JP2002004131A - Reversiblly color-changeable by light melt-spun polyolefin fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a melt-spun polyolefin fiber having a reversible color- changing property, showing a highly concentrated, clear and stable color, the melt-spinning temperature neither lowering to inhibit the thermal decomposition of an organophotochromic compound, nor occuring color unevenness or blooming by increasing the compatibility of the organophotochromic compound. SOLUTION: This melt-spun polyolefin material having the reversible color- changing property is provided by containing the 3 components of the organic photo-chromic compound, a thermal decomposition-inhibiting agent and a high boiling solvent as indispensable components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoreversible color-changing polyolefin melt spun product. More specifically, by changing the color reversibly by irradiation of sunlight or black light, for example, doll hair, wig, false hair, hair piece, hair accessories, fabrics, etc. The present invention relates to a sharp and stable photoreversible color-changing polyolefin melt spun product.

[0002]

2. Description of the Related Art Attempts have been made to color molded articles such as fibers with a coloring agent such as a pigment.

[0003] In the coloring technique of such a molded product, there is a method of spinning the pigment by directly kneading the pigment into the base polymer depending on the pigment (Japanese Patent Laid-Open No. 1-168911). Since it is difficult to uniformly disperse the pigment in a pigment, a masterbatch (polymer) containing a pigment at a high concentration is usually prepared, and the masterbatch is added to a pigment-free base polymer and molded (Japanese Patent Application Laid-Open No. Sho 62). -39208).

In the case where the coloring agent is an organic photochromic compound, if the compound is mixed with various fiber types other than polyolefins, such as polyester, nylon, and acryl, it will not exhibit photoreversible discoloration. For use in the body, it is virtually impossible to use other than a polyolefin resin as a fiber type.

[0005] In addition, when a photoreversible discolorable polyolefin melt spun product is obtained using an organic photochromic compound, various problems as described below are accumulated, and it is necessary to solve the problem. .

(I) When exposed to a high temperature such as the melt spinning temperature, the organic photochromic compound not only exhibits thermal decomposition and no longer exhibits photochromic properties, but also produces unpleasant coloring of the melt spun body itself due to the decomposition product. Take on.

(Ii) Therefore, the melt spinning temperature must be lowered, but this makes it impossible to use a yarn-molding grade resin, and generally has a lower softening point (or a higher melt flow index). The use of molding grade resin is forced. However, using such a grade of resin makes it impossible to satisfy various performances and strengths normally required for a spun body, so that only a spun body with inferior performance can be obtained.

(Iii) As described above, since the organic photochromic compound is difficult to dissolve in the polyolefin resin and cannot be present at a uniform concentration, it is necessary to prepare a master batch which requires complicated and strict process control in advance. Otherwise, color unevenness occurs.

(Iv) Since the organic photochromic compound is hardly compatible with the polyolefin resin as described above, most of the organic photochromic compound exists in a crystalline state, so that not only the photoreversible discoloration property is lowered but also the blooming or migration occurs. No longer exhibit photochromic properties over time.

As described above, it is necessary to solve a difficult problem in a method of obtaining a photoreversible discolorable polyolefin melt spun body by using an organic photochromic compound as a coloring agent. The only methods are U.S. Pat. Nos. 5,213,733 and 5,422,181.

[0011] The above-mentioned US patent discloses a method in which the desired photoreversible discoloration is obtained by employing the above-mentioned masterbatch method and spinning at a spinning temperature of less than 250 ° C and a spinning diameter of at least 0.3 mm. It seems that a polyolefin melt spun body has been obtained.

[0012] However, this US patent is not complete in that it employs a masterbatch method which requires complicated and strict process control and requires tedious operation means of strict control of spinning conditions. Absent.

As described above, at present, there is no method for easily producing a melt-spun photoreversible color-changing polyolefin satisfying sufficient performance.

[0014]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to effectively suppress the thermal decomposition of an organic photochromic compound during melt spinning. This eliminates the need to limit the melt spinning temperature to a low temperature and enhances the compatibility of the organic photochromic compound, resulting in high-density, clear and stable photoreversible color change without color unevenness or blooming. It is an object of the present invention to provide a fused polyolefin melt spun body.

[0015]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and found that the conventional problems can be eliminated by melt-spinning the organic photochromic compound in the presence of a specific component. The inventor has obtained the knowledge that it can be made, and further studied based on this knowledge, and has finally completed the present invention.

That is, the photoreversible color-changing polyolefin melt spun body of the present invention has the following constitution.

