomers include condensation method, anionic polymerization and living cationic polymerization (Takayuki Otsu, "Chemistry of Chemistry Monograph 15 Revised Polymer Chemistry", Kagaku Dojin, Kyoto). However, it is difficult to completely react the condensation of the polymer, and in the anionic and cationic polymerization, the water must be completely removed from the polymerization system, and the polymerization must be performed at a low temperature, which makes the polymerization operation difficult. Is. Furthermore, the monomer is limited to anionically and cationically polymerizable monomers.

Further, as a method for producing a block copolymer oligomer using a radical initiator, a macroazo initiator (Akira Ueda, Overseas Polymer Research, Vol. 41, page 68 (199)
5)), a polyperoxide initiator (Takashi Yamamoto et al., Journal of the Chemical Society of Japan, 1992 (11), page 1269 (199).
2)) is available. The former has a problem of recombination, and the latter is inefficient because chain transfer such as hydrogen abstraction easily occurs. Moreover, it is difficult to control the molecular weight by the method using these radical initiators.

Polymers containing the following hydrophilic and hydrophobic components have been reported as antifouling agents for fibers.

[0005]

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(POSherman et al., Text.Res.J., Vol. 3
9,449 (1969))

[0007]

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(Random copolymer oligomer x: y =
2: 1) (AGPittman et al., Text. Chemist Color., Vol. 3,175
(1971))

[0009]

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(BM Latta et al., Text.Res.J., Vol. 51, 5
79 (1981)) All of the above compounds are difficult to synthesize and have a drawback of poor adhesion to cellulose fibers.

[0011]

The synthesis of block copolymers by condensation of polymers is difficult to completely react. The synthesis of the block copolymer oligomer by anionic polymerization and living cationic polymerization is limited to a small number of monomers capable of anionic and cationic polymerization. Further, in anionic and cationic polymerization, water must be completely removed from the polymerization system, and the polymerization must be carried out at a low temperature, which makes the polymerization operation difficult (Takayuki Otsu,
"Chemistry monograph 15 revised chemistry of polymer synthesis", Kagaku Dojin, Kyoto).

As a method for producing a block copolymer oligomer, a macroazo initiator (Akira Ueda, Overseas Polymer Research, 41
Vol. 68, p. (1995)) is radical polymerization, and there are many applicable monomers. The polymerization operation and the radical polymerization can be performed in an aqueous system, which is easy, but recombination easily occurs, and the efficiency is poor. Also, it is difficult to control the molecular weight. Radical initiator polyperoxide initiator (Takashi Yamamoto et al., Journal of the Chemical Society of Japan, 1992 (11), p. 1269 (199)
In 2)), chain transfer such as hydrogen abstraction is likely to occur, resulting in poor efficiency. And it is difficult to control the molecular weight.

Conventional antifouling agents have poor adhesion to cellulosic fibers. A modification of this is that the N-methylol acrylamide component can be reacted with the cellulose by acid catalysis by incorporating it into the polymer.

[0014]

DISCLOSURE OF THE INVENTION The present invention provides the following block copolymer oligomer, a method for producing the same, an antifouling agent and a fiber product.

Item 1. A method for producing a hydrophilic-hydrophobic-fiber reactive ternary block copolymer oligomer, which comprises polymerizing a polymerization initiator, a hydrophilic monomer, a hydrophobic monomer and a fiber reactive monomer under light irradiation.

Item 2. A method for producing a hydrophobic-fiber-reactive binary block copolymer oligomer, which comprises polymerizing a polymerization initiator, a hydrophobic monomer and a fiber-reactive monomer under light irradiation.

Item 3. (1) Polymerization initiator is tetraethyl thiuram disulfide, (2) Hydrophilic monomer is lower alkoxy ethylene glycol (meth) acrylate, lower alkoxy propylene glycol (meth) acrylate, methacrylic acid, methacrylic acid salt, acrylic acid, acrylic acid At least one selected from the group consisting of salts
Seed, (3) hydrophobic monomer, perfluoroalkyl (meth) acrylate, (4) fiber-reactive monomer,
Item 2. The method according to Item 1, which is N-methylol (meth) acrylamide.

Item 4. The hydrophilic-hydrophobic-fiber-reactive block copolymer oligomer obtained by the method according to Item 1 or 3, is subjected to light irradiation treatment in the presence of a chain transfer agent, heat treatment in the presence of an acid, and treatment with an amine. A method for producing a hydrophilic-hydrophobic-fiber-reactive block copolymer oligomer, characterized in that the terminal diethyldithiocarbamate group is eliminated by performing any treatment selected from the group consisting of:

Item 5. It has a hydrophilic block, a hydrophobic block and a fiber-reactive block, and has a number average molecular weight of 600.
The ternary block copolymer oligomer is about 10,000.

Item 6. The terpolymer block copolymer oligomer according to claim 5, wherein the terminal contains a diethyldithiocarbamate group.

Item 7. (1) The hydrophilic monomer is at least one selected from the group consisting of lower alkoxy ethylene glycol (meth) acrylate, lower alkoxy propylene glycol (meth) acrylate, methacrylic acid, methacrylic acid salt, acrylic acid, and acrylate salt,
(2) The hydrophobic monomer is perfluoroalkyl (meth) acrylate, and (3) the fiber-reactive monomer is N-.
Item 5 or 6 which is methylol (meth) acrylamide
The ternary block copolymer oligomer according to 1.

