JP6180744B2 - Oil and fat-containing rayon fiber, method for producing the same, and fiber structure - Google Patents

Description

  The present invention relates to a rayon fiber containing a specific fat and oil, a method for producing the same, and a fiber structure.

  It is known that rayon fibers using regenerated cellulose are produced by various methods such as a viscose method, a copper ammonia method, and a solvent spinning method. Since rayon fiber is made of cellulose as a substrate, it itself has a gentle nature to the skin. Conventionally, various proposals have been made to further demonstrate the properties of rayon fibers. For example, as proposals regarding regenerated cellulose fibers kneaded with fatty acids (oils and fats), proposals for kneading oleic acid or metal salts of oleic acid (Patent Document 1), proposals for kneading γ-linolenic acid emulsion (Patent Document 2) -3), proposal to knead docosahexaenoic acid (DHA) emulsion (Patent Document 4), proposal to knead emulsion of γ-linolenic acid (Patent Document 5), knead oleic acid or salt thereof, cellular region Proposal of Rayon Fiber (Patent Document 6) Formed with Cation, Proposal of Rayon Fiber Formed with Cellulose Region by Kneading Fatty Acid or its Salt and Fat-soluble Antioxidant (Patent Document 7), Rice Oil, γ-Oryzanol , A proposal to knead an emulsion containing ferulic acid (Patent Document 8), a proposal to knead an olive oil emulsion (Patent Document 9), and added a phase change material enclosed in a microcapsule Proposal of cellulose fibers (Patent Document 10), and the like. Patent Document 11 proposes a non-woven fabric for cosmetics and beauty using oil-containing fibers such as rayon fibers containing oil such as squalane as raw material fibers.

  Since the fatty acids used in Patent Documents 1 to 7 have a melting point of 14 ° C. or lower, they are liquid at room temperature and can be easily emulsified. In addition, the rice oil used in Patent Document 8 and the olive oil used in Patent Document 9 contain a large amount of unsaturated fatty acids, so have a low melting point and can be easily emulsified. In Patent Document 10, fats and oils or fatty acids are added as microcapsules. Squalane used as an oil component in Patent Document 11 is liquid at room temperature and can be easily emulsified.

  As described above, oils and fats that are liquid at 20 ° C. or lower (melting point: 20 ° C. or lower) have high fluidity and are easy to adjust to the skin, and are relatively easy to emulsify. However, liquid fats and oils at 20 ° C. or less have a high content of unsaturated fatty acids containing double bonds, and are likely to be oxidized. For this reason, it is necessary to prevent oxidation of fats and oils, particularly when liquid fats and oils are contained in the fiber at 20 ° C. or lower. Therefore, in order to prevent the oxidation of fats and oils, a technique for adding an antioxidant to the fats and oils has been proposed. For example, Patent Documents 2 to 5 describe that 3,5-di-butylhydroxytoluene, a sulfur-based antioxidant, and tocopherols are used in combination with a fatty acid as an antioxidant. Further, Patent Document 8 using rice bran oil as fats and oils suggests that 0.5 to 2% by weight of ferulic acid is contained, and Patent Document 7 proposes that a fat-soluble antioxidant is contained in fatty acids.

JP-A-53-143722 JP 2002-161428 A JP 09-296322 A JP 09-296321 A JP 08-337918 A JP 2007-138324 A JP 2008-28579 A JP 2007-314914 A JP 2008-303245 A Special table 2009-544866 gazette JP 2010-195735 A

  On the other hand, fats and oils are oxidized over time, and odors may be generated. In addition, when an antioxidant is added to obtain an antioxidant effect on fats and oils, odor and coloring may occur due to the oxidation effect of the antioxidant itself.

  In order to solve the conventional problems, the present invention disperses fats and oils in cellulose constituting rayon fibers in a state of good oxidation stability, and also contains fats and oils containing rayon fibers that suppress the occurrence of odor and / or coloring, A manufacturing method and a fiber structure are provided.

The fat and oil-containing rayon fiber of the present invention is a fat and oil-containing rayon fiber in which fat and oil and an antioxidant are contained in the rayon fiber, the cellulose and the fat and oil in the rayon fiber are in an incompatible state, and the fat and oil is Finely dispersed in the cellulose, the fats and oils contain at least one fatty acid component selected from fatty acids and glycerin esters thereof, and the antioxidant contains 80% by mass or more of α-type tocopherol and tocotrienol as essential components. Antioxidant, antioxidant containing 80% by mass or more as essential components of γ-type tocopherol and tocotrienol , antioxidant containing 80% by mass or more of α-type tocopherol, γ-type tocopherol and tocotrienol as essential components, α-type tocopherol as essential components antioxidants including 80 mass% or more, gamma-type Tokofu Antioxidants including 80 mass% or more roles as an essential component, or wherein the tocotrienol is an antioxidant containing more than 55 wt% as an essential component.