1. A photoreversible color-changing polyolefin melt spun body comprising three essential components of an organic photochromic compound, a thermal decomposition inhibitor, and a high boiling point solvent.

2. 2. The photoreversible color-changing polyolefin melt according to the above 1, wherein the amounts of the thermal decomposition inhibitor and the high boiling point solvent are in the range of 0.1 to 50 parts by weight and 2 to 300 parts by weight, respectively, based on 1 part by weight of the organic photochromic compound. Spun body.

3. 2. The photoreversible color-changing polyolefin melt spun according to 1 above, wherein the high-boiling-point solvent is compatible with the polyolefin resin and the organic photochromic compound is dissolved at least 0.1% or more at a melting point or more.

4. 2. The melt-spun photoreversible color-changing polyolefin according to the above 1, wherein the thermal decomposition inhibitor is a hindered amine compound and / or a hindered phenol compound.

5. Without passing through the masterbatch manufacturing process, the essential components consisting of the organic photochromic compound, the thermal decomposition inhibitor and the high boiling point solvent are directly added to and mixed with the polyolefin resin as the base polymer, and the resulting mixture is directly melt-spun. 5. The process for producing a photoreversible color-changing polyolefin melt spun according to the above item 1, 2, 3 or 4.

The greatest feature of the present invention is that a specific component coexists with the organic photochromic compound.

That is, the photoreversible color-changing polyolefin melt spun body of the present invention is obtained by directly adding three components of an organic photochromic compound, a thermal decomposition inhibitor and a high boiling point solvent to a polyolefin resin without going through a masterbatch production step.
It is manufactured by a method in which the obtained mixture is melt-spun as it is.

By the way, in order to obtain a photoreversible color-changing polyolefin melt spun body, it is necessary to add an organic photochromic compound to the spun body. However, the compound becomes unstable due to heat and is hardly compatible with the polyolefin. It was difficult to knead the compound directly into the spun body.

Therefore, as described above, conventionally, in order to obtain a photoreversible color-changing polyolefin melt spun body, first, an organic photochromic compound is dissolved in the same or the same type of polymer as the polyolefin resin constituting the melt spun body. After producing a master batch, melt spinning was performed using the master batch (US Pat. No. 5,213,733).
issue).

As described above, in a method for producing a melt-spun photoreversible color-changing polyolefin, it was considered that the above-mentioned masterbatch step was essential.

However, the production of this master batch requires complicated and strict process control, and these polymers are inferior in the dissolving power of the organic photochromic compound.
At first glance, even when it appears that the organic photochromic compound could be uniformly dissolved in the master batch, the organic photochromic compound will be non-uniformly present in the final melt spun body, resulting in uneven color and This was the cause of blooming. Moreover, since no means for suppressing the thermal decomposition of the organic photochromic compound has been provided, thermal decomposition easily occurs by applying the melting temperature at the time of manufacturing the master batch or the melting temperature at the time of spinning, and the intended performance is completely reduced. There was a problem that was not shown.

On the other hand, in the present invention, the use of a combination of a high boiling point solvent and a thermal decomposition inhibitor makes it possible to omit the master batch production step.

That is, the present invention dramatically improves the solubility of an organic photochromic compound by using a high boiling point solvent, and furthermore, by using a thermal decomposition inhibitor,
By suppressing the thermal decomposition of organic photochromic compounds, it is possible to obtain high-concentration, clear and stable photoreversible color-changing polyolefin melt spun products without performing a masterbatch manufacturing process that requires strict process control. It was done.

In the present invention, by employing the above-mentioned means, the production of the photoreversible color-changing polyolefin melt spun body of the present invention is simplified, and the organic photochromic compound is thermally decomposed, As a result, the present invention does not cause any blooming or migration, and as a result, in the present invention, the photoreversible color change has excellent sharpness, high density, and excellent stability over time without any occurrence of color unevenness. It has become possible to obtain a polyolefin melt spun body.

Further, the present invention is advantageous in that strict management of spinning conditions as in the conventional method is not required, and that the spinning conditions and the like may be appropriately set.

As described above, in the past, although the master batch production process was an essential requirement and was not performed, the present invention provides the above two means, namely, pyrolysis. The adoption of the means of an inhibitor and a high boiling point solvent not only made it possible to obtain a photoreversible color-changing polyolefin melt spun body having the above excellent properties, but also simplified the setting of the spinning conditions. This is an unexpected result, and it will be understood that the selection of the thermal decomposition inhibitor and the high boiling point solvent of the present invention has a special significance.