Item 8. It has a hydrophobic block and a hydrophilic fiber-reactive block, and has a number average molecular weight of 600 to 10,0.
Hydrophobic-hydrophilic fiber-reactive binary block copolymer oligomer of 00.

Item 9. An antifouling agent comprising the hydrophilic-hydrophobic-fiber reactive block copolymer oligomer according to any one of items 5 to 7 as an essential component.

Item 10. Item 9. An antifouling agent comprising the hydrophobic-hydrophilic fiber-reactive binary block copolymer oligomer according to item 8 as an essential component.

Item 11. Item 9. A fiber product obtained by processing with the stainproofing agent according to Item 9 or 10.

Further, the present invention provides the following manufacturing method.

Item A. (i) a step of polymerizing a hydrophilic (or hydrophobic) monomer in the presence of a polymerization initiator, (ii) a step of polymerizing the obtained hydrophilic (or hydrophobic) block and a fiber-reactive monomer under light irradiation , (Iii) Hydrophilic-hydrophobic-fiber reaction including a step of polymerizing the obtained hydrophilic (or hydrophobic) -fiber-reactive block copolymer oligomer and a hydrophobic (or hydrophilic) monomer under light irradiation. Method for producing a terpolymer block copolymer oligomer having a terpolymer property.

Item B. (i) a step of polymerizing a hydrophilic (or hydrophobic) monomer in the presence of a polymerization initiator, (ii) the resulting hydrophilic (or hydrophobic) block and hydrophobic (or hydrophilic)
A step of polymerizing the monomer under light irradiation, (iii) the hydrophilicity-the step of polymerizing the resulting hydrophilic-hydrophobic block copolymer oligomer and the fiber-reactive monomer under light irradiation-
A method for producing a hydrophobic-fiber reactive ternary block copolymer oligomer.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION In the binary block copolymer oligomer of the present invention, when the fiber-reactive monomer is hydrophilic, the fiber-reactive block can serve also as the hydrophilic block, so that the ternary block copolymer oligomer can be used. It has the same antifouling effect as the copolymer oligomer.

In the block copolymer of the present invention, it is important that the hydrophilic block, the hydrophobic block and the fiber-reactive block are separated, and the monomer (hydrophilic, hydrophobic,
A copolymer in which (fiber reactivity) is randomly bonded has a weak antifouling effect and is not included in the present invention.

The term "block" in the present invention means that hydrophilic, hydrophobic or fiber-reactive monomers are not randomly bonded. For example, one molecule of hydrophilic monomer is contained in one copolymer. If included only, the hydrophilic block consists of this one molecule of hydrophilic monomer. Similarly,
The hydrophobic block and the fiber-reactive block are composed of one or more molecules of the corresponding monomers.

The "oligomer" of the present invention means that the block copolymer of the present invention is intended for those having a number average molecular weight of 10,000 or less. Therefore, when the molecular weight of the monomer is large, the upper limit of the number of monomers is small, and when the molecular weight of the monomer is small, the upper limit of the number of monomers is large.

The polymerization initiator used in the production method of the present invention is preferably one which can control the initiation and termination of the reaction in order to produce a block copolymer so as to combine two or three blocks stepwise. . Examples of such an initiator include tetraethylthiuram disulfide (TD) and PAT, TPSN, TMPSN, PPE and BDC whose structures are shown below.

[0034]

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And the like, preferably tetraethylthiuram disulfide (TD).

As the hydrophilic monomer, methoxyethylene glycol 1000 methacrylate, polyethylene glycol monomethacrylate (Blenmer P manufactured by NOF CORPORATION)
E), esters of (meth) acrylic acid such as methoxyethylene glycol 400 acrylate and (poly) ethylene glycol or polypropylene glycol having an alkoxy group having 1 to 4 carbon atoms at the terminal, methacrylic acid or its salt, acrylic acid or its salt Etc. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,
Examples thereof include alkoxy groups such as isobutoxy, sec-butoxy and tert-butoxy. Examples of the (meth) acrylic acid salt include alkali metal salts such as sodium, potassium and lithium, and alkaline earth metal salts such as calcium and magnesium.

As the hydrophobic monomer, perfluoroalkylethyl (meth) such as perfluorooctylethyl methacrylate and perfluorooctylethyl acrylate is used.
Acrylate; Perfluoroalkyl (meth) acrylate such as perfluorooctyl methacrylate, perfluorononyl methacrylate, perfluorodecyl methacrylate; Perfluoroalkylmethyl (meth) acrylate such as perfluorooctylmethyl methacrylate; Preferably 3-18, more preferably 4-16, and even more preferably 6-12) 6 carbon atoms in which a majority of hydrogen atoms of the alkyl group are substituted with fluorine atoms.
-25 (preferably 6-21, more preferably 7-1)
9, and more preferably 9 to 15) fluorinated alkyl (meth) acrylates.

Examples of the fiber-reactive monomer include monomers having an N-methylol group and a reactive double bond, and specific examples thereof include N-methylol acrylamide and N-.
Examples include hydrophilic fiber-reactive monomers such as methylol methacrylamide, and preferably N-methylol acrylamide. The fiber-reactive monomer of the present invention reacts with a hydroxyl group of a cellulose fiber to form a covalent bond, but does not react with a fiber having no hydroxyl group such as polyester, but by incorporating a fiber-reactive block, these fibers are added to these fibers. Strongly adheres to it. In addition, in this specification, a hydrophilic fiber-reactive monomer may be described as a "hydrophilic fiber-reactive monomer", and examples of such a monomer include N-methylol acrylamide and N-methylol methacrylamide.

