JP3485056B2 - Fiber treatment agent, treatment liquid, treatment method and treated fiber - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fiber treating agent containing a copolymer obtained by polymerizing a composition containing a phosphorylcholine group-containing monomer as a main component, a fiber treating agent solution thereof, a fiber treating method and the above-mentioned method. The present invention relates to a fiber to be treated which has been treated by a treatment method. More specifically, the present invention relates to a fiber treatment agent which imparts hydrophilicity to fibers and improves the feel when contacting the skin.

[0002]

2. Description of the Related Art Phosphorylcholine group-containing polymers are excellent in biocompatibility such as blood compatibility, complement deactivation, and nonadsorption of biological substances due to the phospholipid-like structure derived from biological membranes. It is known to have excellent properties such as antifouling property and moisturizing property, and active research and development has been conducted on the synthesis of polymers and their use for the purpose of developing biomaterials that utilize their respective functions. ing. Among them, JP-A-9
JP-A-315935 and JP-A-9-315949 disclose that a phosphorylcholine group-containing polymer has an effect of protecting the skin when it is used as a cosmetic, but it treats a fiber or a cloth. It has not been known that the effect of improving the touch to the skin and imparting hygroscopicity by doing so.

Further, Polym. Preprints,
Japan, Vol. 47, No. 3, pp. 606,
In 1999, a method of graft-polymerizing a phosphorylcholine group-containing monomer onto silk was disclosed. The above-mentioned method has a problem that the production efficiency is very low because the polymerization operation is complicated and a step of removing the initiator, residual monomer and the like which may be toxic is required. There is a demand for a material which, by a simple method, treats a fiber, a cloth or the like to improve the tactile sensation to the skin and impart hygroscopicity.

[0004]

The first object of the present invention is to provide a fiber treating agent comprising a copolymer obtained by polymerizing a specific phosphorylcholine-like group-containing monomer. Moreover, the 2nd objective of this invention is to provide the fiber treatment agent solution. A third object of the present invention is to provide a fiber treatment method. Further, a fourth object of the present invention is to provide a fiber to be treated which is treated by the above treatment method.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above-mentioned problems, and as a result, as a result, polymerization of a monomer composition containing a specific phosphorylcholine-like group-containing monomer is obtained. The present invention has been completed based on the finding that treating the coalescence into fibers imparts hydrophilicity and improves the feel of the cloth when it comes into contact with the skin.

[1] The following equation (1)

[0007]

[Chemical 3]

{Wherein X represents a divalent organic residue, Y represents an alkyleneoxy group having 1 to 6 carbon atoms, and Z represents
Represents a hydrogen atom or R ⁵ —O— (C═O) — (wherein R ⁵ represents an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms). R ¹ represents a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ are the same or different groups and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group. m is 0
Or 1 is shown. n is an integer of 1 to 4. } Phosphorylcholine-like group-containing monomer 20 to 9 represented by component A
8 mol% and 2 to 80 mol% of B component hydrophobic monomer
Molecular weight of 1000, which is obtained by polymerizing a monomer composition consisting of
A fiber treating agent containing a polymer of 00 to 2,000,000 as an active ingredient.

[ 2 ] A monomer composition comprising 20 to 85 mol% of a phosphorylcholine-like group-containing monomer of the component A and 15 to 80 mol% of a hydrophilic monomer of the component C is polymerized.
A polymer having a molecular weight of 100,000 to 2,000,000
Fiber treatment agent as an active ingredient.

[ 3 ] 20 to 88 mol% of the phosphorylcholine-like group-containing monomer of the A component , 2 to 40 mol% of the hydrophobic monomer of the B component, and 10 to 70 m of the hydrophilic monomer of the C component.
molecular weight obtained by polymerizing a monomer composition consisting of ol%
100,000 to 2,000,000 polymers as active ingredients
Fiber treatment agent.

[ 4 ] The phosphorylcholine-like group-containing monomer of the formula (1) of the component A is 2-{(meth) acryloyloxy} ethyl-2 '-(trimethylammonio) ethyl phosphate, and the component B is The hydrophobic monomer has the formula (2)

[0012]

[Chemical 4]

{Wherein L ¹ is --C ₆ H ₄ -,-
C ₆ H ₁₀ -,-(C = O) -O-,-O-,-(C =
O) NH-, -O- (C = O)-and -O- (C =
O) represents a group selected from the group consisting of -O-, L ² is
Hydrogen _{atom, - (CH 2) g -L} 3, - ((CH 2) p -O) h
-Indicates a hydrophobic functional group selected from L ³ . g and h are 1
24 and p each represent an integer of 3 to 5, and L ³ represents a hydrogen atom, a methyl group, a functional group selected from —C ₆ H ₅ , and —O—C ₆ H ₅ . } The fiber treatment agent according to the above [ 1 ], which is a hydrophobic monomer represented by