Hereinafter, the present invention will be described in more detail.

1. Constituents of the photoreversible polyolefin melt spun body The photoreversible polyolefin melt spun body of the present invention is composed of an organic photochromic compound, a thermal decomposition inhibitor and a high-boiling solvent as three essential components, If any one of the components is missing, the desired effect cannot be achieved.

The above-mentioned essential components of the present invention can be directly mixed with the polyolefin resin which is the base of the melt spun body during the production of the melt spun body, so that a complicated master batch production step is not required. The fact that a spun body can be manufactured is one of the major features of the present invention.

The melt spun body of the present invention is produced by mixing the above essential three components and the base component polyolefin resin and spinning the mixture. First, the components of the spun body will be described. .

(A) Organic Photochromic Compound The organic photochromic compound of the present invention is used for imparting photoreversible discoloration to a polyolefin melt spun product.

The organic photochromic compound of the present invention refers to an organic compound having a function of changing color reversibly by light of a specific wavelength, and a compound having a function of developing color by the light and decoloring by heat. included.

The structure of the organic photochromic compound of the present invention is not particularly limited as long as it is a conventionally known organic photochromic compound, and various compounds can be selected over a wide range.

For example, various types such as azobenzene, thioindigo, dithizone metal complex, spiropyran, naphthopyran, spirooxazine, spirothiopyran, fulgide, dihydroprene, triphenylmethane, diarylethene, viologen, etc. An organic photochromic compound can be arbitrarily selected and used.

Among these, structurally, photoresponsiveness,
It is preferable to use spiropyran-based, naphthopyran-based, benzopyran-based or spirooxazine-based ones, which have excellent properties in terms of concentration at the time of color development, repetitive use, etc. It is preferable to use a compound having a molecular weight of 300 or more, which has a property of making the blooming phenomenon difficult to occur.

More specific examples of these compounds include 1,3-dihydro-1,3,3-trimethyl-6 '
-(1-piperidinyl) -spiro [2H-indole-
2,3 ′-[3H] naphtho [2,1-b] [1,4] oxazine], 6 ′-(2,3-dihydro-1H-indole-1
-Yl) -1,3-dihydro-1,3,3-trimethyl-spiro [2H-indole-2,3 '-[3H] naphtho
[2,1-b] [1,4] oxazine], 1,3-dihydro-1,3,3-trimethyl-6 '-(1-piperidinyl)
-4- (trifluoromethyl) -spiro [2H-indole-2,3 '-[3H] naphtho [2,1-b] [1,4] oxazine], 1,3-dihydro-1,3,3 , 4,5-Pentamethyl-spiro [2H-indole-2,3 '-[3
H] naphtho [2,1-b] [1,4] oxazine], 3,3-
Examples thereof include diphenyl-3H-naphtho [2,1-b] pyran and 6-methoxy-2,2-diphenyl-2H-1-benzopyran, but are not limited thereto.

In the present invention, each of the organic photochromic compounds can be used alone or in combination of two or more. The amount of the organic photochromic compound is not particularly limited, but is usually based on the total weight of the spun body. 0.001
-5% by weight, preferably 0.01-1% by weight,
A sufficient coloring density can be obtained during light irradiation.

(B) Thermal Decomposition Inhibitor The thermal decomposition inhibitor of the present invention is used to prevent thermal decomposition of an organic photochromic compound.
The type of the thermal decomposition inhibitor of the present invention is not particularly limited as long as it has a function of effectively suppressing the decomposition of the organic photochromic compound by heat. Specifically, it is preferable to use a hindered amine compound and / or a hindered phenol compound.

The above compounds are generally known to have an effect of improving the photostability of the organic photochromic compound. However, the organic photochromic compound may be used in a special environment such as that employed in the present invention, that is, in a polyolefin resin. The effect of effectively suppressing the thermal decomposition of the compound is an effect that was first discovered by the study of the present inventors, and is a novel effect that has never been known before.

Although the detailed mechanism of how the compound used as a thermal decomposition inhibitor of the present invention acts to suppress the thermal decomposition of an organic photochromic compound has not been elucidated yet, the compound and an organic photochromic compound have not been elucidated yet. It is speculated that a kind of complex is formed between the photochromic compounds, which may dramatically improve the stability of the organic photochromic compound when heated.

Such a presumption can be inferred from the following functions and effects of the above-mentioned thermal decomposition inhibiting compound.