Fibers treated with the ternary block copolymer oligomer of the present invention include natural cellulose such as cotton and hemp, regenerated cellulose such as rayon, or a mixed fiber thereof such as cellulose fiber, polyester, nylon, Acrylic is mentioned, and cellulose fiber and polyester are preferable. The fiber is in the form of a primary processed product such as a yarn, a knit, a woven fabric, a knitted fabric, a non-woven fabric, or the like of the invention.
It is treated with an antifouling agent containing the original block copolymer oligomer as an essential component.

The textile product of the present invention means, for example, a product such as clothing, bedding and interior made of the above-mentioned cellulose fiber or polyester.

The amount of the stainproofing agent used varies depending on the type of fiber and is not particularly limited, but the block copolymer, which is an essential component, is usually used in an amount of 0. It is used in an amount of about 1 to 3% by weight.

The ternary block copolymer oligomer of the present invention may have at least one molecule each of the hydrophilic monomer, the hydrophobic monomer and the fiber-reactive monomer. From the viewpoint of improving antifouling properties, it is preferable that the oligomers have the same hydrophilicity and hydrophobicity. As a criterion for determining hydrophilicity and hydrophobicity, for example, a block copolymer composed of one molecule of methoxyethylene glycol 1000 methacrylate as a hydrophilic monomer and one molecule of perfluorooctylmethyl methacrylate as a hydrophobic monomer has a slightly high hydrophobicity. When 1 molecule of hydrophilic N-methylol acrylamide as a fiber-reactive monomer is further added to 2 molecules,
The ternary block copolymer oligomer composed of the three molecules has a hydrophilic property and a hydrophobic property in a well-balanced state, and the antifouling property is also high. The number average molecular weight of the copolymer oligomer is
600 to 10,000, preferably 1000 to 600
It is about 0, more preferably about 1500 to 3000.

The hydrophilic-hydrophobic-fiber-reactive block copolymer oligomer and the hydrophobic-hydrophilic fiber-reactive block copolymer oligomer can be synthesized, for example, by using tetrahydrofuran (THF), dioxane, or a water mixed solvent thereof. Are synthesized.

Methoxyethylene glycol 1000 methacrylate and polyethylene glycol monomethacrylate (Blenmer PE manufactured by NOF CORPORATION) are exemplified as preferable hydrophilic polymers.

When tetraethyl thiuram disulfide is used as the polymerization initiator, the disulfide is decomposed by heat and light (ultraviolet light) to be added to the monomer. This thermal reaction can be performed at a reaction temperature of about 60 ° C. to 100 ° C., and the photoreaction can be performed at room temperature. Decomposition of the diethyldithiocarbamate group is carried out by using light (ultraviolet ray), and the monomer of the second component is added, and the step is further repeated to add the monomer of the third component to form a ternary block copolymer oligomer. To synthesize. For the binary block copolymer oligomer, the step of adding the third component may be omitted. The copolymer oligomer is usually obtained as an oligomer. This photoreaction can also be performed at room temperature.

The elimination of the diethyldithiocarbamate group at the terminal of the ternary block copolymer oligomer is carried out by irradiating light in the presence of a chain transfer agent, heating in the presence of an acid, or reaction with an amine. Can be done by. As the chain transfer agent, thiols such as 2-ethylhexyl thioglycolate, alcohols such as isopropanol, amines and phenols are used.
As the acid, magnesium chloride, hydrochloric acid, sulfuric acid, phosphoric acid,
Examples thereof include inorganic acids such as hydrobromic acid, and organic acids such as p-toluenesulfonic acid, methanesulfonic acid, acetic acid and trifluoroacetic acid. Examples of the amine include aromatic or aliphatic primary or secondary amines such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine and aniline.

The antifouling treatment of the fiber with the binary or ternary block copolymer oligomer is carried out by a usual method. That is, the block copolymer oligomer is put in a predetermined concentration in water, and the pad catalyst is prepared by using an acid catalyst such as magnesium chloride.
Process by dry-cure method.

At this time, by heating in the presence of an acid catalyst, the terminal dithiocarbamate group of the block copolymer oligomer is decomposed.

In the processing with the ternary block copolymer oligomer of the present invention, when the work cloth is present in the air, the hydrophobic groups are exposed on the surface, exhibiting hydrophobicity and making it difficult to stain.
When washed in water, hydrophilic groups are exposed to the surface to show hydrophilicity, which facilitates the removal of attached dirt. The ternary block copolymer oligomer is more preferable than the ternary random copolymer oligomer because of its large antifouling effect.

Since this block copolymer oligomer is an oligomer having a number average molecular weight of 600 to 10,000,
The texture of the processed cloth is also good.

According to the hydrophilic-hydrophobic block copolymer oligomer of the present invention and the method for producing the same and its use as an antifouling agent, a hydrophilic initiator having a molecular weight of up to 10,000 can be prepared by using the radical initiator tetraethylthiuram disulfide. A hydrophobic block copolymer oligomer can be synthesized. Radical polymerization does not require removal of water from the system,
The polymerization temperature can be room temperature to 100 ° C, and the polymerization operation is simple.

The processing of the fiber by the hydrophilic-hydrophobic block copolymer oligomer (oligomer) can be carried out by an ordinary method. When processed by using an acid catalyst, the N-methylol group of the copolymer oligomer becomes a cellulose fiber. Reacting,
It has a wash resistance.