[ 5 ] The phosphorylcholine-like group-containing monomer of the formula (1) of the component A is 2-{(meth) acryloyloxy} ethyl-2 '-(trimethylammonio) ethyl phosphate, and the component C The hydrophilic monomer is selected from the group consisting of a hydroxy group, a carboxyl group, a phosphonic acid group, a sulfonic acid group, an amide group, an amino group, a dialkylamino group, a trialkylamino base, a trialkylphosphonium base and a polyoxyethylene group. The fiber treatment agent according to the above [ 2 ], which is a hydrophilic monomer.

[ 6 ] The phosphorylcholine-like group-containing monomer of the formula (1) of the component A is 2-{(meth) acryloyloxy} ethyl-2 '-(trimethylammonio) ethyl phosphate, and the component B is The hydrophobic monomer is a hydrophobic monomer which is a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 18 carbon atoms, and the hydrophilic monomer of the C component is 1 to 4 carbon atoms. The fiber treatment agent according to the above [ 3 ], which is a hydrophilic monomer composed of (meth) acrylic acid hydroxyalkyl ester having a hydroxyalkyl group and (meth) acrylic acid.

[ 7 ] The hydrophilic monomer of component C is a hydrophilic monomer consisting of two components, a (meth) acrylic acid hydroxyalkyl ester having a hydroxyalkyl group having 1 to 4 carbon atoms and (meth) acrylic acid. The fiber treatment agent according to the above [ 6 ], which is a polymer.

[ 8 ] A fiber treatment agent solution containing 0.001 to 1 wt% of the fiber treatment agent of [1] to [ 7 ] as an active ingredient in an aqueous solution.

[ 9 ] A fiber treatment agent composition containing the fiber treatment agent of [1] to [ 7 ] as an active ingredient in an amount of 1 to 40% by weight in an aqueous solution.

[ 10 ] 0.001 to 1% by weight of the fiber treatment agent of [1] to [ 7 ] as an active ingredient in an aqueous solution.
A fiber treating agent solution containing 1 to 10% by weight of a polyhydric alcohol.

[ 11 ] A fiber treatment method characterized in that the fiber treatment agent solution of [ 8 ] or [ 10 ] is used to treat the fibers by dipping or coating and drying at 40 to 180 ° C.

[ 12 ] A fiber treated by the fiber treatment method of [ 11 ] above.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The fiber treating agent of the present invention comprises a monomer composition containing a specific phosphorylcholine-like group-containing monomer (hereinafter abbreviated as PC monomer), which has a specific molecular weight of < A polymer (hereinafter abbreviated as PC polymer) is a main component. Monomer composition comprising a PC monomer, in addition to the phosphorylcholine group-containing monomer, that contain a polymerizable other polymerizable monomers. Specifically, before Symbol of PC polymers, obtained by polymerizing a monomer composition comprising a hydrophobic monomer 2～80Mol% as PC monomer 20～98Mol% and the B component as the component A Polymers can be preferably mentioned.
More preferably, the PC monomer as component A is 40 to 80 m
ol% and hydrophobic monomer 20 to 60 mol% as B component
It is a monomer composition consisting of

When the content of the hydrophobic monomer as the component B is less than 2 mol%, the affinity for the fiber on the hydrophobic surface cannot be sufficiently provided, and when it is more than 80 mol%, the phosphorylcholine-like group (abbreviated as PC group) has. It is not preferable because it is difficult to exhibit good feel and hygroscopicity.

Furthermore, said PC polymer, PC monomer 2 0~85mol% Component A, obtained by polymerizing a monomer composition comprising a hydrophilic monomer 15～80Mol% as component C Weight Preference is given to coalescing. More preferably, PC monomer 4 0～80Mol Component A
%, A monomer composition comprising 20 to 60 mol% of a hydrophilic monomer as the C component.

If the hydrophilic monomer as the component C is less than 15 mol%, it is not possible to have sufficient affinity for the fibers on the hydrophilic surface, and if it is more than 80 mol%, the PC group has good feel and hygroscopicity. It is difficult to exert the effect, which is not preferable.