The method for producing the oil-containing rayon fiber of the present invention comprises preparing an emulsion liquid by mixing oil, an antioxidant and an emulsifier, and mixing the emulsion liquid with a viscose stock solution containing cellulose to produce a viscose liquid for spinning. The spinning viscose liquid is extruded from a nozzle, spun, and coagulated and regenerated to obtain a fat-containing rayon fiber. The fat contains at least one fatty acid component selected from a fatty acid and a glycerin ester thereof, and is oxidized. inhibitor, alpha-type tocopherol and antioxidants containing 80% by mass or more tocotrienol as an essential component, gamma-type tocopherol and antioxidants containing 80% by mass or more tocotrienol as an essential component, alpha type tocopherol, a gamma-type tocopherol and tocotrienol antioxidants including 80 mass% or more as essential components, alpha Antioxidants including tocopherol 80% by mass or more as essential components, and characterized in that it is a γ-type tocopherol antioxidants containing 80% by mass or more as essential components, or antioxidants containing more than 55 wt% as an essential component tocotrienol To do.

  The fiber structure of the present invention includes the oil-and-fat-containing rayon fiber.

  The fat and oil-containing rayon fiber of the present invention comprises a fat and oil containing a fatty acid component in combination with an antioxidant containing 55% by mass or more of at least one vitamin E component selected from the group consisting of α-type tocopherol, γ-type tocopherol and tocotrienol. By making it contain in a fiber, it can be set as the rayon fiber with the favorable familiarity to skin. In addition, the presence of a large number of fats and oils dispersed in the fiber together with antioxidants improves the oxidation stability of the fats and oils, the functions of the fats and oils themselves are exhibited, and the fibers become soft and the fibers are oxidized. It is also possible to prevent the fiber strength from being lowered. Moreover, generation | occurrence | production of an odor and coloring can be suppressed by using together the antioxidant and oil and fat which contain 55 mass% or more of at least 1 vitamin E components chosen from the group which consists of (alpha) -tocopherol, (gamma) -tocopherol, and tocotrienol.

  The production method of the present invention is a fat and oil that is easily oxidized by mixing an emulsion prepared by mixing fat, antioxidant, and emulsifier with a viscose stock solution containing cellulose to obtain a viscose liquid for spinning. However, it can be dispersed and contained in the fiber with good oxidation stability.

  The fiber structure of the present invention is gentle to the skin, has a slimy feeling, and can have a soft texture.

FIG. 1 is a graph showing the change in the peroxide value with time when dl-α-tocopherol is added to camellia oil. FIG. 2 is a graph showing a change with time in the peroxide value when tocotrienol is added to coconut oil. FIG. 3 is a graph showing the change over time in the peroxide value when γ-tocopherol is added to the koji oil. FIG. 4 is a graph showing a change with time in the peroxide value when tocotrienol is added to olive oil.

  The rayon fiber of the present invention is an oil and fat-containing rayon fiber in which oil and fat and an antioxidant are contained in the rayon fiber.

  The fats and oils used in the present invention contain at least one fatty acid component selected from fatty acids and glycerin esters thereof. Examples of the fatty acids include saturated fatty acids and unsaturated fatty acids. Examples of the glycerin esters of the fatty acids include saturated fatty acid glycerin esters, saturated fatty acid mixed glycerin esters, unsaturated fatty acid glycerin esters, and unsaturated fatty acid mixed glycerin esters. And mixed glycerin ester of saturated fatty acid and unsaturated fatty acid. In general, the melting point of a fatty acid increases as the number of carbon atoms increases. When the number of carbon atoms is the same, the melting point of an unsaturated fatty acid tends to be lower than that of a saturated fatty acid. Many of the naturally derived fats and oils containing a fatty acid component and having a melting point of 20 ° C. or less at 20 ° C. have higher fluidity than the solid fats and oils at room temperature, and are easily adapted to the skin. On the other hand, oils and fats that are solid at 20 ° C., particularly naturally-derived oils and fats, often have a melting point of 20 ° C. or higher, and can give a better effect on the skin than liquid oils and fats at room temperature. It is preferable at the point which can provide the function which oil and fat do not have. In the present invention, fats and oils that are liquid at 20 ° C. (hereinafter also referred to as “liquid fats and oils”) mean that the melting point of the fats and oils is 20 ° C. or less, and fats and oils that are solid at 20 ° C. (hereinafter referred to as “solid fats and oils”). The term “oil-like fat” also means that the melting point of the fat is 20 ° C. or higher.

  The fatty acid component contained in the fats and oils used in the present invention may be any of saturated fatty acids, unsaturated fatty acids, and glycerin esters thereof. Although it does not specifically limit as carbon number of a fatty acid, For example, it is preferable that it is C16-22. The unsaturated fatty acid preferably contains at least one selected from palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, erucic acid and the like. The saturated fatty acid preferably contains at least one selected from palmitic acid, stearic acid, arachidic acid, pehenic acid and the like.