[0053]

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

Example 1 Synthesis of Hydrophilic-Hydrophobic-Fiber Reactive Block Copolymer Oligomer 0.025 mol of methoxyethylene glycol 1000 methacrylate and 0.025 mol of tetraethyl thiuram disulfide were placed in a 300 ml eggplant-shaped flask,
It was dissolved in 50 ml of dioxane, stirred at 100 ° C. with a magnetic stirrer, and subjected to an addition reaction for 20 hours. The GPC measurement results of the product were number average molecular weight 1,597, weight average molecular weight 1,718, and weight average molecular weight / number average molecular weight = 1.08 (calculated molecular weight 1,365). Further, add 0.025 mol of N-methylol acrylamide to 50 m.
It was dissolved in 1-dioxane, added to the above polymerization solution, and irradiated with a 400 W high-pressure mercury lamp at room temperature for 5 hours. Then, the number average molecular weight 1,635, the weight average molecular weight 1,739, the weight average molecular weight / number average molecular weight = 1.06 (the calculated molecular weight 1,
A block copolymer oligomer of 466) was obtained.

Further, 0.025 mol of perfluorooctylethyl methacrylate was added, and irradiation was carried out with a 400 W high pressure mercury lamp at room temperature for 13 hours. And the number average molecular weight of 1,777, the weight average molecular weight of 1,833, the weight average molecular weight / the number average molecular weight = 1.06 (the calculated molecular weight of 1,99
A hydrophilic-hydrophobic block copolymer oligomer of 3) was obtained.

Example 2 Synthesis of Hydrophilic-Hydrophobic-Fiber Reactive Block Copolymer Oligomer 0.025 mol of perfluorooctylethyl methacrylate and 0.025 mol of tetraethylthiuram disulfide were placed in a 300 ml eggplant-shaped flask and dioxane 10 was added.
It was dissolved in 0 ml, stirred at 100 ° C. with a magnetic stirrer, and subjected to an addition reaction for 18 hours. Product GPC
The measurement results are number average molecular weight 521, weight average molecular weight 52.
9, weight average molecular weight / number average molecular weight = 1.01 (calculated molecular weight 829). Further, 0.025 mol of methoxyethylene glycol 400 acrylate was added to the above reaction solution, and irradiation was performed with a 100 W high pressure mercury lamp at room temperature for 13.5 hours. And the number average molecular weight 831, the weight average molecular weight 857, the weight average molecular weight / the number average molecular weight = 1.03.
A block copolymer oligomer having a calculated molecular weight of 1,283 was obtained.

Further, 0.025 mol of N-methylol acrylamide was added, and the mixture was irradiated with a 100 W high pressure mercury lamp at room temperature for 26 hours. And number average molecular weight 914, weight average molecular weight 947, weight average molecular weight / number average molecular weight =
A hydrophilic-hydrophobic block copolymer oligomer having a molecular weight of 1.04 (calculated molecular weight 1,384) was obtained.

Example 3 Synthesis of Hydrophilic-Hydrophobic-Fiber Reactive Block Copolymer Oligomer 0.025 mol of perfluorooctylethyl methacrylate and 0.025 mol of tetraethylthiuram disulfide were placed in a 300 ml eggplant-shaped flask and 50 ml of THF was added.
And was stirred with a magnetic stirrer at room temperature and irradiated with a 100 W high-pressure mercury lamp for 15 hours to carry out an addition reaction. The GPC measurement result of the product shows that the number average molecular weight is 574,
The weight average molecular weight was 586, and the weight average molecular weight / number average molecular weight = 1.02 (molecular weight calculated value 829). Methoxyethylene glycol 400 acrylate 0.025
Mols were added to the above reaction solution and irradiated with a 100 W high pressure mercury lamp at room temperature for 12.5 hours. And a number average molecular weight of 8
17, a block copolymer oligomer having a weight average molecular weight of 836 and a weight average molecular weight / number average molecular weight = 1.02 (calculated molecular weight 1,283) was obtained.

Furthermore, methoxyethylene glycol 10
0.025 mol of 00 methacrylate was added, and the mixture was irradiated with a 100 W high pressure mercury lamp at room temperature for 19.5 hours. And the number average molecular weight 1,629, the weight average molecular weight 1,721,
A block copolymer oligomer having a weight average molecular weight / number average molecular weight = 1.06 (calculated molecular weight 2,351) was obtained.

Next, 0.025 mol of N-methylol acrylamide was added, and the mixture was irradiated with a 100 W high pressure mercury lamp at room temperature for 24 hours. And number average molecular weight of 1,70
9, a hydrophilic-hydrophobic block copolymer oligomer having a weight average molecular weight of 1,833 and a weight average molecular weight / number average molecular weight = 1.07 (calculated molecular weight of 2,452) was obtained.

Example 4 Synthesis of Hydrophilic-Hydrophobic-Fiber Reactive Block Copolymer Oligomer 0.025 mol of perfluorooctylethyl methacrylate and 0.025 mol of tetraethylthiuram disulfide were placed in a 300 ml eggplant-shaped flask, and 50 ml of THF was added.
And was stirred with a magnetic stirrer at room temperature and irradiated with a 400 W high pressure mercury lamp for 3 hours to carry out an addition reaction. The GPC measurement results of the product are number average molecular weight 580, weight average molecular weight 586, weight average molecular weight / number average molecular weight =
It was 1.01 (calculated molecular weight: 829). Further, 0.25 mol of methacrylic acid was added to the above reaction solution, and the mixture was irradiated with a 400 W high pressure mercury lamp at room temperature for 12 hours. Then, a block copolymer oligomer having a number average molecular weight of 1,303, a weight average molecular weight of 1,454, and a weight average molecular weight / number average molecular weight = 1.12 (calculated molecular weight of 1,690) was obtained.