That is, since the above-mentioned compound has an action of changing the hue of the organic photochromic compound when the color is formed, various colors are provided even if the same organic photochromic compound is used depending on the kind of the compound. It becomes possible.

Therefore, it is considered that such a favorable operation and effect is exhibited, as described above, as evidence that a complex is formed. Further, the effect on the hue is an extremely effective means when it is necessary to adjust the color to a desired hue.

Further, when the compound coexists, blooming of the organic photochromic compound from the final melt spun body can be effectively prevented.
Providing such a favorable effect also supports that the formation of the complex stabilizes the organic photochromic compound.

In any case, the various excellent effects exhibited by these compounds together with the effect of inhibiting thermal decomposition constitute a major feature of the present invention.

Examples of the compounds which can be used as the thermal decomposition inhibitor of the present invention include:
Bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, poly [{6- (1,
(1,3,3-tetramethylbutyl) amino-1,3,5
-Triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidinyl) imino} hexamethylene
(2,2,6,6-tetramethyl-4-piperidinyl) imino], 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinic acid polycondensate, 2 Bis (1,2,2-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate
2,6,6-pentamethyl-4-piperidinyl), 8-
Benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-
2,4-dione, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3, 9
Condensate with-(2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol, 1,2,2,6
6-pentamethyl-4-piperidinyl-tridecyl-
Mixed tetraesters of 1,2,3,4-butanetetracarboxylic acid, tetra (1,2,2,6,6-pentamethyl-4-piperidinyl) -butanetetracarboxylate, and the like can be mentioned. The compound is not limited to the above, and any known hindered amine compound can be used.

The hindered phenol compounds include, for example, 2,4-di-t-butylphenyl-3 ',
5'-di-t-butyl-4'-hydroxybenzoate, 4,4'-methylenebis- (2,6-di-t-butylphenol), 4,4'-thiobis- (3-methyl-6
-T-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 2,2'-methylenebis (4-methyl-6-t-
Butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 3,9-bis [1,1
-Dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl]
2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis- [methylene-3- (3 ', 5'-di-
t-butyl-4'-hydroxyphenyl) propionate] methane and the like, but are not limited thereto, and any conventionally known hindered phenol compounds can be used. .

In the present invention, at least one kind of a hindered amine compound or a hindered phenol compound is used. However, at least one kind of both a hindered amine compound and a hindered phenol compound can be used. It is preferable to use a compound having a structure having a dophenol structure in one molecule.

Compounds having such a structure include, for example, bis (1,2,2,6,6-pentamethyl-4-
Piperidyl) [[3,5-bis (1,1-dimethylethyl)
-4-hydroxyphenyl] methyl] butylmalonate,
1- [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3-
(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine and the like, but are not limited thereto.

The amount of the thermal decomposition inhibitor used in the present invention is usually
0.1 to 1 part by weight of the organic photochromic compound
It is suitable that the amount is 50 parts by weight, preferably 0.3 to 20 parts by weight. When the amount is less than the above amount, an effective thermal decomposition suppressing effect on the organic photochromic compound cannot be exhibited. On the other hand, if the amount exceeds the above, there is a relatively large amount of those not involved in the complex with the organic photochromic compound, and these not only do not contribute to the effect of suppressing thermal decomposition, but, on the contrary,
It itself causes blooming and migration over time.

In any case, undesirable results may be caused depending on the amount of the thermal decomposition inhibitor used. Therefore, in the present invention, it is preferable to use the optimal amount of the thermal decomposition inhibitor with respect to the organic photochromic compound. is important.

(C) High-boiling solvent The high-boiling solvent of the present invention is used to increase the compatibility of the components of the photoreversible color-changing polyolefin melt spun product.

Accordingly, the high-boiling solvent used in the present invention has a function of exhibiting excellent solubility in the organic photochromic compound and the thermal decomposition inhibitor and exhibiting good compatibility with the polyolefin resin described later. If so, the type does not matter.

The high boiling point solvent of the present invention, having such a function, enables the organic photochromic compound to be uniformly present in the polyolefin melt spun body without color unevenness, and has the same effect as the above-mentioned thermal decomposition inhibitor. This is the most significant feature of the present invention, in that blooming or migration can be effectively prevented.