  It is preferable that the said liquid fat contains saturated fatty acid and unsaturated fatty acid, and it is more preferable that content of saturated fatty acid is 10-40 mass% and content of unsaturated fatty acid is 60-90 mass%. When saturated fatty acid and unsaturated fatty acid are included, it is preferable at the point which can receive the various effects which each fatty acid has.

  Usually, the melting point of fats and oils depends on the melting point of fatty acids contained in the fats and oils. For example, if it is fats and oils containing a plurality of fatty acids, it refers to the melting point when measured as fats and oils, and if the melting point is 20 ° C. or less, it is contained in fats and oils (liquid fats and oils) that are liquid at 20 ° C. Exceeding 20%, it is contained in fats and oils (solid fats and oils) that are solid at 20 ° C.

  When the liquid oil is a naturally derived oil, it may be present as a glycerin ester of a saturated fatty acid and / or an unsaturated fatty acid. By being present as a glycerin ester, the functions of each fatty acid can be exhibited widely. Moreover, about melting | fusing point, when the melting | fusing point of fats and oils is low, fluidity | liquidity becomes high and becomes easy to adapt to skin. Specifically, the melting point of the naturally derived liquid fat is preferably -30 to 20 ° C. More preferably, it is −25 to 15 ° C.

  Examples of the naturally-derived liquid oil include olive oil obtained from olive fruits (usually palmitic acid 9-18%, palmitoleic acid 0-3%, stearic acid 2-4%, oleic acid 60-80%, linole 4-16% acid, 0-1% linolenic acid), grape seed oil obtained from grape seed (usually 6-8% palmitic acid, 3-10% stearic acid, 18-20% oleic acid, linoleic acid 67-71%, including linolenic acid 0-1%), corn oil obtained from corn germ (usually palmitic acid 9-12%, stearic acid 1-3%, oleic acid 25-33%, linoleic acid 50- 60%, including linolenic acid 0-2%), soybean oil obtained from soybean seed (usually 10-12% palmitic acid, 2-5% stearic acid, oleic acid 0-25%, including linoleic acid 50-57%, linolenic acid 5-9%), rice oil obtained from rice bran (usually 0-1% myrrhilic acid, 16-17% palmitic acid, 1-2 stearic acid %, Oleic acid 40-44%, linoleic acid 35-37%, linolenic acid 0-2%, including arachidic acid 0-1%), cottonseed oil obtained from cotton seeds (usually 0-3% myrrhilic acid, 20% to 30% palmitic acid, 1 to 5% stearic acid, 15 to 30% oleic acid, 40 to 52% linoleic acid, 0 to 1% arachidic acid, walnut oil obtained from walnut seeds (usually palmitic) Acid 6-8%, stearic acid 1-3%, oleic acid 14-21%, linoleic acid 57-72% linolenic acid 10% included), peanut oil obtained from peanut seeds (usually palmitic acid 10-12 % Stearic acid 2-5%, oleic acid 40-49%, linoleic acid 30-37%, linolenic acid 0-2%, arachidic acid 1-2%, eicosenoic acid 0-2%, behenic acid 0-4%, lignoserine Rapeseed oil obtained from oilseed rape seeds (usually 3-6% palmitic acid, 1-3% stearic acid, 46-59% oleic acid, 21-32% linoleic acid in low L chic type) , Linolenic acid 9-16%, arachidic acid 0-1%, erucic acid 1-5%), camellia oil obtained from camellia seeds (usually palmitic acid 8%, stearic acid 2%, oleic acid) 79-85%, linoleic acid 3-9%, and linolenic acid 0-1%).

  Among them, preferred liquid oil is cocoon oil. Camellia oil is a vegetable oil obtained from the seeds of the Camellia family Camellia, and is a liquid oil at room temperature (20 ° C.). In Japan it is produced from camellia seeds of camellia knots that are cultivated mainly in Izu Oshima and Nagasaki Goto. In addition, other than the camellia oil produced from camellia seeds of camellia, there are those obtained from seeds such as sasanqua and yucha of sasanqua, or chanoki of tea. The components of coconut oil are mainly composed of glycerin esters of unsaturated fatty acids including oleic acid, and also contain trace amounts of tocopherol and saponin. By using cocoon oil, the stratum corneum protection and dry skin improvement effect of oleic acid can be imparted to the fiber.

  Although the raw material quality of the fatty acid composition of camellia oil varies depending on the production area, harvest time, climatic conditions, etc., it is preferable that the saturated fatty acid is 10 to 30% by mass and the unsaturated fatty acid is 70 to 90% by mass. Within the above range, the function of each fatty acid component can be effectively exhibited.