Next, 0.025 mol of N-methylol acrylamide was dissolved in 50 ml of THF and added,
Irradiation was performed with a 0 W high pressure mercury lamp at room temperature for 5 hours. And the number average molecular weight 1,352, the weight average molecular weight 1,503,
A hydrophilic-hydrophobic block copolymer oligomer having a weight average molecular weight / number average molecular weight = 1.11 (calculated molecular weight 1,791) was obtained. The copolymer oligomer was neutralized with sodium hydroxide.

Example 5 Synthesis of hydrophilic-hydrophobic-fiber reactive block copolymer oligomer 0.025 mol of methoxyethylene glycol 1000 methacrylate and 0.025 mol of tetraethyl thiuram disulfide were placed in a 300 ml eggplant-shaped flask,
It was dissolved in 50 ml of dioxane, stirred at 100 ° C. with a magnetic stirrer, and subjected to an addition reaction for 20 hours. The GPC measurement results of the product were number average molecular weight 1,597, weight average molecular weight 1,718, and weight average molecular weight / number average molecular weight = 1.08 (calculated molecular weight 1,365). Further, add 0.025 mol of N-methylol acrylamide to 50 m.
It was dissolved in 1-dioxane, added to the above polymerization solution, and irradiated with a 400 W high-pressure mercury lamp at room temperature for 5 hours. Then, the number average molecular weight 1,635, the weight average molecular weight 1,739, the weight average molecular weight / number average molecular weight = 1.06 (the calculated molecular weight 1,
A block copolymer oligomer of 466) was obtained.

Furthermore, 0.025 mol of perfluorooctylethyl acrylate was added, and a 100 W high pressure mercury lamp was used.
Irradiation was performed at room temperature for 14 hours. And the number average molecular weight 1,
717, weight average molecular weight 1,819, weight average molecular weight /
A hydrophilic-hydrophobic block copolymer oligomer having a number average molecular weight of 1.06 (calculated molecular weight of 1,984) was obtained.

Example 6 Synthesis of hydrophilic-hydrophobic-fiber reactive block copolymer oligomer 0.025 mol of methoxyethylene glycol 1000 methacrylate and 0.025 mol of tetraethyl thiuram disulfide were placed in a 300 ml eggplant-shaped flask,
It was dissolved in 50 ml of dioxane, stirred at 100 ° C. with a magnetic stirrer, and subjected to an addition reaction for 20 hours. The GPC measurement results of the product were number average molecular weight 1,597, weight average molecular weight 1,718, and weight average molecular weight / number average molecular weight = 1.08 (calculated molecular weight 1,365).

Further, 0.25 mol of acrylic acid was added to the above reaction solution and irradiated with a 400 W high pressure mercury lamp at room temperature for 5 hours. And the number average molecular weight 1,682, the weight average molecular weight 2,023, the weight average molecular weight / the number average molecular weight =
A block copolymer oligomer having a molecular weight of 1.20 (calculated molecular weight 2,212) was obtained.

Next, 0.025 mol of N-methylolacrylamide was dissolved in 50 ml of dioxane, added to the above polymerization solution, and irradiated with a 400 W high pressure mercury lamp at room temperature for 19 hours. And the number average molecular weight 1,752, the weight average molecular weight 2,227, the weight average molecular weight / the number average molecular weight =
A block copolymer oligomer having a molecular weight of 1.27 (calculated molecular weight: 2,313) was obtained.

Then, 0.025 mol of perfluorooctylethyl methacrylate was added, and the mixture was irradiated with a 400 W high pressure mercury lamp at room temperature for 30 hours. And the number average molecular weight 1,850, the weight average molecular weight 2,533, the weight average molecular weight / number average molecular weight = 1.37 (the calculated molecular weight is 2,85
A hydrophilic-hydrophobic block copolymer oligomer of 9) was obtained.

Then, the block copolymer oligomer was neutralized with sodium hydroxide.

Example 7 Synthesis of hydrophilic-hydrophobic-fiber reactive block copolymer oligomer Methoxyethylene glycol 1000 methacrylate 5
3.4 g, N-methylol acrylamide 5.1 g, perfluorooctylethyl methacrylate 26.6 g, tetraethyl thiuram disulfide 0.2966 g (molar ratio 1: 1: 1: 0.02) in 100 ml of THF at room temperature for 5 hours, A hydrophilic-hydrophobic block having a number average molecular weight of 1,677, a weight average molecular weight of 1,799, a weight average molecular weight / number average molecular weight = 1.07 (calculated molecular weight of 1,701), which is polymerized by irradiation with a 400 W high-pressure mercury lamp. A copolymer oligomer was obtained.

Example 8 Synthesis of Hydrophobic-Hydrophilic Fiber Reactive Block Copolymer Oligomer (Binary System) 0.025 mol of perfluorooctylethyl methacrylate and 0.025 mol of tetraethylthiuram disulfide were placed in a 300 ml eggplant type flask. Put, THF 50ml
And was stirred with a magnetic stirrer at room temperature and irradiated with a 400 W high pressure mercury lamp for 3 hours to carry out an addition reaction. The GPC measurement results of the product are number average molecular weight 580, weight average molecular weight 586, weight average molecular weight / number average molecular weight =
It was 1.01 (calculated molecular weight: 829).