Furthermore, the above-mentioned PC polymer contains 20 to 88 mol% of PC monomer as the A component, 2 to 40 mol% of hydrophobic monomer as the B component, and 10 to 70 mol of hydrophilic monomer as the C component. %, A polymer obtained by polymerizing the monomer composition can be preferably mentioned. More preferably, 40 to 70 mol% of PC monomer as the component A,
It is a monomer composition containing 5 to 30 mol% of a hydrophobic monomer as the B component and 20 to 50 mol% of a hydrophilic monomer as the C component.

When the amount of the phosphorylcholine group-containing monomer of the component A is less than 20 mol%, it is difficult to exhibit good touch and hygroscopicity, which is not preferable, and less than 2 mol% of the hydrophobic monomer of the component B, and less than C of the component C. Hydrophilic monomer 10 mol%
If it is less than the above range, affinity for various fibers cannot be imparted, which is not preferable. When the content of the phosphorylcholine group-containing monomer of the component A is more than 88 mol%, it is not preferable because it easily falls off by washing or the like, and the content of the hydrophobic monomer of the component B is 40
When it is more than mol%, the hydrophilicity is less imparted, and when it is more than 70 mol% of the hydrophilic monomer as the component C, it is not preferable because it cannot have an affinity for various fibers.

Here, the PC monomer has the following formula (1):

[0029]

[Chemical 5]

{Wherein, X represents a divalent organic residue, Y represents an alkyleneoxy group having 1 to 6 carbon atoms, and Z represents
Is a hydrogen atom or R ⁵ -O- (C = O)-(However,
R ⁵ is an alkyl group having 1 to 10 carbon atoms or 1 to 1 carbon atoms
0 represents a hydroxyalkyl group). Also, R ¹
Represents a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴
Are the same or different groups, and are hydrogen atom and carbon number 1
~ 6 alkyl groups or hydroxyalkyl groups are shown.
m represents 0 or 1. n is an integer of 1 to 4. } Is represented.

Examples of the divalent organic residue X in the formula (1), for _{example, -C 6 H 4 -, -} C 6 H 10 -, - (C = O)
O—, —O—, —CH ₂ —O—, — (C═O) NH—,
-O- (C = O)-, -O- (C = O) -O-, -C _{6
H 4 -O -, - C 6} H 4 -CH 2 -O -, - C 6 H 4 - (C =
O) O- and the like.

Y in the formula (1) is an alkyleneoxy group having 1 to 6 carbon atoms, and examples thereof include groups such as methyloxy, ethyloxy, propyloxy, butyloxy, pentyloxy and hexyloxy.

Z in the formula (1) is a hydrogen atom or R ⁵
It represents a —O— (C═O) — group. However, R ⁵ has 1 carbon atom
It shows an alkyl group having 10 to 10 or a hydroxyalkyl group having 1 to 10 carbon atoms. Here, as the alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group,
Examples thereof include an octyl group, a nonyl group and a decyl group.

Examples of the hydroxyalkyl group having 1 to 10 carbon atoms include hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 4-hydroxybutyl group and 2-hydroxy group. Butyl group, 5-hydroxypentyl group, 2-hydroxypentyl group, 6-hydroxyhexyl group, 2-hydroxyhexyl group, 7-hydroxyheptyl group, 2-
Hydroxyheptyl group, 8-hydroxyoctyl group, 2
-Hydroxyoctyl group, 9-hydroxynonyl group, 2
-Hydroxynonyl group, 10-hydroxydecyl group, 2
-Hydroxydecyl group and the like.

Specific examples of the PC monomer include, for example,
2-((meth) acryloyloxy) ethyl-2'-
(Trimethylammonio) ethyl phosphate, 3-
((Meth) acryloyloxy) propyl-2 '-(trimethylammonio) ethyl phosphate, 4-((meth) acryloyloxy) butyl-2'-(trimethylammonio) ethyl phosphate, 5-((meth) acryloyloxy ) Pentyl-2 '-(trimethylammonio) ethyl phosphate, 6-((meth) acryloyloxy) hexyl-2'-(trimethylammonio)
Ethyl phosphate, 2-((meth) acryloyloxy) ethyl-2 '-(triethylammonio) ethyl phosphate, 2-((meth) acryloyloxy) ethyl-2'-(tripropylammonio) ethyl phosphate, 2- ((Meth) acryloyloxy) ethyl-
2 '-(tributylammonio) ethyl phosphate,
2-((meth) acryloyloxy) ethyl-2'-
(Tricyclohexylammonio) ethyl phosphate, 2-((meth) acryloyloxy) ethyl-2 '
-(Triphenylammonio) ethyl phosphate,