  A preferred liquid oil is olive oil. Olive oil is a vegetable oil obtained from the fruit of an olive species plant belonging to the genus Oleaceae, and is a liquid oil at room temperature (20 ° C.). The components of olive oil are mainly glycerin esters of unsaturated fatty acids including oleic acid, and also contain trace amounts of tocopherol, β-carotene and polyphenol. By using olive oil, the stratum corneum protection and dry skin improvement effect of oleic acid can be imparted to the fiber.

  The fatty acid composition of olive oil varies depending on the production area, harvest time, climatic conditions, etc., but it is preferable that the saturated fatty acid is 20 to 40% by mass and the unsaturated fatty acid is 60 to 80% by mass. Within the above range, the function of each fatty acid component can be effectively exhibited.

  The solid oil / fat preferably contains a saturated fatty acid and an unsaturated fatty acid, more preferably 30 to 55% by mass of saturated fatty acid and 45 to 70% by mass of unsaturated fatty acid. When saturated fatty acid and unsaturated fatty acid are included, it is preferable at the point which can receive the various effects which each fatty acid has. For example, saturated fatty acids are preferred because they are resistant to spoilage, have very good stability, and have a high moisture effect, and therefore have a moisturizing effect due to the property of retaining moisture in the subcutaneous tissue.

  Usually, melting | fusing point of solid fats and oils depends on melting | fusing point of the fatty acid contained in fats and oils. For example, in the case of fats and oils containing a plurality of fatty acids, the melting point when measured as fats and oils is used. When the melting peak is a single peak, if the melting point is 20 ° C or higher, it is included in the fats and oils that are solid at 20 ° C. In the case where a plurality of melting peaks appear, if at least one melting peak is 20 ° C. or higher, it is contained in the oil that is solid at 20 ° C.

  When the said solid fat is a naturally derived fat, it may exist as a glycerin ester of a saturated fatty acid and / or an unsaturated fatty acid. By being present as a glycerin ester, the functions of each fatty acid can be exhibited widely. Moreover, even if it contains a fatty acid with a high melting point, it has a broad melting peak and shifts to the low melting point side, so that it is easily emulsified. Specifically, the melting point of the naturally derived solid fat is preferably 20 to 82 ° C. More preferably, it is 25-60 degreeC.

  Examples of the naturally-derived solid fats and oils include, for example, Babas oil having a melting point of 22 to 26 ° C. obtained from Babas seed (usually 4.1 to 4.8% caprylic acid, 6.6 to 7.6% capric acid). Lauric acid 44.1-45.1%, myristic acid 15.4-16.5%, palmitic acid 5.8-8.5%, stearic acid 2.7-5.5%, oleic acid 11.9 -16.1%, including linoleic acid 1.4-2.8%); Borneo fat (usually 18% palmitic acid, 43.3% stearic acid, olein) having a melting point of 34-39 ° C. obtained from seeds of shoreastenoptera 37.4% acid, 0.2% linoleic acid, 1.1% arachidic acid); cocoa butter with a melting point of 32-35 ° C. obtained from cocoa seeds (usually 24.4% palmitic acid, 35 stearic acid) .4% oleic acid 8.1%, including linoleic acid 2.1%); palm oil having a melting point of 27-50 ° C. obtained from oil palm seed (usually 0-1% lauric acid, 1-2% myristic acid, 39 palmitic acid 39) -46%, stearic acid 3-5%, oleic acid 38-44%, linoleic acid 8-11% included); butter with a melting point of 25-35 ° C. obtained from dairy cow's milk (usually 3.7% butyric acid, Hexanoic acid 2.3%, octanoic acid 1.4%, decanoic acid 2.9%, lauric acid 3.6%, myristic acid, 11.9%, pentadecanoic acid 1.7%, palmitic acid 33.1%, Heptadecanoic acid 1%, stearic acid 10.0%, arachidic acid 0.2%, behenic acid 0.1%, lignoceric acid 0.1%, decenoic acid 0.3%, myristoleic acid 1.1%, palmitoleic acid 1.7%, heptadecenoic acid 0.3%, ole Acid 21.8%, eicosenoic acid 0.2%, linoleic acid 2.1%, linolenic acid 0.5%, icosatrienoic acid 0.1%, arachidonic acid 0.1%); Shea butter obtained from seed embryos with a melting point of 25-45 ° C. (usually oleic acid 38-50%, stearic acid 34-45%, palmitic acid 3-9%, linoleic acid 5-8%, arachidic acid 1-2 Beef tallow; shortening (edible oil made from vegetable oil, margarine made by removing moisture and additives to obtain high-purity fat); lard; horse oil; sha fat; palm oil and the like.

  In particular, when used in contact with human or animal skin, the solid oil / fat is preferably a solid oil / fat having a melting peak near body temperature. Specifically, the melting point of the solid fat is preferably 30 to 45 ° C. When the melting point is in the above range, the solid oil is softened or melted when it comes into contact with the skin.

