JPH1096166A - Inhibitor of yellowing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an inhibitor of yellowing capable of preventing the yellowing of clothes even until the clothes repeatedly worn and washed are stored in a chest of drawers, etc., for a next season by including a compound having a reactive functional group and a sterically hindered piperidyl group and further a photostabilizing effect. SOLUTION: This inhibitor of yellowing comprises a compound having a reactive functional group, a sterically hindered piperidyl group and a photostabilizing effect such as a compound of the formula. Further, the compound having the photostabilizing effect is preferably a copolymer of a radically polymerizable monomer having the sterically hindered piperidyl group such as 1,2,2,6,6-pentamethyl-4-piperidyl (meth)acrylate and a radically polymerizable monomer having a functional group such as a glycidyl group reactive to a cellulosic woven fabric, or a copolymer of these monomers with another radically polymerizable monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a yellowing inhibitor comprising as an active ingredient a compound having a sterically hindered piperidyl group and having a light stabilizing action. By using this yellowing inhibitor on the fiber substrate, yellowing during storage of clothes repeatedly worn and washed can be suppressed.

[0002]

2. Description of the Related Art A phenomenon of yellowing is observed during repeated wearing and washing of clothes, or during storage after being replaced every season. In particular, it is remarkable in a portion such as a collar and a sleeve that is in good contact with the skin. This is because some of the unsaturated compounds contained in the sebum attached to the worn clothes,
It is presumed that they are not completely removed even during washing, but gradually accumulate and change to a yellow hardly soluble compound by an autoxidation reaction. Several studies have been conducted to suppress such yellowing of clothes. Triolein and squalene in triglycerides, which are considered to be a major contributor to yellowing of the fiber matrix, are applied to clothing as sediment-causing substances. Studies have been made to observe the yellowing of a paper coated with an antioxidant or an organic acid or the like, or in the presence of paper impregnated with them. For example, Japanese paper impregnated with 2,6-di-t-butyl-4-methylphenol as an antioxidant and dried is allowed to coexist with a sample cloth, left in a thermostat at 29 ° C. for one month, and turned yellow. Studies have been conducted to determine the condition, but 2,6-di-t-butyl-4-.
Methyl phenol itself had a disadvantage that it turned into a dark yellow substance and colored the sample cloth. Also, studies have been made using sodium L-ascorbate as an antioxidant, but have the drawback of coloring the sample cloth as with 2,6-di-t-butyl-4-methylphenol. . Also, Kazuko Yamauchi et al. Observed yellowing of a sample cloth using citric acid as an organic acid. The Japanese paper impregnated with citric acid and dried is allowed to coexist with the sample cloth, and
When stored in a 9 ° C thermostat for one month, the b value of the sample cloth with citric acid was smaller in the sample cloth with citric acid and in the sample without citric acid but the suppression effect. Is low (Kazuko Yamauchi et al., Textile Consumption Science, 35
Vol. 382, 1994).

Further, when a fiber substrate is treated with diphenylpicrylhydrazyl, galvinoxyl, or the like, which is known as a radical scavenger, the color of the compound itself is added, so that it is hard to use as a yellowing inhibitor. In addition, a method of removing yellowing of underwear using a bleach containing peroxide, alkali serine protease ゛ and a hydroxy alkaline earth metal has been proposed (for example, Japanese Patent Application Laid-Open No. 04-372695). Not done.
Generally, sterically hindered piperidyl group-containing light stabilizers (known as hindered amine light stabilizers (HALS)) are widely used as stabilizers for polymer materials such as plastics, rubber, fibers, paints, and inks. ing. The use of a light stabilizer having such a sterically hindered piperidyl group as a yellowing inhibitor has not been known until now. Therefore, no effective material has been found to suppress the yellowing of clothes stored in a closet by repeating washing and wearing. Also, many attempts have been made to fix a fiber treatment agent or the like to cellulose fibers in consideration of improvement in durability, but the yellowing inhibitor is provided with a functional group that reacts with the cellulosic fabric to suppress yellowing. Although it has been maintained for a long time, it has not yet been developed.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of such a problem. Even if clothes that have been repeatedly worn and washed are stored in a closet or the like until the next season, the yellow color of the clothes can be reduced. An object of the present invention is to provide a compound which suppresses the change.