2-((meth) acryloyloxy) ethyl-2 '-(trimethanolammonio) ethyl phosphate, 2-((meth) acryloyloxy) propyl-2'-(trimethylammonio) ethyl phosphate, 2- ((Meth) acryloyloxy) butyl-2 '
-(Trimethylammonio) ethyl phosphate, 2-
((Meth) acryloyloxy) pentyl-2 '-(trimethylammonio) ethyl phosphate, 2-((meth) acryloyloxy) hexyl-2'-(trimethylammonio) ethyl phosphate,

2- (vinyloxy) ethyl-2 '-(trimethylammonio) ethyl phosphate, 2- (allyloxy) ethyl-2'-(trimethylammonio) ethyl phosphate, 2- (p-vinylbenzyloxy)
Ethyl-2 '-(trimethylammonio) ethyl phosphate, 2- (p-vinylbenzoyloxy) ethyl-
2 '-(trimethylammonio) ethyl phosphate,
2- (Styryloxy) ethyl-2 '-(trimethylammonio) ethyl phosphate, 2- (p-vinylbenzyl) ethyl-2'-(trimethylammonio) ethyl phosphate, 2- (vinyloxycarbonyl) ethyl-2 '-(Trimethylammonio) ethyl phosphate, 2- (allyloxycarbonyl) ethyl-2'-
(Trimethylammonio) ethyl phosphate,

2- (acryloylamino) ethyl-2 '
-(Trimethylammonio) ethyl phosphate, 2-
(Vinylcarbonylamino) ethyl-2 ′-(trimethylammonio) ethyl phosphate,

Ethyl- (2'-trimethylammonioethylphosphorylethyl) fumarate, butyl- (2'-
Trimethylammonioethylphosphorylethyl) fumarate, hydroxyethyl- (2'-trimethylammonioethylphosphorylethyl) fumarate, ethyl-
Examples thereof include (2′-trimethylammonioethylphosphorylethyl) malate, butyl- (2′-trimethylammonioethylphosphorylethyl) malate, and hydroxyethyl- (2′-trimethylammonioethylphosphorylethyl) malate.

Of these, 2-((meth) acryloyloxy) ethyl-2 '-(trimethylammonio) ethyl phosphate is preferable, and 2- (methacryloyloxy) ethyl-2'-(trimethylammonio) ethyl phosphate is ( Hereinafter, abbreviated as MPC) is more preferable in terms of availability, hygroscopicity, and good feel.

When the PC monomer is polymerized, the above-mentioned PC is used.
One of the monomers may be used alone, or two or more of them may be used as a mixture.

The PC monomer can be produced by a known method.
For example, JP-A-54-63025 and JP-A-58-58
It can be manufactured according to a known method disclosed in Japanese Patent No. 154591 or the like.

The B component hydrophobic monomer copolymerized with the PC monomer is represented by the formula (2):

[0044]

[Chemical 6]

(In the formula, L ¹ is -C ₆ H ₄ -,-
_{C 6 H 10 -, - (} C = O) O -, - O -, - (C = O)
NH-, -O- (C = O)-and -O- (C = O)-
Represents a group selected from the group consisting of O-, L ² is a hydrogen atom, — (CH ₂ ) _g —L ³ , — ((CH ₂ ) _p —O) h—L ³
A hydrophobic functional group selected from g and h are 1 to 24,
p represents an integer of 3 to 5, wherein L ³ is a hydrogen atom,
A functional group selected from a methyl group, —C ₆ H ₅ , and —O—C ₆ H ₅ is shown. ).

Specific examples of the hydrophobic monomer as the component B include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2- (meth) acrylate.
Linear or branched alkyl (meth) acrylates such as ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate; benzyl (meth) acrylate , Phenoxyethyl (meth) acrylate and other aromatic (meth) acrylates; polypropylene glycol (meth)
Hydrophobic polyalkylene glycol (meth) acrylates such as acrylates; styrene-based monomers such as styrene, methylstyrene, chloromethylstyrene; vinyl ether-based monomers such as methyl vinyl ether, butyl vinyl ether; vinyl acetate, vinyl propionate, etc. Examples thereof include vinyl ester-based monomers. These 1 type (s) or 2 or more types are used.

The hydrophilic monomer as the component C is, for example, a hydroxy group, a carboxyl group, a phosphonic acid group, a sulfonic acid group, an amide group, an amino group, a dialkylamino group, a trialkylamino base, a trialkylphosphonium base or a polyalkyl group. It is a monomer having a hydrophilic group selected from the group consisting of oxyethylene groups. Furthermore, specifically, for example,
Hydroxy group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; carboxylic acids such as acrylic acid and methacrylic acid (MAc); styrene sulfone Ionic group-containing monomers such as acid, (meth) acryloyloxyphosphonic acid, 2-hydroxy-3- (meth) acryloxypropyltrimethylammonium chloride; (meth) acrylamide,
Nitrogen-containing monomers such as aminoethyl methacrylate and dimethylaminoethyl (meth) acrylate; polyethylene glycol (meth) acrylate and the like. These 1 type (s) or 2 or more types are used.