Next, 0.025 mol of N-methylol acrylamide was dissolved in 50 ml of THF and added to 40
A hydrophobic-hydrophilic fiber-reactive block copolymer oligomer (binary system) was obtained by irradiation with a 0 W high-pressure mercury lamp at room temperature for 5 hours.

Example 9 (1) Elimination of dithiocarbamate group I 5 g of the hydrophilic-hydrophobic-fiber reactive block copolymer oligomer obtained in Example 1 was added to 50 ml of THF, and 100 ml of chain transfer agent isopropanol was added to 300 ml of eggplant type. It was placed in a flask and irradiated with a 400 W high pressure mercury lamp for 30 hours. After that, the solvent and the chain transfer agent are distilled off and reprecipitation is carried out.
When the infrared absorption spectrum of the obtained block copolymer oligomer was measured, it was 1195 cm ⁻¹ (νC = S),
1495 cm ^-1 (νC = S), 1270 cm ^-1 (νC-
It was found that the absorption of the dithiocarbamate group in the vicinity of N) had disappeared and that it had been eliminated.

(2) Elimination of dithiocarbamate group II 5 g of the hydrophilic-hydrophobic-fiber reactive block copolymer oligomer obtained in Example 1, 50 ml of THF, n-
20 ml of propylamine was placed in a 300 ml eggplant-shaped flask and reacted by stirring at 60 ° C. for 30 hours. Then, the solvent and di-n-propylamine were distilled off and reprecipitated, and the infrared spectrum of the obtained block copolymer was measured to find that it was 1195 cm ⁻¹ (νC = S), 1495 cm ^−1.
(ΝC = S), the absorption of the dithiocarbamate group near 1270 cm ⁻¹ (νC—N) disappeared, and it was revealed that the dithiocarbamate group was eliminated.

(3) Elimination of dithiocarbamate group III When 5 g of the hydrophilic-hydrophobic-fiber reactive block copolymer oligomer obtained in Example 8 was treated under the same conditions as in (1) above, IR Removal of the dithiocarbamate group was confirmed by the disappearance of the peak.

Comparative Example 1 Synthesis of Hydrophilic Polymer Methoxyethylene glycol 400 acrylate 90.
8 g, N-methylol acrylamide 10.1 g (molar ratio 2: 1) in 300 ml isopropanol, using 0.2 g of benzoyl peroxide as an initiator and 1 ml of chain transfer agent 2-ethylhexyl thioglycolate at 60 ° C. for 25 hours. Polymerization gave 103.7 g of hydrophilic polymer.

Comparative Example 2 Synthesis of Hydrophilic Polymer Methoxyethylene glycol 400 acrylate 90.
8 g, N, N-dimethylaminoethyl acrylate methyl chloride quaternary salt 38.8 g and N-methylol acrylamide 10.1 g (molar ratio 2: 2: 1) were polymerized in the same manner as in Comparative Example 1 to prepare hydrophilic polymer 138. 5 g was obtained.

Comparative Example 3 Synthesis of Hydrophilic Block Copolymer Oligomer 0.025 mol of methoxyethylene glycol 1000 methacrylate and 0.025 mol of tetraethyl thiuram disulfide were placed in a 300 ml eggplant-shaped flask,
It was dissolved in 50 ml of dioxane, stirred at 100 ° C. with a magnetic stirrer, and subjected to an addition reaction for 20 hours. The GPC measurement results of the product were number average molecular weight 1,597, weight average molecular weight 1,718, and weight average molecular weight / number average molecular weight = 1.08 (calculated molecular weight 1,365). Further, add 0.025 mol of N-methylol acrylamide to 50 m.
It was dissolved in 1 dioxane, added to the above reaction solution, and irradiated with a 400 W high-pressure mercury lamp at room temperature for 5 hours. Then, the solvent is distilled off to obtain a number average molecular weight of 1,635 and a weight average molecular weight of 1,
A hydrophilic block copolymer oligomer of 739, weight average molecular weight / number average molecular weight = 1.06 (calculated molecular weight 1,466) was obtained.

Comparative Example 4 Synthesis of random copolymer oligomer Methoxyethylene glycol 1000 methacrylate 5
3.4 g, perfluorooctylethyl methacrylate 2
6.6 g and N-methylol acrylamide 5.1 g (molar ratio 1: 1: 1) were polymerized in the same manner as in Comparative Example 1 to obtain 84.0 g of a random copolymer oligomer.

Production Example 1 10% of the copolymer oligomer synthesized in Example 1 and a 3% aqueous solution of magnesium chloride hexahydrate were padded, and 100 ° C.
It was dried for 3 minutes, cured at 150 ° C. for 3 minutes, washed with hot water and dried to process cotton broad and polyester taffeta.

The processed cloth was subjected to the following soil release test and anti-soil redeposition test.

Friction electrification voltage (rotary static tester) of polyester processed cloth (after washing 10 times) is 60V.
(Unprocessed cloth 3,400V).

Water repellency of the processed cloth (spray method) is 40% cotton
(Unprocessed cloth 0%), Polyester 30% (Unprocessed cloth 10
%)Met.

The tear strength of the processed cloth is 520 g of cotton length.
f (unprocessed cloth 1,040 gf), cotton weft 460 gf (unprocessed cloth 800 gf), polyester vertical 2,380 g
f (unprocessed cloth 2,130 gf) and polyester weft 2,470 gf (unprocessed cloth 1,830 gf).

Production Example 2 A 10% aqueous solution of the copolymer oligomer synthesized in Example 2 and a 3% aqueous solution of magnesium chloride hexahydrate were used as a pad, and 100 ° C.
It was dried for 3 minutes, cured at 150 ° C. for 3 minutes, washed with hot water and dried to process cotton broad and polyester taffeta.