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, by applying a compound containing a sterically hindered piperidyl group as an active ingredient to a fiber substrate of clothes. The present inventors have found that clothing which has been repeatedly worn and washed can be prevented from yellowing while being stored in a closet or the like until the next season. That is, the present invention provides 1) a yellowing inhibitor characterized by comprising a compound having a reactive functional group and having a sterically hindered piperidyl group and having a light stabilizing effect, and 2) a compound having a light stabilizing effect. A copolymer of a radical polymerizable monomer having a radical polymerizable unsaturated group and a sterically hindered piperidyl group and a radical polymerizable monomer having a functional group that reacts with a cellulosic fabric, or A yellowing inhibitor characterized by being a copolymer with another radically polymerizable monomer; and 3) a yellowing inhibitor characterized by that a functional group that reacts with a cellulosic fabric is a glycidyl group. .

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the yellowing inhibitor of the present invention will be described in detail. The compound used in the yellowing inhibitor of the present invention has at least one functional group and a sterically hindered piperidyl group which react with the cellulosic fabric, and has a light stabilizing effect. The cellulosic fabric in the present invention refers to a fabric woven from cellulosic fibers obtained by singly or blending cellulosic fibers such as cotton, rayon, and polynosic, and generally has a hydroxyl group as a reactive group. doing.

The functional group that reacts with the cellulosic fiber can be selected from groups that react with the hydroxyl group of the cellulosic fiber. Generally, acid halides, acid anhydrides, isocyanate groups, blocked isocyanate groups, halogenated Examples thereof include an alkyl group and a glycidyl group. A glycidyl group is preferable since the reaction is completed under mild processing conditions and the reaction product itself does not turn yellow. Examples of a compound having a light-stabilizing action having a reactive functional group and having a sterically hindered piperidyl group include, for example,

[0008]

Embedded image

And the like. [In the formula, n is the number of repeating units. Radical polymerizable monomer having a radically polymerizable unsaturated group and a sterically hindered piperidyl group, a radical polymerizable monomer having a functional group that reacts with a cellulosic fabric, and other radicals having a light stabilizing action. The yellowing inhibitor composed of a copolymer with a polymerizable monomer can be synthesized, for example, as follows. At least one radical polymerizable unsaturated group and one sterically hindered piperidyl group are present in the molecule.
As the monomer having each, the following general formula,

[0010]

Embedded image Wherein the symbols R ¹ may be the same or different,
A linear or branched alkyl group having from 3 to 3 carbon atoms, a phenyl group and an alkoxy group having 1 to 18 carbon atoms, wherein R ² is a hydrogen atom, 1 to 3 carbon atoms; Represents a group selected from a linear or branched alkyl group having an atom, a phenyl group and an alkoxy group having 1 to 18 carbon atoms. R ³ is a hydrogen atom or a group having 1 to 3 carbon atoms.
Represents a single bond, a substituted or unsubstituted phenylene group or a group represented by the following structure,

Embedded image Alternatively, R ⁴ represents an alkylene group having 1 to 22 carbon atoms (exemplified below), a phenylene group, or a plurality of these groups bonded to each other. The following groups are shown. ]

Embedded image Can be used. The structure is not particularly limited as long as it shows various structures depending on the combination of the defined groups (R, Y) and follows the definition, but does not include structures that are theoretically impossible in organic chemistry.

The monomer can be used without any particular limitation as long as it has at least one radically polymerizable unsaturated group and at least one sterically hindered piperidyl group in the molecule. , 2,6,6-pentamethyl-4-piperidyl (meth) acrylate, 1-ethyl-
2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, N- [1,2,2,6,6-pentamethyl-4-piperidyl] (meth) acrylamide, N
-[1-Ethyl-2,2,6,6-tetramethyl-4-
(Piperidyl) (meth) acrylates such as (meth) acrylamide, and (meth) acrylamides. Of these, considering the availability, etc.,
1,2,2,6,6-pentamethyl-4-piperidyl methacrylate and 1-ethyl-2,2,6,6-tetramethyl-4-piperidyl methacrylate are preferred.
In addition, these monomers can be freely selected and used as long as problems such as gelation do not occur during polymerization, and these monomers can be used alone or in combination of two or more kinds. .

The radical polymerizable monomer having a functional group that reacts with the cellulosic fabric is not particularly limited as long as it is a radical polymerizable monomer that reacts with a hydroxyl group contained in the cellulosic fabric. A radical polymerizable monomer having an acid halide, an acid anhydride, an isocyanate group, a blocked isocyanate group, an alkyl halide, a glycidyl group or the like is used. A radical polymerizable monomer having a glycidyl group is preferred in that the reaction with the hydroxyl group of the cellulosic fabric is completed under mild processing conditions and the copolymer itself does not yellow. Examples of the radical polymerizable monomer having a glycidyl group include glycidyl (meth) acrylate, methyl glycidyl methacrylate, and a (meth) acrylate having an alicyclic epoxy group (eg, a cyclomer series manufactured by Daicel Chemical Industries, Ltd. Cyclomer M100, Cyclomer A200, Cyclomer M101), vinyl compound having an alicyclic epoxy group (eg, Celloxide 200 manufactured by Daicel Chemical Industries, Ltd.)
0) and the like.