The PC polymer is a monomer composition of the A component PC monomer and the B component hydrophobic monomer, the A component PC monomer and the C component hydrophilic monomer. Or a composition obtained by polymerizing a monomer composition of the component A PC monomer, the component B hydrophobic monomer and the component C hydrophilic monomer. , Can be produced by ordinary radical copolymerization.

The molecular weight of the PC polymer of the present invention is the weight average.
In, Oh in the range of 1 00,000～2,000,000
It

The material of the fibers which can be treated in the present invention is not particularly limited. Any material can be used as long as it can be used for ordinary clothes, for example, natural fibers such as cotton, hemp, silk, wool and collagen fibers; acrylic fibers, rayon, nylon, vinylon, polyester, polypropylene, polyvinyl chloride. ,polyethylene,
Examples include synthetic fibers such as polymetaphenylene isophthalamide, aramid, and polyarylate.

The fibers which can be treated in the present invention also include papers composed mainly of cellulose fibers such as tissue paper and toilet paper which may be used in contact with human skin. .

The shape of the fiber treated with the fiber treatment agent of the present invention may be a thread-like, string-like or rope-like fiber, or may be a cloth-like one.

Specific examples of the relatively hydrophobic fiber include rayon, polyester, polypropylene, polyvinyl chloride, polyethylene, polymetaphenylene isophthalamide, aramid, polyarylate and the like.

Examples of the relatively hydrophilic fiber include cotton, hemp, silk, wool, collagen fiber, acrylic fiber, nylon and vinylon.

The PC polymer obtained as described above is
The properties differ slightly depending on the compounding components of the monomer, and in that case, it is desirable to consider the combination of the above-mentioned monomer and the fiber to be treated.

For example, a PC copolymer composed of a PC monomer of component A and a hydrophobic group-containing monomer of component B is suitable for treating the above-mentioned fiber having a relatively hydrophobic surface. Feel and hygroscopicity can be imparted. The PC copolymer composed of the PC monomer of the A component and the hydrophilic group-containing monomer of the C component has a good feel and hygroscopicity when treating the above-mentioned fiber having a relatively hydrophilic surface. Can be granted.

PC composed of PC monomer of component A, hydrophobic group-containing monomer of component B, and hydrophilic group-containing monomer of component C
The copolymer can impart good feel and hygroscopicity when treating fibers having any surface regardless of hydrophilicity or hydrophobicity.

Among the above monomer compositions constituting the copolymer of the component A, the component B and the component C, the hydrophobic monomer of the component B has an alkyl group having 1 to 18 carbon atoms ( Meta)
At least 1 selected from alkyl acrylate
Hydrophobic monomer of a kind, and the hydrophilic monomer of C component is a group consisting of (meth) acrylic acid hydroxyalkyl ester having a hydroxyalkyl group having 1 to 4 carbon atoms and (meth) acrylic acid. When a fiber treatment agent which is at least one hydrophilic monomer selected from the above is used, a copolymer having a high affinity for fibers and capable of maintaining a good feel and hygroscopicity for a long time is obtained. Is most preferable because

Among the above-mentioned monomer compositions, the hydrophilic monomer of the component C is one selected from (meth) acrylic acid hydroxyalkyl ester having a hydroxyalkyl group having 1 to 4 carbon atoms and (meth) When a hydrophilic monomer consisting of two components with acrylic acid is used, a fiber treating agent having a higher effect can be obtained.

The method of treating the fibers with the PC polymer of the present invention is (a) a method of dipping the fibers in an aqueous solution of the PC polymer and then drying, or (b) an aqueous solution of the PC polymer directly on the fibers. Examples include a method of applying and drying. The concentration of the PC polymer is preferably 0.001 to 1% by weight of an aqueous solution.

If the concentration of the PC polymer is lower than 0.001% by weight, the PC polymer cannot be sufficiently adsorbed on the fiber, so that the effect cannot be sufficiently exhibited.
If the concentration is higher than the weight%, the PC polymer may remain unnecessarily and the flexibility of the fiber may be impaired, which is not preferable.

When it is desired to completely dry the fibers after treating the fibers, the drying temperature is preferably in the range of 40 to 180 ° C., and the temperature lower than 40 ° C. is due to the inherent hygroscopicity of the phosphorylcholine group-containing polymer. Since it cannot be dried sufficiently and the temperature higher than 180 ° C. may decompose the phosphorylcholine group, it is not preferable.