The processed cloth was subjected to the following soil release test and anti-soil redeposition test.

Production Example 3 10% aqueous solution of the copolymer oligomer synthesized in Example 3 and a 3% aqueous solution of magnesium chloride hexahydrate were padded at 100 ° C.
It was dried for 3 minutes, cured at 150 ° C. for 3 minutes, washed with hot water and dried to process cotton broad and polyester taffeta.

The processed cloth was subjected to the following soil release test and anti-soil redeposition test.

Production Example 4 10% of the copolymer oligomer synthesized in Example 4 and a 3% aqueous solution of magnesium chloride hexahydrate were padded, and 100 ° C.
It was dried for 3 minutes, cured at 150 ° C. for 3 minutes, washed with hot water and dried to process cotton broad and polyester taffeta.

The processed cloth was subjected to the following soil release test and anti-soil redeposition test.

Comparative Production Example 1 Antifouling Treatment with Hydrophilic Polymer Methoxyethylene glycol 400 acrylate 90.
8 g, N-methylol acrylamide 10.1 g (molar ratio 2: 1) in 300 ml isopropanol, using 0.2 g of benzoyl peroxide as an initiator and 1 ml of chain transfer agent 2-ethylhexyl thioglycolate at 60 ° C. for 25 hours. Polymerization gave 103.7 g of hydrophilic polymer.

10% of this polymer, magnesium chloride 6
Pad with 3% aqueous solution of hydrate, dry at 100 ° C for 3 minutes, cure at 150 ° C for 3 minutes, and then rinse with hot water,
It was dried and processed into cotton broad and polyester taffeta.

The processed cloth was subjected to the following soil release test and anti-redeposition test.

Friction electrification voltage (rotary static tester) of polyester processed cloth (after washing 10 times) is 65V.
(Unprocessed cloth 3,400V).

Comparative Production Example 2 Antifouling Treatment with Hydrophilic Polymer Methoxyethylene glycol 400 acrylate 90.
8 g, N, N-dimethylaminoethyl acrylate methyl chloride quaternary salt 38.8 g and N-methylol acrylamide 10.1 g (molar ratio 2: 2: 1) were polymerized in the same manner as in Comparative Example 1 to prepare hydrophilic polymer 138. 5 g was obtained.

Cotton broad and polyester taffeta were processed with this polymer in the same manner as in Comparative Example 1.

The processed cloth was subjected to the following soil release test and anti-soil redeposition test.

The friction electrification voltage (rotary static tester) of the polyester processed cloth (after washing 10 times) is 2,20.
It was 0V (raw fabric 3,400V).

Comparative Production Example 3 Antifouling Treatment with Hydrophilic Block Copolymer Oligomer 0.025 mol of methoxyethylene glycol 1000 methacrylate and 0.025 mol of tetraethyl thiuram disulfide were placed in a 300 ml eggplant-shaped flask,
It was dissolved in 50 ml of dioxane, stirred at 100 ° C. with a magnetic stirrer, and subjected to an addition reaction for 20 hours. The GPC measurement results of the product were number average molecular weight 1,597, weight average molecular weight 1,718, and weight average molecular weight / number average molecular weight = 1.08 (calculated molecular weight 1,365). Further, add 0.025 mol of N-methylol acrylamide to 50 m.
It was dissolved in 1 dioxane, added to the above reaction solution, and irradiated with a 400 W high-pressure mercury lamp at room temperature for 5 hours. Then, the solvent is distilled off to obtain a number average molecular weight of 1,635 and a weight average molecular weight of 1,
A hydrophilic block copolymer oligomer of 739, weight average molecular weight / number average molecular weight = 1.06 (calculated molecular weight 1,466) was obtained.

10% of this block copolymer oligomer,
Pad with 3% aqueous solution of magnesium chloride hexahydrate, 10
Dry at 0 ℃ for 3 minutes, cure at 150 ℃ for 3 minutes,
Then, it was washed with hot water and dried to process cotton broad and polyester taffeta.

The processed cloth was subjected to the following soil release test and anti-redeposition test.

Comparative Production Example 4 Antifouling treatment with random copolymer oligomer Methoxyethylene glycol 1000 methacrylate 5
3.4 g, perfluorooctylethyl methacrylate 2
6.6 g and N-methylol acrylamide 5.1 g (molar ratio 1: 1: 1) were polymerized in the same manner as in Comparative Example 1 to obtain 84.0 g of a random copolymer oligomer.

Cotton broad and polyester taffeta were processed with this polymer in the same manner as in Comparative Example 1.

The processed cloth was subjected to the following soil release test and anti-soil redeposition test.

<Test Example I> Soil Release Test A dirty motor oil and India ink were applied to predetermined positions on the antifouling cloths obtained in the above Production Examples 1 to 4 and Comparative Production Examples 1 to 4, respectively, and left for 2 hours. Then, a contaminated cloth was created. Next, these contaminated cloths were washed and the degree of stain removal was evaluated according to the following five-grade evaluation criteria.

Grade 1: No detachment of dirt was observed.

Grade 2: Slight removal of dirt.

Grade 3: Stain removal is moderate.

Grade 4: Clear removal of stains.

Grade 5: Only traces of dirt can be confirmed, or almost no dirt can be confirmed.

The results are shown in Tables 1 and 2 below.