A compound having a light stabilizing action is combined with a radical polymerizable monomer having a radical polymerizable unsaturated group and a sterically hindered piperidyl group and a radical polymerizable monomer having a functional group which reacts with a cellulosic fabric. As other radically polymerizable monomers that can be used, any one having a radical polymerization ability can be generally used. For example, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate,
Alkyl (C 1-22) such as 2-ethylhexyl (meth) acrylate and stearyl (meth) acrylate
(Meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate (eg, Nippon Kayaku Co., Ltd.)
Such as a ring structure or a ring structure containing a hetero atom or a substituted or unsubstituted phenyl group-containing organic group (meth) acrylate,
Alkyl ethers (meth) such as 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and n-butoxyethyl (meth) acrylate
Ring structure such as acrylate, phenoxyethyla (meth) acrylate, phenoxy polyethylene glycol acrylate (eg, Biscoat # 150, Osaka Organic Chemical Industry Co., Ltd.) or a ring structure containing a hetero atom, or a substituted or unsubstituted phenyl group-containing organic group ether (Meth) acrylate, methoxypolyethylene glycol monomethacrylate (Example: Blemmer PME series manufactured by NOF Corporation, PM
E-100, PME-200, PME-400), (meth) acrylate of alkoxypolyethylene glycol or alkoxypolypropylene glycol such as ethoxydiethylene glycol (meth) acrylate, light acrylate N
P-8EA, NP-4EA (both are manufactured by Kyoeisha Chemical Co., Ltd.), (meth) acrylates of a substituted or unsubstituted phenyl group-containing alkoxypolyethylene glycol or alkoxypolypropylene glycol having a ring structure or a hetero atom, In addition, monomers having a plurality of radically polymerizable groups such as allyl (meth) acrylate, triethylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate are also included. This includes urethane (meth) acrylates (eg, Kyoeisha Chemical Co., Ltd., urethane acrylate series, AH-6
00, AI-600, AT-600), methacryl group-modified polyorganosiloxane (eg, Shin-Etsu Chemical Co., Ltd.)
X-22-164B, X-22-164C, X-2
2-174DX) such as polymers and oligomers, and relatively high molecular weight macromonomers.

(Meth) acrylonitrile, N, N-dimethylacrylamide, N-isopropylacrylamide, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylate, N- (meth) acrylmorpholine, etc. Acrylate amide compounds and derivatives thereof may be mentioned. Aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, and vinyltoluene; vinylcyclohexane; 2-vinylpyridine;
Vinyl compounds having a ring structure such as vinylpyridine, N-vinyl-2-pyrrolidone, vinyloxazoline or a ring structure group containing a hetero atom (excluding an epoxy group-containing organic group). Maleimide derivatives such as N-phenylmaleimide, N- (2-methylphenyl) maleimide, N-cyclohexylmaleimide Maleic esters such as diethyl maleate, di-2-ethylhexyl maleate, diethyl fumarate, di-2-ethylhexyl Examples thereof include fumarate esters such as fumarate, aliphatic vinyl compounds such as vinyl chloride and derivatives thereof, and aliphatic vinyl esters such as vinyl acetate and vinyl propionate.

Such radically polymerizable unsaturated monomers can be selected within a range that does not cause problems such as gelation during polymerization, and these monomers may be used alone or in combination of two or more. can do. Considering the simplicity of polymerization and the variety of polymer properties, (meth) acrylates are preferred for use as the main component in view of their abundance. For the purposes of the present invention, these radically polymerizable unsaturated monomers may not be included.