Such a high boiling point solvent is preferably compatible with the polyolefin resin and dissolves at least 0.1% or more of the organic photochromic compound at the melting point or more, more preferably 0.3% or more. It is preferable that the compound dissolves as described above. If the dissolving power is lower than the above value, the supporting power (dissolving action) for the organic photochromic compound in the melt spun body will be inferior. As a result, not only does the organic photochromic compound cause blooming and migration over time, but also the molecular behavior of the organic photochromic compound itself is suppressed, so that it does not exhibit sharp photochromic properties at the time of light reception.

The reason why the upper limit of the dissolving power is not particularly set is that, as is clear from the above description, the higher the dissolving power for the organic photochromic compound, the more advantageous effects are brought about in the present invention. .

As the high boiling point solvent of the present invention, various compounds can be selected over a wide range without any particular limitation as long as the above conditions are satisfied.

For example, higher alcohols such as myristyl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol; palmitic acid, stearic acid,
Higher fatty acids such as 12-hydroxystearic acid, calcium stearate, butyl stearate, lauryl laurate, cetyl myristate, stearyl stearate, amide myristate, amide stearate, ethylenebisstearamide, distearyl ketone; dioctyl phthalate Plasticizers such as, diethylhexyl phthalate, diisononyl phthalate, dioctyl adipate, diisodecyl adipate, dioctyl azelate, dibutyl sebacate, tributyl citrate, tributyl phosphate, chlorinated paraffin, diethylene glycol dibenzoate, etc .; paraffin wax, liquid paraffin, microcrystalline Wax, polyethylene wax, polypropylene wax, beeswax, montan wax, anhydrous lanoli , There may be mentioned waxes such as carnauba wax, but is not limited thereto.

In the present invention, these compounds can be used alone or in combination of two or more. The amount of the compounds used is not particularly limited. It is suitable that the amount is in the range of 2 to 300 parts by weight, preferably 5 to 200 parts by weight with respect to parts by weight. When the ratio is below the above range, the concentration of the organic photochromic compound in the spun body becomes relatively low due to the balance with the dissolving power for the organic photochromic compound, and a remarkable photochromic effect cannot be obtained. On the other hand, if it exceeds the above range, the fiber strength of the melt spun body is reduced.

(D) Polyolefin resin The polyolefin resin used in the present invention constitutes the base of the melt spun body, and any conventionally known polyolefin resin having a fiber forming ability can be used.
There is no limitation.

For example, polyethylene, polypropylene,
Ethylene-propylene copolymers, ethylene-propylene-diene terpolymers and the like can be mentioned, and acrylonitrile, (meth) acrylic acid, (meth) acrylate, vinyl acetate, styrene, Examples thereof include those in which a different kind of monomer such as vinyl chloride is copolymerized in a small amount, those in which these are partially cross-linked, and mixtures thereof. Further, in addition to those exemplified above, a small amount of a different polymer such as nylon, urethane, acrylic, vinylon, polyester, polyvinyl chloride, or saran may be added, and these are also the polyolefins referred to in the present invention. It is included in the resin.

(E) Other Components In the present invention, a viscosity modifier described later can be added together with the above-mentioned essential three components, and other known additives can be optionally used in combination.

Examples of these additives include organic pigments, inorganic pigments, fluorescent pigments, luminous pigments, pearl pigments, metallic pigments, ultraviolet light-emitting pigments, gold powder, silver powder, glass powder, thermochromic microcapsule pigments, and fragrances. Including pigments such as microcapsules, UV absorbers,
Antioxidants, light stabilizers, extenders, electrochromic agents, liquid crystals, dyes, fluorescent dyes, fluorescent brighteners, fragrances, flame retardants, flame retardants, deodorants, antibacterial agents, preservatives, fungicides, Examples include repellents, photocatalysts, and the like, but are not limited thereto.

2. Molding method of photoreversible discolorable polyolefin melt spun body The photoreversible discolorable polyolefin melt spun body of the present invention is, as described above, without passing through a masterbatch production step, of an organic photochromic compound, a thermal decomposition inhibitor and a high boiling point solvent. The three essential components can be directly added to and mixed with the polyolefin resin as the base polymer, and the resulting mixture can be produced by melt spinning as it is.

Hereinafter, the method of mixing the raw materials and the melt spinning method in the method of forming the melt spun body will be described.

(A) Method of Mixing Production Materials Production materials comprising an organic photochromic compound, a thermal decomposition inhibitor and a high-boiling-point solvent and three essential components and a polyolefin resin as a base polymer are prepared, for example, by the following method. , But is not limited thereto.

1) A method in which the above three essential components are separately added to a polyolefin resin.

2) A method of preliminarily powder-blending the above three essential components and then blending the mixed powder with a polyolefin resin.