However, even when it is used for domestic washing or soft finishing, or when it is used for business purposes, it can be dried at room temperature if there is no problem in the state of absorbing moisture after the treatment. .

Furthermore, 0.001 to 0.001 of the PC copolymer is used.
A 1% by weight aqueous solution includes, for example, ethylene glycol,
1 ppm of polyhydric alcohol such as 1,3-butanediol, 1,4-butanediol, glycerin and sorbitol
Addition in a range of from 10 to 10% by weight is more preferable because the fibers and the phosphorylcholine group-containing polymer can be made to be compatible with each other.

The treatment liquid for the phosphorylcholine group-containing polymer used in the present invention is usually a concentrated liquid of 1 to 40% by weight, and when necessary, it may be diluted with water or the like to prepare a treatment liquid for fibers. Practically preferable.

If desired, other components such as a surfactant, a softening agent, a solvent, a dye, a moisturizer, an antibacterial agent, and a fragrance may be added to the treatment liquid of the present invention.

The fiber or cloth treated with the fiber treating agent of the present invention can be used for modifying fibers after manufacturing, modifying cloth as a fabric, modifying after manufacturing as clothes, and the like. It can be applied to business, and can also be applied to cases such as household laundry and soft finishing.

[0068]

The fiber treating agent of the present invention is obtained by polymerizing a monomer containing a phosphorylcholine group-containing polymer having a specific composition range, and is a fiber treating agent which can be treated by a simple method. Fiber treating agent treatment solution of the present invention, dipping, or by treating fibers or fabric with a simple process of coating a solution that can be processed by drying at about. Further, the above-mentioned treatment method is a simple treatment method capable of imparting hydrophilicity and a property of improving the feel of the cloth upon contact with the skin by drying after treating the fiber with the treatment liquid. Further, the fiber or cloth treated with the fiber treating agent of the present invention is imparted with the property of being hydrophilic and improving the feel of the cloth at the time of contact with the skin, so that it can impart hygroscopicity and is excellent in the feel at the time of contact. Become fibers.

[0069]

EXAMPLES The present invention will be described in detail below with reference to examples. Next, a method for analyzing the weight average molecular weight of the polymer used will be shown. <Measurement of weight average molecular weight> Gel permeation chromatography (GP) using a phosphate buffer (pH 7.4, 20 mM) as an eluent.
C), polyethylene glycol standard, UV (210n
m) and the refractive index.

Synthesis Example 1; Synthesis of Polymer 1 MPC; 35.7 g, n-butyl methacrylate (BM
A); 4.3 g (monomer composition molar ratio, MPC / BMA =
80/20) was dissolved in 160 g of ethanol, placed in a four-necked flask, and blown with nitrogen for 30 minutes, and then 0.82 g of azobisisobutyronitrile was added at 60 ° C. to carry out a polymerization reaction for 8 hours. The polymerization solution was added dropwise to 3 liters of diethyl ether with stirring, and the deposited precipitate was filtered and filtered.
Vacuum drying was performed for 8 hours at room temperature to obtain 29.6 g of powder. The molecular weight evaluated by GPC is 15
It was 3,000. This is Polymer 1.

Synthetic Examples 2 to 6; Synthesis of Polymers 2 to 6 By following the same procedure as in Synthetic Example 1 except that the types of monomers, composition ratios and solvent species are changed in accordance with the polymer 1 of Synthetic Example 1 above. Got united. The polymer of the obtained copolymer composition is shown below. Polymer 2; MPC0.5-BMA0.2-MAc0.
3, weight average molecular weight 354,000, polymer 3; MPC0.9-SMA0.1, weight average molecular weight 210,000, polymer 4; MPC0.4-MMA0.2-MAc0.
2-HEMA0.2, weight average molecular weight 429,000, polymer 5; MPC0.7-QA0.3, weight average molecular weight 252,000, polymer 6; MPC0.5-BMA0.2-QA0.
3, weight average molecular weight 106,000.

[0072]

[Table 1]

Note: The abbreviations used in the table are as follows. MPC; 2- (methacryloyloxy) ethyl-2'-
(Trimethylammonio) ethyl phosphate, BMA; n-butyl methacrylate, MAc; methacrylic acid, SMA; stearyl methacrylate, MMA; methyl methacrylate, 2-HEMA; 2-hydroxyethyl methacrylate, QA; 2-hydroxy-3-methacryloxy Propyltrimethylammonium chloride.