The weight ratio of a radical polymerizable monomer having a radical polymerizable unsaturated group and a sterically hindered piperidyl group to a radical polymerizable monomer having a functional group which reacts with a cellulosic fabric, and And the weight ratio of each of the other radically polymerizable monomers is fixed to the cellulose fibers obtained by using the yellowing inhibitor of the present invention alone or by blending the cellulose fibers such as cotton, rayon and polynosic. The radical polymerizable monomer having a radical polymerizable unsaturated group and a sterically hindered piperidyl group is not limited to 0.1% by weight or more, and is not particularly limited as long as it can exert a sufficient effect when prepared. The radical polymerizable monomer having a functional group to be used is used in a range of 0.5% by weight or more, and other radical polymerizable monomers are used in a range of 0.6% by weight or more. Radical polymerizable monomer having a radical polymerizable unsaturated group and sterically hindered piperidyl group, radical polymerizable monomer having a functional group that reacts with a cellulosic fabric, and co-polymerization with other radical polymerizable monomers The number average molecular weight of the union is generally 5,000 to 100,000, preferably 6,
It is desirable that it is 000-80,000. A chain transfer agent may be used to adjust the molecular weight. Examples of the chain transfer agent include compounds having a mercapto group,
For example, n-octyl mercaptan, n-dodecyl mercaptan, t-nonyl mercaptan, t-dodecyl mercaptan and the like can be exemplified.

Further, a polyorganosiloxane compound in which the main chain skeleton containing one or more mercapto groups is polysilsesquioxane or polydialkylsiloxane can also be used. For example, when the main chain skeleton is polysilsesquioxane, the polysilsesquioxane containing one or more mercapto groups may be one having a mercapto group introduced into a side chain (a) and one having a mercapto group introduced into a terminal of the main chain. (B) exists. The polysilsesquioxane (a) containing one or more mercapto groups in the side chain has, for example, a structure represented by the following formula (A), wherein R ^m , R ⁿ
Is a side chain organic ^{group, -O-R q, -O-} R r, -O-
R ^s and —O—R ^t are terminal groups of the main chain, and p is the number of repeating units.

[0018]

Embedded image

In the mercapto group-containing polysilsesquioxane (a) according to the present invention, the main chain terminal group (in the formula (A),
^{-O-R q, -O-R} r, -O-R s, -O-R t) is trialkyl silylating, trialkylsilyl group ^{(-O-SiR a R b R} c: R a, R ^b and R ^c represent the same or different alkyl groups). Further, a side chain organic group (in the formula (A), -OR ^m ,-
O-R ⁿ ) is present in the mercapto group-containing polysilsesquioxane at least one or more, and each of these side-chain organic groups includes an alkyl group, an aralkyl group, and a substituted or unsubstituted phenyl group. What is chosen (a)
And (c) comprising a mercapto group represented by the following formula (II) ((a) and (c)). Such a mercapto group [1] is contained in the mercaptan group-containing polysilsesquioxane among all side chain organic groups.
Usually, it is desirable that the average number per molecule be 5.0 or less, preferably 3.2 or less, and more preferably 1.6 or less. —R ⁵ —SH (II) (In the formula (II), R ⁵ represents an alkyl group, an alkenyl group, an aralkyl group, or a substituted or unsubstituted phenyl group.)

The number average molecular weight of the mercapto group-containing polysilsesquioxane according to the present invention is from 500 to 5
000, preferably 1,000 to 10,000.
0. The polysilsesquioxane (b) containing at least one mercapto group at the terminal of the main chain has, for example, a structure represented by the following formula (B), wherein R ^m , R ⁿ
Is a side chain organic group, and is represented by —O—R ^u , —O—R ^v , or —O—.
R ^w and —O—R ^y are terminal groups of the main chain, and p is a repeating unit.

[0021]

Embedded image

In the polysilsesquioxane containing a mercapto group according to the present invention, the main chain terminal group (in the formula (B), -O-
R ^u , —O—R ^v , —O—R ^w , and —O—R ^y ) are trialkylsilylated or at least one of the main chain terminal groups is a trialkylsilyloxy group containing a mercapto group; Has become. The terminal trialkylsilyloxy group containing no mercapto group is —O—SiR ^a R ^b R
^c (R ^a , R ^b , and R ^c represent the same or different alkyl groups), and the trialkylsilyloxy group containing a mercapto group is represented by —O—Si (R ^a R ^b ) R ^d
SH (R ^d represents an alkyl group, an aralkyl group, or a substituted or unsubstituted phenyl group).

The mercapto group at the terminal of the main chain is
In the polysilsesquioxane, of all the main chain terminal groups,
In general, it is desirable that the average number per molecule is 4.0 or less, preferably 3.2 or less, more preferably 1.6 or less.