3) A method in which a mixture obtained by uniformly melting and mixing the above-mentioned essential three components is blended as a pellet or a cooled pulverized body.

The mixture for melt spinning mixed by such a method is directly subjected to the next melt spinning step.

Therefore, in the present invention, the master batch manufacturing step, which is essential in the conventional method, is no longer necessary, but this is one of the major features of the present invention.

When the mixed powder or the molten mixture is mixed with the polyolefin resin and melt-spinning is performed, if the kneading with the polyolefin resin becomes impossible due to a decrease in the melt viscosity or the like, the viscosity is adjusted. For the purpose, a resin component which is the same as or different from the polyolefin resin can be added to the mixed powder or the molten mixture.

(B) Melt-spinning method The melt-spinning mixture obtained by the above-mentioned method for mixing the raw materials is directly subjected to melt-spinning, and the melt-spinning method of the present invention may be any of conventionally known methods. Adoption is not a problem, and there is no limitation.

In the melt spinning method of the present invention, the melting temperature, spinning speed, draw ratio, diameter and shape of the spinneret, etc.
All conventionally known conditions can be applied.

As described above, despite the use of a special component such as an organic photochromic compound, it is a major feature of the present invention that such conditions can be applied without any limitation. Its industrial applicability is enormous.

In particular, the melting temperature may be any temperature as long as it is higher than the melting point of the polyolefin and lower than the decomposition temperature of the organic photochromic compound.
It is good to carry out at 300 ° C, preferably 180-270 ° C. Prior art, for example, as in the aforementioned U.S. Pat.
There is no need to limit it to below 0 ° C.

The photoreversible color-changing polyolefin melt spun body of the present invention can have various cross-sectional shapes (for example, a circle, an ellipse, a star, a triangle, a gear, etc.) by arbitrarily adjusting the conditions as described above. And thickness (for example, 0.1 to 500 μm)
And various properties such as fiber strength can be freely adjusted.

As described above, known additives can be arbitrarily blended into the photoreversible color-changing polyolefin melt spun body of the present invention.

3. Use The photoreversible color-changing polyolefin melt spun body of the present invention can be suitably used particularly for materials having commercial value in color, for example, fabrics, clothing, bedding, doll hair, wigs, false hair, hair pieces, hair accessories, and the like.

[0086]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

In the following description, “part” or “%”
The term "parts" means "parts by weight" or "% by weight" unless otherwise specified.

[0088]

Example 1 As an organic photochromic compound, 6'-
(2,3-dihydro-1H-indol-1-yl)-
1,3-dihydro-1,3,3-trimethyl-spiro
[2H-indole-2,3 '-[3H] naphtho [2,1-
b] [1,4] oxazine] 1 part, bis as a thermal decomposition inhibitor
One part of (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and 50 parts of ethylenebisstearamide as a high boiling point solvent are uniformly mixed in a V-type tumbler, and the powder of the essential three components of the present invention is mixed. A blend was obtained.

5 parts of the powder blend obtained in this manner was mixed with 95 parts of a polyolefin resin (yarn molding grade polypropylene resin; Novatec PP FY6 (melt flow index: 2.3 g / 10 min), manufactured by Nippon Polychem). After uniformly mixing with a mold tumbler, the mixture was put into a melt spinning device and heated to 240 ° C.
, And stretched 7 times with a stretching roll to obtain a photoreversible color-changing polypropylene melt spun body of the present invention having a thickness of about 70 μm.

When the melt spun product was exposed to sunlight, it developed a strong reddish blue color. On the other hand, when the sunlight irradiation was stopped, it became colorless, and such discoloration could be repeated reversibly many times.

The performance of the melt spun body is shown in Table 1 below.
Are described together.

[0092]

Example 2 In the powder blend of Example 1,
Furthermore, 4,4'-thiobis- (3-
(Methyl-6-t-butylphenol) A photoreversible discolorable polypropylene melt spun body of the present invention was obtained in the same manner except that 1 part of methyl-6-t-butylphenol was added.

When the melt-spun product was exposed to sunlight, it developed a strong yellowish blue color. On the other hand, when the sunlight irradiation was stopped, it became colorless, and such discoloration could be repeated reversibly many times. As described above, since the hue at the time of color development was different from that of Example 1, it was confirmed that the thermal decomposition inhibitor also had the function of adjusting the hue.

The performance of the melt spun body is shown in Table 1 below.
Are described together.