  In the melting point of the solid fat, the broader melting peak is more stable against changes in the ambient temperature of the fat-containing rayon fiber and the fiber structure, the familiarity to the skin is good, and the texture is also flexible, preferable. For example, when the melting peak measured by the DSC method described later is a single peak, it can be said that the peak is broader as the half-value width in the melting peak is larger. The half width at the melting peak of the solid oil is preferably 3 to 20 ° C. More preferably, it is 5-15 degreeC. Moreover, when the melting peak measured by DSC method mentioned later has a some peak, it is preferable that the number of melting peaks is 2-8. Moreover, it is preferable that the difference of the minimum temperature and the maximum temperature is 10-60 degreeC among each melting peak. Oils and fats having such a plurality of melting peaks are preferred because they are stable against changes in the atmospheric temperature of the oil-and-fat rayon fibers and fiber structures, are well-familiar with the skin, and are soft to the touch. In the present invention, the “half-value width at the melting peak” is the intersection of the perpendicular line drawn from the vertex X of the melting peak (endothermic peak) measured by the DSC method to the temperature axis and the baseline of the endothermic peak as Y. When the point of bisecting the line segment XY is M, and the intersection points of the straight line passing through M and parallel to the temperature axis and the endothermic curve are N1 and N2, respectively, the line segment N1-N2 Length (temperature range).

  Among them, a preferred solid fat is a shea butter. Shea butter is a vegetable oil obtained from the seeds of the seeds of shea butter of the Acetaceae family, and is a waxy solid at room temperature (20 ° C.). Mainly produced in Nigeria, Mali, Burkina Faso and Ghana in Africa. Although it is edible, it is widely known in recent years that it is mixed with hand creams, soaps, cosmetics and the like. The component of shea butter is mainly composed of glycerin esters of fatty acids including stearic acid and oleic acid, and also contains trace amounts of tocopherol, carotenoids, and triterpenes. By using shea butter, there may be a protective effect of sebum possessed by stearic acid, an antioxidant effect, an oil replenishment effect of sebum, a stratum corneum protection possessed by oleic acid, and a dry skin improving effect.

  The raw material quality of shea butter varies depending on the production area, harvest time, climatic conditions, etc., but the fatty acid composition of shea butter is preferably 30 to 55% by mass of saturated fatty acid and 45 to 70% by mass of unsaturated fatty acid. Within the above range, the function of each fatty acid component can be effectively exhibited.

  The melting point of shea butter has a broad melting peak and is preferably 35 to 40 ° C. The half width at the melting peak of shea butter is preferably 5 to 15 ° C.

  Of the above fats and oils, the use of fats and oils close to the fatty acid composition of human sebum is preferred because it is familiar to the skin. Such fats and oils preferably contain palmitic acid as a saturated fatty acid in an amount of 10% by mass or more of the fatty acid composition of the fats and oils. More preferably, it contains 15 to 35% by mass. Palmitic acid has a function of preventing the growth of sebaceous glands, and has a function of stabilizing vitamin A that activates cells such as skin, hair, and mucous membranes. Moreover, it is preferable to contain oleic acid as an unsaturated fatty acid 10 mass% or more of the fatty acid composition of fats and oils. More preferably, the content is 15 to 55% by mass. Examples of fats and oils that satisfy the above fatty acid composition range include beef tallow, shortening, cocoa butter, butter, horse oil, and borneo fat.

  In the oil-containing rayon fiber of the present invention, the oil / fat is preferably present in the range of 0.5 to 15% by mass with respect to cellulose. More preferably, it is 0.8-14 mass%, More preferably, it is the range of 1-10 mass%. If it is the said range, effects, such as drying of skin, prevention of aging, stratum corneum protection by oleic acid, improvement of dry skin, promotion of metabolism by linoleic acid, normalization of skin cell function by linolenic acid, can be expected.

  The antioxidant used in the present invention contains 55% by mass or more of at least one vitamin E component selected from the group consisting of α-type tocopherol, γ-type tocopherol and tocotrienol. By using the antioxidant and the fats and oils in combination, the fats and oils can be prevented from being oxidized. As a result, a decrease in fiber strength due to the oxidation of the fats and oils can be prevented, and the generation of odor and / or coloring can be prevented and suppressed.