The number average molecular weight of the mercapto group-containing polysilsesquioxane according to the present invention is from 500 to 5
000, preferably 1,000 to 10,000.
0. The polysilsesquioxane (a) having a mercapto group introduced into a side chain is obtained by reacting a non-trialkylated polysilsesquioxane containing a mercapto group with a trialkylsilylating agent as described below. can get. The non-trialkylated mercapto group-containing polysilsesquioxane may be a trialkoxysilane having a mercapto group and / or a trialkoxysilane having an alkyl group, an alkenyl group, an aralkyl group, or a substituted or unsubstituted phenyl group. And / or by hydrolytic condensation with trichlorosilane. The amount of water used for the hydrolytic condensation is generally in a molar ratio of 2 to a polysilsesquioxane production monomer selected from alkoxysilanes.
A value of 4 times is desirable. If the value is less than 4 times, the rate of the hydrolysis / condensation reaction becomes low, and it takes a long time to complete the reaction, or gelation occurs due to insufficient reaction.
Even if the water used for the hydrolysis-condensation reaction is more than 4 times in molar ratio to the polysilsesquioxane-producing monomer selected from alkoxysilane, the reaction completion time does not change.

The concentration of the acid catalyst used for the condensation is generally in the range of 0.005 to 0.05 in terms of a molar ratio with respect to the monomer for producing possilsesquioxane selected from alkoxysilanes.
Is desirable. The temperature in the hydrolytic condensation can be arbitrarily selected, but in consideration of generation of reaction heat and construction of a silsesquioxane structure, the reaction initiation temperature is preferably as low as −20 to 50 ° C. From the viewpoint of constructing a silsesquioxane structure, -10 to 30 is preferable.
C, more preferably -5 to 15C.
With the generation of heat of the hydrolysis-condensation reaction, the solution changes from a state in which two layers are separated to a homogeneous solution, and the solution temperature usually rises by 30 to 50 ° C. from the reaction start temperature. Since the temperature rises, it is desirable to continue the reaction by increasing the solution temperature in order to further promote the condensation. The reaction temperature at this time is preferably 20 to 100 ° C., and more preferably 30 to 95 ° C., and still more preferably 50 to 90 ° C., from the viewpoint of shortening the reaction time and constructing a silsesquioxane structure.
It is good to be. As the trialkyl silylating agent,
Those which do not contain halosilane and are not easily affected by excess water required for the hydrolysis reaction, or those which themselves hydrolyze in an acidic atmosphere to become a silylating agent are used, and generally used silyl Agents can be used. For example, trimethylsilanol, hexamethinedisiloxane, hexaethyldisiloxane and the like can be mentioned. Usually, the reaction is obtained by adding a trialkylsilylating agent to the polysilsesquioxane solution containing a non-trialkylsilylated mercapto group obtained as described above. This trialkyl silylating agent (eg, hexamethyldisiloxane) is
Usually, it is used in an amount of about 1.2 to 5 times.

In addition, such a trialkylsilylation reaction is carried out at the same temperature as that described above, that is, usually from 20 to 100.
° C, preferably 30 to 95 ° C, more preferably 50 to 95 ° C.
Performed at 90 ° C. In order to stop such a reaction, for example, a methanol solution of calcium hydroxide or the like is used.

The polysilsesquioxane (b) containing at least one mercapto group at the terminal of the main chain can be prepared in substantially the same manner as the polysilsesquioxane (a) having a mercapto group introduced into the side chain. It can be produced, and the amount of water for hydrolytic condensation during production, the type of catalyst, the amount of catalyst and the reaction temperature are the same as in the above-mentioned method. In the case of producing a polysilsesquioxane (b) having a mercapto group introduced into a terminal, a point different from the polysilsesquioxane (a) having a mercapto group introduced into a side chain will be described. In the production of the polysilsesquioxane (b) having a mercapto group introduced at the terminal, it is not necessary to use a trialkoxysilane and / or trichlorosilane having a mercapto group. The silylating agent is both the above-mentioned silylating agent and a silylating agent having a mercapto group, and the ratio of each may be adjusted according to the amount of mercaptan to be introduced. Examples of the silylating agent having a mercapto group include 1,3-bis (3-mercaptopropyl) tetramethyldisiloxane, dimethylmercaptopropylmethoxysilane, and the like. When the main chain skeleton is a polydialkylsiloxane, the polydialkylsiloxane containing one or more mercapto groups may be a polydialkylsiloxane having a mercapto group introduced into a side chain (side chain type) or a mercapto group at both ends of the polydialkylsiloxane. Group-introduced (both terminals), polydialkylsiloxane having a mercapto group at one terminal (single-terminal), and polydialkylsiloxane having mercapto groups introduced into both the side chain and both terminals (side) Type). If you show a representative example,

[0028]

Embedded image And the like.