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[Table 1] Soil releasability (cotton broad with 100% cotton) Dirty motor oil ink After processing after washing 10 times After processing after washing 10 times Production example 1 3rd grade 3rd grade 3rd grade 3rd production example 2 3rd grade 3rd grade 2nd class 2nd class manufacturing example 3 3rd class 3rd class 2nd class 2nd class manufacturing example 4 4th class 4th class 3rd class 3rd class Comparative manufacturing example 1 1st class 1st class 2nd class 1st class Comparative manufacturing example 2 2nd class 2nd class 2nd class 1st class Comparative Production Example 3 2nd Grade 2nd Grade 2nd Grade 1st Comparative Production Example 4 2nd Grade 2nd Grade 2nd Grade 1st Grade Unprocessed Fabric 1st Grade 1st Grade 1st Grade 1st Grade

[0113]

[Table 2] Soil releasability (polyester taffeta made of 100% polyester) Dirty motor oil ink After processing after washing 10 times After processing after washing 10 times 3rd class 3rd class manufacturing example 3 4th class 4th class 3rd class 3rd class manufacturing example 4 5th class 5th class 4th class 4th class comparative manufacturing example 1 4th class 4th class 2nd class 2nd class comparative manufacturing example 2 2nd class 2nd class 2nd class Comparative Manufacturing Example 3 3rd Class 3rd Class 2nd Class 2nd Comparative Comparative Example 4 3rd Class 3rd Class 2nd Class 2nd Class Untreated Cloth 1st Class 1st Class 2nd Class 2nd Class <Test Example II> Recontamination Prevention Test .3 ml / liter and household detergent 2.
After making a solution in which 5 g / liter was dissolved and washing the laundry, the degree of contamination was 1 to 5 on the JIS contamination gray scale.
It was judged by grade. 1 in JIS pollution gray scale
The grade is when the pollution is severe, and the grade 5 is when there is no pollution. The results are shown in Tables 3 and 4 below.

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[Table 3]

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[Table 4]

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Industrial Applicability The hydrophilic-hydrophobic block copolymer oligomer (oligomer) production method of the present invention and its use as an antifouling agent can be synthesized by radical polymerization to obtain a block copolymer oligomer (oligomer). Depending on the method, the fibers can be antifouling processed.

The radical polymerization is advantageous in that the polymerization operation is easy, it is most industrially used, and it can be polymerized even in an aqueous system.

The hydrophilic-hydrophobic block copolymer oligomer of the present invention may be used as a compatibilizer for polymer alloys and a surface modifier for plastics (adhesiveness, water repellent, antifogging agent, etc.). is there.

Front page continuation (72) Inventor Shizuo Kubota 567 Higashi-Shibuda, Katsuragi-cho, Ito-gun, Wakayama

Claims (11)

[Claims] 1. A hydrophilic-hydrophobic-fiber reactive terpolymer block copolymer oligomer characterized by polymerizing a polymerization initiator, a hydrophilic monomer, a hydrophobic monomer and a fiber reactive monomer under light irradiation. Manufacturing method. 2. A method for producing a hydrophobic-fiber-reactive binary block copolymer oligomer, which comprises polymerizing a polymerization initiator, a hydrophobic monomer and a fiber-reactive monomer under light irradiation. 3. A polymerization initiator (1) is tetraethylthiuram disulfide, and (2) a hydrophilic monomer is lower alkoxyethylene glycol (meth) acrylate, lower alkoxypropylene glycol (meth) acrylate,
At least one selected from the group consisting of methacrylic acid, methacrylic acid salt, acrylic acid, and acrylic acid salt, (3) the hydrophobic monomer is perfluoroalkyl (meth) acrylate, and (4) the fiber-reactive monomer is N-. The method according to claim 1, which is methylol (meth) acrylamide. 4. A hydrophilic-hydrophobic-fiber-reactive block copolymer oligomer obtained by the method according to claim 1 or 3 is irradiated with light in the presence of a chain transfer agent, and heated in the presence of an acid. Of the hydrophilic-hydrophobic-fiber-reactive block copolymer oligomer, characterized in that the terminal diethyldithiocarbamate group is eliminated by performing any treatment selected from the group consisting of treatment and treatment with amine. Manufacturing method. 5. A hydrophilic block, a hydrophobic block and a fiber-reactive block having a number average molecular weight of 600 to 10,
Terpolymer block copolymer oligomer of 000. 6. The terpolymer block copolymer oligomer according to claim 5, which contains a diethyldithiocarbamate group at the terminal. 7. (1) The hydrophilic monomer is selected from the group consisting of lower alkoxy ethylene glycol (meth) acrylate, lower alkoxy propylene glycol (meth) acrylate, methacrylic acid, methacrylic acid salt, acrylic acid and acrylate. 7. The method according to claim 5, wherein at least one kind of (2) the hydrophobic monomer is perfluoroalkyl (meth) acrylate, and (3) the fiber-reactive monomer is N-methylol (meth) acrylamide.
Original block copolymer oligomer 8. A hydrophobic-hydrophilic fiber-reactive binary block copolymer oligomer having a hydrophobic block and a hydrophilic fiber-reactive block and having a number average molecular weight of 600 to 10,000. 9. The hydrophilic property according to any one of claims 5 to 7.
An antifouling agent containing a hydrophobic-fiber reactive block copolymer oligomer as an essential component. 10. An antifouling agent containing the hydrophobic-hydrophilic fiber-reactive binary block copolymer oligomer according to claim 8 as an essential component. 11. A fiber product obtained by processing with the stainproofing agent according to claim 9 or 10.