The antioxidant may be an antioxidant containing 55% by mass or more of at least one vitamin E component (hereinafter referred to as an essential component) selected from the group consisting of α-type tocopherol, γ-type tocopherol and tocotrienol. There is no particular limitation. From the viewpoint of being excellent in the antioxidant effect on fats and oils, it is preferable to contain 55% by mass or more of γ-type tocopherol, and more preferably 80% by mass or more of γ-type tocopherol. Further, from the viewpoint of being excellent in the effect of suppressing the generation of odor and coloring while effectively preventing the oxidation of fats and oils, it is preferable to contain 55% by mass or more of tocotrienol, and more preferably to contain 60% by mass or more of tocotrienol. . The tocotrienol may include any of α-type, β-type, γ-type, and δ-type tocotrienol, and includes 20% by mass or more of α-type tocotrienol and / or γ-type tocotrienol from the viewpoint of being excellent in the antioxidant effect on fats and oils. It is preferable that α-type tocotrienol and γ-type tocotrienol are contained in a total of 50% by mass or more. Moreover, it is preferable that 55 mass% or more of alpha-type tocopherol is included from the viewpoint that it is excellent in the effect which suppresses generation | occurrence | production of coloring, preventing oxidation of fats and oils, and it is more preferable that 80 mass% or more of alpha-type tocopherol is included. As the antioxidant containing 55% by mass or more of the essential vitamin E component, for example, in the case of γ-type tocopherol, “γ70” manufactured by J-Oil Mills, “Gamma Bright 90” manufactured by Eisai Food Chemical Co., Tocotrienol In this case, “ Orizatocotrienol- 70”, “ Orizatocotrienol- 90” manufactured by Oriza Oil Chemical Co., Ltd., “ Tokolite (registered trademark) 92 ” manufactured by Eisai Food Chemical Co., Ltd. and the like can be mentioned.

  The antioxidant may contain other components in addition to the essential components. As said other component, you may use any of a fat-soluble antioxidant and water-soluble antioxidant, for example. From the viewpoint of compatibility with fats and oils, the other component is preferably a fat-soluble antioxidant.

  Examples of the fat-soluble antioxidant include natural antioxidants such as β-type tocopherol, δ-type tocopherol, β-carotene and ubiquinol (CoQ10), and BHT (dibutylhydroxytoluene) and BHA (butylhydroxyanisole). Examples include synthetic antioxidants. Of these, natural antioxidants are preferred from the viewpoint of low irritation to the skin.

  Examples of the water-soluble antioxidant include ascorbic acid, isoascorbic acid; catechin, anthocyanin, tannin, quercetin (glucosides such as rutin and quercitrin, and enzyme treatment and chemical treatment such as enzyme-treated isoquercitrin. Flavonoids such as myrcitrin, myricetin and isoflavone; phenolic acids such as chlorogenic acid, ellagic acid and curcumin; polyphenols such as apple polyphenol and cacao mass polyphenol; and water-soluble carotenoids such as astaxanthin and lutein It is preferable that it is at least one. In addition, the plant extract containing the water-soluble antioxidant may be an extract of tea, rosemary, strawberries, strawberries, bayberry, etc., for example. The plant extract is not particularly limited, and examples thereof include a plant solvent extract obtained by powdering the plant and then using a solvent such as water or hydrous alcohol, or a solution obtained by concentrating or drying the plant extract. . Moreover, you may use the commercially available persimmon fruit juice containing anthocyanin, grape skin pigment | dye, etc.

  The antioxidant is preferably added in an amount of 0.03 to 15% by mass with respect to fats and oils from the viewpoint of more effectively suppressing the generation of odor and coloring while preventing the oxidation of fats and oils more effectively. . Further, when the antioxidant contains 55% by mass or more of at least one vitamin E component selected from the group consisting of γ-type tocopherol and tocotrienol, generation of odor and coloring while preventing oxidation of fats and oils more effectively From the viewpoint of more effectively suppressing the amount of oil and fat, a range of 0.04 to 8% by mass is preferable, and 0.06 to 3.0% by mass is more preferable.

  The effect of the above-mentioned antioxidants on fats and oils can be confirmed by the active oxygen method (AOM). In the active oxygen method (AOM), a sample (for example, a mixture of oil and fat and an antioxidant) is heated to 98 ° C., and at the same time, air is blown into the sample to promote oxidation and to stabilize the oil and fat in a short time. This is a test method to be evaluated, and the degree of oxidation is confirmed by measuring the peroxide value (POV) of the sample at regular intervals. POV is suitable for investigating changes in fat oxidation over time.

The principle of POV measurement is as follows. POV refers to hydroperoxide (peroxide) produced by fats and oils taking in oxygen in the air and reacting with potassium iodide (KI) as shown by the following chemical formula (1) to liberate iodine (I ₂ ) Is titrated with a sodium thiosulfate solution as represented by the following chemical formula (2), and is expressed in milliequivalents (unit: meq / kg) with respect to 1 kg of the sample.