The number of mercapto groups in the polydialkylsiloxane containing a mercapto group is usually 4.0 or less, preferably 3.2 or less, more preferably 1.6 or less per molecule in the polydialkylsiloxane.
It is desirable that the number is not more than the number. The number average molecular weight of the mercapto group-containing polydialkylsiloxane according to the present invention is 5
00 to 50,000, preferably 1,000 to 1
It is 0000. The amount of the polyorganosiloxane compound containing one or more mercapto groups is usually 100 parts by weight of a monomer having a radical polymerizable unsaturated group and a sterically hindered piperidyl group and 100 parts by weight of another radical polymerizable monomer. 0.1 to 50 parts by weight, preferably 0.1 to 4 parts by weight
What is necessary is just to select in the range of 0 weight part.

A copolymer of the radical polymerizable monomer having a sterically hindered piperidyl group according to the present invention and a radical polymerizable monomer having a functional group which reacts with a cellulosic fabric;
The yellowing inhibitor composed of a copolymer of these monomers and other radically polymerizable monomers can be synthesized according to the following procedure.

That is, the radical polymerizable monomer having a sterically hindered piperidyl group, the radical polymerizable monomer having a functional group which reacts with the cellulosic fabric, and other radical polymerizable monomers have a predetermined ratio of chain. A transfer agent is blended as required, and polymerization is carried out in the presence of a radical polymerization initiator under ordinary conditions. As the radical polymerization initiator, any one can be used as long as it is generally used as a general radical polymerization reaction initiator. For example, an azo-based polymerization initiator [for example, 2,2′-azobis (isobutylnitrile),
2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2-cyano-2-propylazo-formamide, dimethyl 2,2′-azobis (2-methylpropionate) and the like] And these can be used in combination. The above polymerization reaction is usually performed in the presence of an organic solvent. As the organic solvent, any solvent can be used as long as it is substantially inert to the monomer used. For example, hydrocarbons [eg, benzene,
Toluene, xylene, cyclohexane, etc.], esters [ethyl acetate, butyl acetate, amyl acetate, etc.], ketones [acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.], ethers [tetrahydrofuran, 1,4-dioxane, etc.] ], Amides [eg, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpropionamide, etc.], pyrrolidones [eg, 1-
Methyl-2-pyrrolidone, ε-caprolactam, etc.], glycol ether acetates [diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, etc.] And the like.

The reaction temperature is not particularly limited, but may be any temperature at which the radical polymerization initiator is decomposed, and is usually 50 to 50.
180 ° C. is preferable, and a method of gradually increasing the temperature from a low temperature to a high temperature may be employed. The reaction time is not particularly limited, but is usually preferably 1 to 24 hours. The number average molecular weight thus obtained is 5,000-100,000,
Preferably, it is 6,000 to 30,000. The reaction product obtained by the production method of the present invention,
Depending on the purpose of use, it may be used as it is as a yellowing inhibitor. In addition, column chromatography, reprecipitation,
It can be purified by a known method such as dialysis.

The fiber substrate using the yellowing inhibitor comprising a compound having a functional group which reacts with the cellulosic fabric of the present invention and having a sterically hindered piperidyl group as an active ingredient is a cellulosic fiber such as cotton, rayon and polynosic. In this case, a cellulosic fiber obtained by singly or blending the fiber may be used.
The yellowing inhibitor in the present invention is usually used as a 0.1 to 50% by weight solution. The solvent used is not particularly limited as long as it dissolves or disperses the yellowing inhibitor.
For example, in addition to the above-mentioned organic solvents, water may be used, and a mixed solvent of two or more thereof may be used. When reacting the yellowing inhibitor with a cellulosic fabric, the cellulose-based fabric is impregnated with a solution of the yellowing inhibitor, squeezed with a roller, and then at 60 to 170 ° C, preferably 80 to 160 ° C.
To perform a dry heat treatment. The heat treatment time is not particularly limited as long as the reaction is sufficiently advanced, and can be appropriately set according to the basis weight of the cellulosic fabric. As the reaction catalyst, an acid or an alkali can be used, but a strong acid metal salt such as zinc borofluoride or magnesium borofluoride is generally used.