Examples 1 to 6 2.0 g of polymers 1 to 6 were dissolved in 398 g of pure water to prepare a treatment liquid (0.5% by weight). A test cloth made of 100% acrylic (abbreviated as A in the table) with a side length of 5 cm is dipped in the treatment liquid, thoroughly infiltrated the treatment liquid for about 5 minutes, then taken out, lightly dried with a dryer, and then heated at 120 ° C. It was hung in an air circulation type drying chamber and dried for 15 minutes. Two types of test cloths made of 100% polyester (abbreviated as P in the table) and 100% nylon (abbreviated as N in the table) were treated in the same manner. A drop of pure water was dropped onto the obtained test cloth with a dropper, the time until the water droplet soaked into the cloth and disappeared was measured, and the average value was evaluated for each of the 5 sheets. The higher the hygroscopicity of the cloth, the shorter the time it takes for the water droplets to disappear. The average value of the five sheets is shown in Table 1. Further, the treated cloth was immersed in 100 mL of pure water, lightly stirred for 10 minutes and washed with water. The disappearance time of water droplets after repeating this water washing 10 times was evaluated in the same manner as above, and the average value thereof is shown in Table 2.

Comparative Examples 1 to 5 Pure water only (Comparative Example 1), polyvinylpyrrolidone (molecular weight 160,000) (Comparative Example 2), polyvinyl alcohol (molecular weight 133,000) (Comparative Example 3), poly (acrylic acid 0) 8-butyl acrylate 0.2) (molecular weight;
Unknown) (Comparative Example 4), poly (vinyl methyl ether) 0.
A 0.5 wt% aqueous solution of 5-maleic acid 0.5) (molecular weight; unknown) (Comparative Example 5) was used as a treatment liquid. A test cloth was prepared using the above treatment liquid in the same manner as in Example 1, and the disappearance time of water droplets was evaluated. Further, the disappearance time of water droplets after washing with water was also evaluated in the same manner. The obtained values are shown in Table 1.

[0076]

[Table 2]

[0077]

[Table 3]

Examples 7 and 8 2.0 g of Polymers 2 and 4 were each added to pure water 397.29.
g, and 0.8 g of 1,3-butanediol was added to each to prepare a treatment liquid (polymer 0.5% by weight). Five test cloths were prepared for each cloth in the same manner as in Example 1,
The disappearance time of water drops was evaluated. Further, the disappearance time of water droplets after washing with water was also evaluated in the same manner. The obtained values are shown in Table 4.

[0079]

[Table 4]

Examples 9 and 10, Comparative Examples 6 and 7 The polyester test cloths prepared in Examples 4 and 8 and Comparative Examples 1 and 2 (corresponding to Examples 9 and 10 and Comparative Examples 6 and 7, respectively) were used. Using 15 men and women of 24 to 48 years old as subjects, lightly rub the inside of the dry forearm, scored 4, 3, 2, 1 in order from the one with the best feeling at that time, and evaluate the average value. The results are shown in Table 5. Similarly, scores were assigned in order of good feeling when wiping the inside of the forearm from which water droplets were dropped, and the average value was evaluated. The results are shown in Table 5.

[0081]

[Table 5]

From the above results, in comparison with Comparative Examples 1 to 5,
With the treatment liquids of Examples 1 to 8, cloths having high hygroscopicity were obtained. In particular, in Examples 7 and 8, high hygroscopicity was maintained by adding the polyhydric alcohol, even after washing with water 10 times, as compared with Examples 2 and 4 (corresponding to the system in which the polyhydric alcohol was not added). In addition, it can be seen from the results in Table 5 that with the treatment liquids of Examples 9 and 10, fabrics having a good feel were obtained as compared with Comparative Examples 6 and 7.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08F 218/00 C08F 218/00 218/02 218/02 220/04 220/04 220/06 220/06 220/10 220/10 220/18 220/18 220/28 220/28 220/54 220/54 230/02 230/02 C08K 5/053 C08K 5/053 C08L 23/02 C08L 23/02 25/00 25/00 29/10 29/10 31 / 00 31/00 31/02 31/02 33/02 33/02 33/04 33/04 33/08 33/08 33/10 33/10 33/14 33/14 33/24 33/24 43/02 43/02 (58) Fields investigated (Int.Cl. ⁷ , DB name) D06M 15/00-15/72 C08L 23/00-43/02 C08K 5/053 C08F 30/02-230/02

Claims (12)