Specifically, POV is measured as follows.
(1) A sample 3 g is accurately weighed and placed in a stoppered Erlenmeyer flask, and 35 ml of a mixed solution of chloroform and glacial acetic acid (volume ratio 2: 3) is added and dissolved. If it does not dissolve uniformly, add a mixture of chloroform and glacial acetic acid (volume ratio 2: 3) as appropriate.
(2) Next, 1 ml of a saturated potassium iodide solution was added while passing nitrogen gas or carbon dioxide through the air in the flask, immediately plugged and mixed for about 1 minute, and then 0.01 N thiosulfuric acid using starch test solution as an indicator. Titrate with sodium solution and calculate the peroxide value (POV) by the following formula.
Peroxide value (meq / kg) = (a / S) × 10
S: Sample collection amount (g), a: 0.01N sodium thiosulfate solution titration (ml)
(3) AOM stability is displayed by the time (hr) required for POV to reach 100 and the time (hr) required for POV to reach 200. It means that oxidation of fats and oils progresses in a short time, so that each numerical value is small.

  From the viewpoint that the characteristics of fats and oils can be exhibited by being uniformly finely dispersed in the fibers, in the fat and oil-containing rayon fibers, the average particle diameter of the particles containing the fats and oils is 0.02 to 0.8 μm. preferable. More preferably, the average particle size of the oil-containing particles is 0.04 to 0.5 μm, and more preferably 0.06 to 0.25 μm.

The average particle diameter of the particles containing the oil and fat in the oil and fat-containing rayon fiber can be measured using the oil and fat-containing rayon fiber after the deoiling treatment. Specifically, by measuring the average pore diameter of the voids in the oil-containing rayon fiber after deoiling treatment, the average particle diameter of the particles containing the oil in the oil-containing rayon fiber can be confirmed. . Since the voids in the oil-containing rayon fiber after deoiling treatment are formed by the removal of the oil and fat finely dispersed by deoiling treatment, the voids in the oil-containing rayon fiber after deoiling treatment By measuring the average pore diameter, the average particle diameter of the particles containing the oil and fat in the oil and fat-containing rayon fiber can be confirmed. The average pore diameter of the voids after the deoiling treatment of the oil-and-fat-containing rayon fiber is measured using a cross-sectional photograph (scanning electron micrograph, magnification 3000 times) of the fiber after the deoiling treatment. Specifically, the cross-sectional photograph of the fiber after deoiling treatment (scanning electron micrograph, magnification 3000 times) is magnified to a magnification of 9010 by image processing, and the cross-section of any fiber is sampled from the printed paper, The diameter of the void existing between the outer periphery of the fiber and the inside of 3 μm in the fiber cross section is measured, and the average diameter of the 100 measured voids is taken as the average pore diameter of the void. In addition, an elliptical space | gap part is converted into a perfect circle diameter from the area calculated by measuring a long diameter and a short diameter, and is set as the diameter of a space | gap part. In the above, the deoiling process is performed as follows.
(I) About 2.3 g of a sample is precisely weighed and packed in a sample tube having a small hole at the bottom.
(II) The bottom hole is closed, and 10 ml of methanol as an extraction solvent is poured into the sample tube, allowed to stand for a certain period of time and allowed to permeate, and then the methanol treatment liquid is extracted by a press device.
(III) Using the same sample, the extraction by the above operation (II) was repeated 20 times, and then the sample taken out from the sample tube was washed with water, dried at 105 ° C. for 2 hours, and the fiber after the deoiling treatment was performed. Obtained.

  The fat and oil-containing rayon fiber of the present invention is not particularly limited, but is preferably produced as follows. An emulsion obtained by emulsifying oil and fat is added to a viscose stock solution containing cellulose to prepare a viscose solution for spinning, and the obtained viscose solution for spinning is spun to obtain an oil-containing rayon fiber. Can do.

  The oil / fat, the antioxidant and the emulsifier are mixed to prepare an emulsion. The proportion of the antioxidant in the emulsion is preferably 0.005 to 6.0% by mass. More preferably, it is 0.01-4.0 mass%, More preferably, it is 0.02-2.0 mass%. If it is within the above range, the oxidation stability of the oil and fat is improved, the function of the oil and fat itself is exhibited, and the fiber has a soft texture, and the decrease in fiber strength due to the oxidation of the oil and fat can be prevented. As the emulsification method, known emulsification methods such as phase inversion emulsification method and forced emulsification method can be used.

  The emulsifier is not particularly limited as long as it can be mixed with the oil and fat and the antioxidant to prepare an emulsion. For example, polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ether, polyoxyalkylene alkenyl ethers such as polyoxyethylene alkenyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene styrenated ruphenyl ether, polyoxyalkylene alkyl styrenated And ruphenyl ether, polyoxyalkylene cumyl phenyl ether, polyoxyalkylene β-naphthyl ether, polyoxyalkylene castor oil ether, polyoxyalkylene hardened castor oil ether, and the like. In particular, polyoxyethylene alkyl ether and / or polyoxyethylene alkenyl ether are preferable.

  It is preferable that the addition amount of the said emulsifier is 7-60 mass% with respect to fats and oils. More preferably, it is 15-50 mass%, More preferably, it is 15-35 mass%. If the amount of the emulsifier added is 7% by mass or more, an emulsion liquid having good stability is easily obtained. Moreover, if the total addition amount of an emulsifier is 60 mass% or less, generation | occurrence | production of many foams will be suppressed in a scouring process, and it will be hard to become abnormal scouring.