[0034]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. [Synthesis Example 1] Glycidylation of SANOL LS-2626 In a 1-liter reaction vessel equipped with a condenser and a thermometer, 180.5 g of SANOL LS-2626 (manufactured by Sankyo Co., Ltd.)
Made),

Embedded image 462.6 g of epichlorohydrin and 2.5 mL of water were added and stirred. Heat until solids dissolve, 102.0
g of sodium hydroxide was added in 6.0 g portions.
Stirred until the exotherm ceased. The temperature of the solution was reduced to 150 ° C. or lower, and excess epichlorohydrin was distilled off with an aspirator while maintaining the temperature. Sodium chloride was precipitated by adding 25 mL of benzene and suction-filtered. Further, the precipitate was washed with 25 mL of benzene, and the solvent was distilled off under reduced pressure together with the filtrate to obtain a brown viscous liquid. Purification by silica gel column chromatography gave 117.
0 g of a colorless target product was obtained. The compound represented by the formula (1) obtained here is referred to as Compound A.

Synthesis Example 2 Mercaptilization and glycidylation of 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate 239.3 g of 1,9.3 was added to a 1-liter reaction vessel equipped with a condenser and a thermometer. 2,2,6,6-pentamethyl-4
-Piperidinyl methacrylate, 78.1 g of 2-mercaptoethanol, 15.0 g of dimethyl 2,2'-azobis (2-methylpropionate) and 300 mL of butyl acetate were added, and the mixture was stirred under a nitrogen atmosphere. The reaction was carried out at 80 ° C. for 7 hours and further at 90 ° C. for 1 hour, and cooled to room temperature. After the solvent was distilled off, the residue was dissolved in 300 mL of tetrahydrofuran and added to a 1-liter reaction vessel equipped with a condenser. After adding 24.0 g of sodium hydride and stirring for 1 hour, 111.0 g of epichlorohydrin was added,
Refluxed for 6 hours. After completion of the reaction, 300 mL of diethyl ether was added, and the reaction solution was washed with 0.5 M aqueous hydrochloric acid (100 mL) and saturated aqueous sodium chloride (100 mL), dried over magnesium sulfate, evaporated, and purified by silica gel column chromatography. This gave 268.9 g of the desired product. The compound represented by the above formula (2) obtained here is compound B
And

[Synthesis Example 3] Synthesis of polymer having glycidyl group and sterically hindered piperidyl group 1,2,2,6,6 in a 500 cc flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. 33.0 g of pentamethyl-4-piperidyl methacrylate (manufactured by Asahi Denka Co., Ltd.), 33.0 g of Blemmer PME 400 (manufactured by Nippon Oil & Fats, methoxypolyethylene glycol monomethacrylate), 28.0 g of methyl methacrylate and glycidyl methacrylate were 5. After charging 0 g, 200.0 g of butyl acetate and 2.0 g of dimethyl 2,2'-azobis (2-methylpropionate) were added, and the mixture was heated with stirring under a nitrogen atmosphere and kept at reflux for 10 hours. . After cooling to room temperature, 295.3 g of a clear, colorless solution were obtained. The molecular weight of the obtained product was measured by gel permeation chromatography (hereinafter abbreviated as GPC) (in terms of polystyrene). As a result, Mn was 20,000 (where Mn is the number average molecular weight). The polymer obtained here is referred to as a polymer A solution.

Synthesis Example 4 Synthesis of Polymer Having Glycidyl Group and Sterically Hindered Piperidyl Group Synthesis of Mercapto Group-Containing Polysilsesquioxane In a 500 cc flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser tube. 9.9 g of 3-mercaptopropyltrimethoxysilane, 199.5 g of methyltriethoxysilane, 5.9 g of phenyltrimethoxysilane and 64.8 g of pure water, and the solution was stirred at a temperature of 5 ° C. under a nitrogen stream. Kept. 3.6% while stirring
Was added dropwise over 30 minutes, and the solution temperature was maintained at 10 ° C. for 1 hour. Next, raise the temperature of the solution to 70
After raising the temperature to 3 ° C. and reacting for 3 hours, 29.1 g of hexaethyldisiloxane was added, and stirring was further continued at 70 ° C. for 3 hours. The solution temperature was lowered to 40 ° C., and 13.4 g of a 4.3 wt% methanol solution of potassium hydroxide was added. Then, the mixture was stirred at room temperature for 2 hours and left for 12 hours. The lower layer was extracted and 150 g of butyl acetate was added. After stirring, the mixture was concentrated at 40 ° C. under a reduced pressure of 200 mmHg to give 150 g.
After distilling off the liquid, butyl acetate was further added at normal pressure for 2 hours.
00g was added and stirred for 1 hour. After the obtained solution was filtered, it was further concentrated under reduced pressure to obtain 82.6 g of a colorless, transparent, viscous liquid. The molecular weight of the obtained product is represented by G
As a result of measurement with a PC (in terms of polystyrene), Mn = 33
00. From the IR spectrum and the Raman spectrum, an absorption based on a mercapto group appeared around 2560 cm @ -1. The obtained polymer is referred to as a mercapto group-containing polysilsesquioxane.