[0095]

Comparative Example 1 In the powder blend of Example 1,
A polypropylene melt spun body for comparison was obtained in the same manner as above except that 1 part of the thermal decomposition inhibitor was not used.

When this melt spun product was exposed to sunlight, it slightly developed a blue color. However, even when the sunlight irradiation was stopped, it showed a light brown color and did not show a clear discoloration effect. This is probably because the organic photochromic compound was thermally decomposed.

The performance of this melt spun body is shown in Table 1 below.
Are described together.

[0098]

Comparative Example 2 In the powder blend of Example 1,
A polypropylene melt spun body for comparison was obtained in the same manner except that 50 parts of a polypropylene resin (Novectec PP FY6) was used instead of 50 parts of the high boiling point solvent.

When the melted spun product was exposed to sunlight, it developed a blue color. However, a uniform colored state was not obtained in the entire melted spun product, and color unevenness occurred.

Further, when the melt spun product was left for 60 days, a blooming phenomenon of the organic photochromic compound was confirmed.

The performance of the melt spun body is shown in Table 1 below.
Are described together.

[0102]

Comparative Example 3 In the powder blend of Example 1,
Without using 1 part of the thermal decomposition inhibitor, a high boiling solvent 50
Part is replaced by polypropylene resin (Novec PP
Except for using 50 parts of FY6), a polypropylene melt spun body for comparison was obtained in the same manner except for using 50 parts.

When the melted spun product was exposed to sunlight, it developed a blue color, but the coloration was non-uniform, and when it was not irradiated with sunlight, it exhibited a light brown color.

Further, when this melt spun product was left for 60 days, a blooming phenomenon of the organic photochromic compound was confirmed.

The performance of this melt-spun product is shown in Table 1 below.
Are described together.

[0106]

[Table 1] The symbols (○, Δ, ×) in Table 1 mean the following: (1) Color development upon light irradiation: ○ = good.

△ = low color density.

X = The color density is very low.

(2) Color unevenness during light irradiation: ＝= No color unevenness occurred over the entire melt spun body.

Δ = Partial color unevenness occurred.

X = Color unevenness is remarkable.

(3) Coloring property under non-light irradiation: ＝= No coloration.

△ = slightly tan.

X = Light brown color and light discoloration itself is unclear.

(4) Blooming: ＝= No blooming occurs even if left for 60 days.

Δ = blooming is observed after standing for 60 days.

× = Blooming is remarkable after standing for 60 days.

Example 3 As an organic photochromic compound, 3,3
1 part of -diphenyl-3H-naphtho [2,1-b] pyran,
As a thermal decomposition inhibitor, 1- [2- [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionyloxy]
Ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6
0.5 part of 6-tetramethylpiperidine and 30 parts of paraffin wax as a high boiling point solvent were uniformly mixed by a V-type tumbler to obtain a powder blend of three essential components of the present invention.

To 10 parts of the powder blend, a polypropylene resin (Novatec PP BC03C (melt flow index: 30.
0 g / 10 min), 10 parts of Nippon Polychem Co., Ltd.) was added, and after tumbling and mixing, a pellet-shaped molten mixture was obtained with a pellet production apparatus.

10 parts of the molten mixture was mixed with a polypropylene resin (Novatec PP, supra) as a polyolefin resin.
FY6) After tumbling and mixing with 90 parts, this mixture is put into a melt spinning apparatus, melt-spun at 230 ° C., and stretched 8 times by a stretching roll, whereby the photoreversible color change of the present invention having a thickness of about 60 μm is obtained. A polypropylene melt spun product was obtained.

When the molten spun product was exposed to sunlight, the color of the product became yellow. On the other hand, when the sunlight irradiation was stopped, the product became colorless. Such discoloration could be repeated reversibly many times.

This melt-spun product did not show any color unevenness at the time of coloring, and no blooming phenomenon was observed even after standing for 60 days. In addition, since unnecessary coloration was not exhibited at the time of decoloration, it was confirmed that thermal decomposition of the organic photochromic compound was suppressed.