(57) [Claims] 1. The following formula (1): {However, in the formula, X represents a divalent organic residue, Y represents an alkyleneoxy group having 1 to 6 carbon atoms, Z is a hydrogen atom or R ⁵ —O— (C═O) — (however, R ⁵ has 1 carbon
10 represents an alkyl group having 10 to 10 or a hydroxyalkyl group having 1 to 10 carbon atoms). R ¹ represents a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ are the same or different groups and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group. m is 0 or 1
Indicates. n is an integer of 1 to 4. } A component represented by
20 to 98 mol of a phosphorylcholine-like group-containing monomer of
% And a hydrophobic monomer of component B of 2 to 80 mol% , a molecular weight of 100,000 to 2 obtained by polymerizing a monomer composition.
A fiber treatment agent containing 000000 polymer as an active ingredient. The method according to claim 2, wherein the formula (1) phosphorylcholine-like group A component represented by containing comprising a hydrophilic monomer 15～80Mol% monomer 20～85Mol% and C component monomer composition Polymerized, molecular weight 100,000-2000
A fiber treatment agent containing 000 polymer as an active ingredient. 3. A phosphorylcholine-like group-containing monomer of component A represented by the formula (1), 20 to 88 mol%, a hydrophobic monomer of B component, 2 to 40 mol%, and a hydrophilic monomer of C component. a monomer composition comprising 10～70Mol%
Polymerized, with a molecular weight of 100,000 to 2,000,000
A fiber treatment agent containing a polymer as an active ingredient. 4. The phosphorylcholine-like group-containing monomer of the formula (1) of the component A is 2-{(meth) acryloyloxy} ethyl-2 ′-(trimethylammonio) ethyl phosphate, and the hydrophobic component B is used. Of the formula (2) {In the formula, L ¹ _{is, -C 6 H 4 -, -} C 6 H 10 -, -
(C = O) -O-, -O-,-(C = O) NH-, -O
A group selected from the group consisting of — (C═O) — and —O— (C═O) —O—, wherein L ² is a hydrogen atom, — (C
H ² ) _g —L ³ and — ((CH ₂ ) _p —O) _h —L ³ represent a hydrophobic functional group. g and h are 1 to 24, p is 3 to 5
It indicates the integer, L ³ represents a hydrogen atom, a methyl group, -C
A functional group selected from ₆ H ₅ and —O—C ₆ H ₅ is shown. Fiber treatment agent of claim 1 wherein the hydrophobic monomer represented by}. 5. The phosphorylcholine-like group-containing monomer of the formula (1) of the component A is 2-{(meth) acryloyloxy} ethyl-2 ′-(trimethylammonio) ethyl phosphate, and the hydrophilicity of the component C is obtained. The monomer is hydroxy group, carboxyl group, phosphonic acid group, sulfonic acid group,
The fiber treatment according to claim 2 , which is a hydrophilic monomer having a hydrophilic group selected from the group consisting of an amide group, an amino group, a dialkylamino group, a trialkylamino base, a trialkylphosphonium base and a polyoxyethylene group. Agent. 6. The phosphorylcholine-like group-containing monomer of the formula (1) of the component A is 2-{(meth) acryloyloxy} ethyl-2 ′-(trimethylammonio) ethyl phosphate, and the hydrophobic component of the component B is used. Monomer has 1 carbon
Is a hydrophobic monomer of a (meth) acrylic acid alkyl ester having an alkyl group of 18 to 18, and the hydrophilic monomer of the C component is a (meth) acrylic acid hydroxy having a hydroxyalkyl group of 1 to 4 carbon atoms. The fiber treating agent according to claim 3, which is a hydrophilic monomer selected from the group consisting of alkyl esters and (meth) acrylic acid. 7. The hydrophilic monomer of component C has 1 to 4 carbon atoms.
Of (meth) acrylic acid hydroxyalkyl ester having a hydroxyalkyl group of (2) and (meth) acrylic acid
The fiber treating agent according to claim 6, which is a hydrophilic monomer composed of components. 8. The method of claim 1 fiber treatment agent solution containing 0.001 wt% in the aqueous solution as an active ingredient a fiber treatment agent according to 7 Izure or one of. 9. claims 1-7 Izure or fiber treatment agent composition containing 40 wt% in the aqueous solution as an active ingredient a fiber treatment agent according to one of. 10. The aqueous solution as an active ingredient a fiber treatment agent according to item 1 either of claims 1-7 0.001
% By weight, and further contains 1 ppm of polyhydric alcohol
A fiber treatment agent solution containing 10% by weight. 11. A fiber treatment agent solution according to claim 8 or 10 is used to treat fibers by dipping or coating,
A fiber treatment method, which comprises drying at 40 to 180 ° C. 12. A fiber treated by the fiber treatment method according to claim 11 .