Next, 1,500 cc flask was equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser tube.
33.0 g of 2, 2, 6, 6-pentamethyl-4-piperidyl methacrylate (manufactured by Asahi Denka Co., Ltd.), Blemmer PM
50.0 g of E400 (manufactured by NOF CORPORATION), 11.0 g of methyl methacrylate, 5.0 g of glycidyl methacrylate and 3.0 g of mercapto group-containing polysilsesquioxane were charged, and then 200.0 g of butyl acetate. Dimethyl 2,2'-azobis (2-methylpropionate) (2.0 g) was added, and the mixture was heated with stirring under a nitrogen atmosphere and kept at reflux for 10 hours. After cooling to room temperature, 29
6.2 g of a clear, colorless solution were obtained. As a result of measuring the molecular weight of the obtained product by GPC, Mn was 11,000. The absorption due to the mercapto group near 2560 cm ^-1 in the Raman spectrum due to the mercapto-containing polysilsesquioxane had disappeared. The obtained polymer is referred to as a polymer B solution.

Example 1 Evaluation of Yellowing Inhibiting Effect of Cotton A 20% by weight solution of Compounds A and B and Polymers A and B obtained in Synthesis Examples 1 to 4 in butyl acetate was prepared. A standard cotton cloth of the Japan Oil Chemistry Association was cut into 4 × 4 cm, and each of the extraction treatments with benzene and diethyl ether was immersed in a degreased cloth, and squeezed with a roller to a squeezing ratio of 80%. Next, drying treatment was performed in a dryer at room temperature under a nitrogen stream for one day. As a catalyst, an aqueous solution containing 4% by weight of zinc borofluoride was impregnated with a standard cotton cloth on which the compounds A and B and the polymers A and B were fixed.
Squeeze with a roller to a squeezing ratio of 80%, dry at 120 ° C for 1 minute under a nitrogen atmosphere, cure at 165 ° C for 2 minutes under a nitrogen atmosphere, and compound A, B and polymer on a standard cotton cloth. A and B were combined. After cooling to room temperature under a nitrogen atmosphere, a solution of squalene (manufactured by Tokyo Chemical Industry Co., Ltd.), which is one of sebum stain components attached to underwear, was applied to a cotton cloth treated with compounds A and B and polymers A and B. The weight of squalene after drying was adjusted to 20 mg per cloth. After drying, each test cotton cloth was left in a thermostat at 29 ° C. for 6 months.

After taking out from the thermostat, the yellowing degree was evaluated by measuring the Δb value of the sample cloth with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd.). (When replacing colors with numerical values, there is a display unit called Lab. Lightness is represented by L, and hue and saturation are represented by a and b.
b indicates the yellow-blue direction of the color. Here, the b value was measured as the degree of yellowness, and the yellowing degree was indicated by the Δb value. B) = b1−b0 b1: b value of test cloth after treatment b0: b value of test cloth before treatment As a result, the Δb values of cloths treated with Compounds A and B and polymers A and B were 1. 32, 1.29, 1.14
And 1.02. On the other hand, the untreated cloth similarly coated with squalene had a Δb value of 9.50.

Example 2 Evaluation of the Yellowing Inhibiting Effect of Cotton In order to double the compounds A and B and the polymers A and B to be bonded to the standard cotton cloth in Example 1, the concentration of each solution was set to 40% by weight. %, The same process as in Example 1 was performed, and the Δb value was observed.
1, 1.10, 0.85 and 0.92.

[0042]

The yellowing inhibitor of the present invention comprising a compound containing a sterically hindered piperidyl group as an active ingredient can be worn and washed by treating a fiber substrate by a method conventionally used in the field of textiles. Is repeated, it is possible to suppress the phenomenon that the one stored in a storage box such as a closet turns yellow.

Claims (3)

[Claims] 1. A yellowing inhibitor comprising a compound having a light-stabilizing action having a reactive functional group and having a sterically hindered piperidyl group. 2. A copolymer of a radically polymerizable monomer having a sterically hindered piperidyl group and a radically polymerizable monomer having a functional group capable of reacting with a cellulosic fabric, or The yellowing inhibitor according to claim 1, which is a copolymer of the monomer and another radical polymerizable monomer. 3. The yellowing inhibitor according to claim 1, wherein the functional group that reacts with the cellulosic fabric is a glycidyl group.