[0122]

Example 4 1,3 as an organic photochromic compound
-Dihydro-1,3,3-trimethyl-6 '-(1-piperidinyl) -spiro [2H-indole-2,3'-
1 part of [3H] naphtho [2,1-b] [1,4] oxazine]
As a thermal decomposition inhibitor, 0.5 part of a mixed tetraester of 1,2,2,6,6-pentamethyl-4-piperidinyl-tridecyl-1,2,3,4-butanetetracarboxylic acid, and 3,9-bis [1,1-dimethyl-2- [β
-(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-
0.5 parts of tetraoxaspiro [5,5] undecane, 20 parts of distearyl ketone as a high-boiling solvent, 20 parts of the same polyethylene wax, 30 parts of a polypropylene resin (Novatec PP BC03C described above) as a viscosity modifier and 0 parts of an organic yellow pigment After tumbling and mixing .2 parts, a molten mixture containing the essential three components of the present invention in the form of pellets was obtained by a pelletizer.

Next, 10 parts of the molten mixture was mixed with a polypropylene resin (Novatech P.C.) as a polyolefin resin.
PMA6 (melt flow index: 1.4 g / 10
min), tumbler mixed with 90 parts of Nippon Polychem Co., Ltd.
, And 10 times stretched by a stretching roll to obtain a photoreversible color-changing polypropylene melt spun body of the present invention having a thickness of about 50 μm.

In this embodiment, the conventional method (US Pat.
Despite the high spinning temperature of 260 ° C., which cannot be considered in JP-A No. 213,733), the obtained melt-spun body exhibited the following excellent properties.

1) When the sunlight was applied to the melt-spun product, the color of the product became blond. On the other hand, when the sunlight irradiation was stopped, the color of the product became yellow, and such discoloration could be repeated reversibly many times.

2) The melt spun body did not show any color unevenness during color development, and did not show any blooming phenomenon even after standing for 60 days.

3) Unnecessary coloration was not exhibited at the time of decoloring, and it was confirmed that thermal decomposition of the organic photochromic compound was suppressed.

According to the results of the above Examples and Comparative Examples,
By using the thermal decomposition inhibitor and the high boiling point solvent of the present invention, the thermal decomposition and blooming phenomenon of the organic photochromic compound are suppressed, and the photoresponsiveness is dramatically improved. Although a melt-spun photoreversible color-changing polyolefin having excellent stability over time has been obtained, it is clear that such an excellent effect was achieved by a synergistic effect of the two agents.

[0129]

(1) The use of the thermal decomposition inhibitor and the high boiling point solvent of the present invention eliminates the need for a complicated master batch production process which has been conventionally required, and simplifies the production process.

(2) The present invention is very advantageous in that there is no strict restriction on spinning conditions such as the melting temperature as in the prior art, and a conventionally known melt spinning method can be employed.

(3) By using the above-mentioned thermal decomposition inhibitor and high boiling point solvent, thermal decomposition and blooming of the organic photochromic compound are suppressed.

(4) As a result, according to the present invention, a photoreversible color-changing polyolefin melt spun body having a sharply high density with excellent photoresponsiveness and excellent in stability over time without any occurrence of color unevenness, etc. It became possible to provide.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/375 C08K 5/375 C08L 23/02 C08L 23/02 D01F 1/10 D01F 1/10 (72) Inventor Ryuichi Hoshikawa 29, Nishino-rimiyacho, Yamashina-ku, Kyoto, Kyoto Prefecture F-term (reference) 4J002 BB031 BB121 BB151 EA046 EL096 EL126 EQ016 EU087 EU157 EU187 EU236 EV086 EV306 FD067 GK01 HA31 4L001 BB FF04 JJ16 JJ19 JJ28 LA01

Claims (5)

[Claims] 1. A photoreversible color-changing polyolefin melt spun comprising three essential components of an organic photochromic compound, a thermal decomposition inhibitor and a high boiling point solvent. 2. The method according to claim 1, wherein the amounts of the thermal decomposition inhibitor and the high boiling point solvent are in the range of 0.1 to 50 parts by weight and 2 to 300 parts by weight, respectively, based on 1 part by weight of the organic photochromic compound. Photoreversible discolorable polyolefin melt spun body. 3. The photoreversible color-changing polyolefin melt spun according to claim 1, wherein the high-boiling point solvent is compatible with the polyolefin resin and the organic photochromic compound is dissolved at least 0.1% or more at a melting point or more. . 4. The photoreversible color-changing polyolefin melt spun according to claim 1, wherein the thermal decomposition inhibitor is a hindered amine compound and / or a hindered phenol compound. 5. An essential component comprising an organic photochromic compound, a thermal decomposition inhibitor and a high boiling point solvent is directly added to and mixed with a polyolefin resin as a base polymer without passing through a masterbatch production step. The method for producing a melt-spun photoreversible color-changing polyolefin according to claim 1, wherein the mixture is melt-spun as it is.