  The average particle size of the emulsion in the emulsion is preferably 0.02 to 1 μm. The more preferable average particle diameter is 0.05 to 0.8 μm, more preferably 0.08 to 0.6 μm, still more preferably 0.1 to 0.4 μm, and particularly preferably less than 0.3 μm. . When the average particle diameter is within the above range, oil and fat are finely dispersed, and rayon fibers including a large number of fine regions are obtained, which is preferable. The average particle size can be controlled by the composition of the emulsifier, the added amount of the emulsifier, and the emulsification conditions. The emulsion liquid preferably contains 3% or less of particles having an emulsion particle diameter of 3 μm or more. More preferably, it is 1% or less, More preferably, it is 0.1% or less. When the particle diameter of the emulsion is within the above range, oil and fat are finely dispersed, and rayon fibers containing a large number of fine regions are obtained, which is preferable. In the present invention, the particle diameter and average particle diameter of the emulsion are those measured and calculated by a light scattering method.

  As the spinning solution (viscose solution), a viscose stock solution containing 7 to 10% by mass of cellulose, 5 to 8% by mass of sodium hydroxide, and 2 to 3.5% by mass of carbon disulfide may be prepared and used. . At this time, additives such as ethylenediaminetetraacetic acid (EDTA) and titanium dioxide can be used as necessary. The temperature of the spinning solution (viscose solution) is preferably maintained at 19 to 23 ° C. The emulsion solution obtained above is mixed with the viscose stock solution containing cellulose to prepare a spinning viscose solution (oil-containing rayon fiber spinning viscose solution).

  The addition amount of the fat is preferably in the range of 0.5 to 15% by mass with respect to cellulose. More preferably, it is 0.8-14 mass%, More preferably, it is the range of 1-10 mass%. If it is the said range, effects, such as drying of skin, prevention of aging, stratum corneum protection by oleic acid, improvement of dry skin, promotion of metabolism by linoleic acid, normalization of skin cell function by linolenic acid, can be expected. The addition amount of the antioxidant is preferably in the range of 0.03 to 15% by mass, more preferably in the range of 0.04 to 8.0% by mass, and still more preferably 0.06 to 3% with respect to the fats and oils. The range is 0.0 mass%.

  The spinning bath (Mueller bath) preferably contains 95 to 130 g / liter of sulfuric acid, 10 to 17 g / liter of zinc sulfate, 290 to 370 g / liter of sodium sulfate, and preferably has a temperature of 45 to 60 ° C. A more preferable sulfuric acid concentration is 100 to 120 g / liter. As the spinning nozzle, for example, a normal circular nozzle can be used. The selection of the spinning nozzle depends on the target production amount, but preferably has a circular nozzle having a diameter of 0.05 to 0.12 mm and 1000 to 20000 holes.

  Using the spinning nozzle, the spinning viscose liquid is extruded into a spinning bath, spun, and coagulated and regenerated. The spinning speed is preferably in the range of 35 to 70 m / min. Further, the stretching ratio is preferably 39 to 50%. Here, the stretch ratio indicates how many percent the stretched length is increased when the stretched length is 100%. In terms of magnification, the ratio is 1 before stretching and 1.39 to 1.50 after stretching.

  The obtained rayon fiber yarn is cut into a predetermined length and scoured. The scouring step is preferably performed in the order of hot water treatment, hydrosulfurization treatment, bleaching, pickling, and oil application.

  Then, after removing an excess oil agent and water | moisture content from a fiber by methods, such as a compression roller and vacuum suction, you may give a drying process as needed.

  The oil-containing rayon fiber of the present invention preferably has a fineness of 0.3 to 6.0 dtex. More preferably, it is 0.6-4.0 dtex, More preferably, it is 0.9-3.3 dtex. If the fineness is less than 0.3 dtex, single fiber breakage tends to occur during stretching. If the fineness exceeds 6.0 dtex, it may be difficult to use for clothing.

  The fat and oil-containing rayon fiber of the present invention is provided in the form of long fibers (for example, tow, filament, nonwoven fabric, etc.), short fibers (for example, raw paper for wet papermaking, raw cotton for airlaid nonwoven fabric, raw cotton for cards, etc.) It is preferable to form a fiber structure. The fiber structure is preferably, for example, tow, filament, spun yarn, batting (padded cotton), paper, non-woven fabric, woven fabric, or knitted fabric, and is a kind selected from the group consisting of spun yarn, knitted fabric, woven fabric, and non-woven fabric. Is more preferable.

  The fiber structure of the present invention has a good texture because the rayon fiber contains fats and oils. This texture will be described in detail. When the oil-containing rayon fiber of the present invention is used, the surface has a slimy feeling and a soft texture is expressed when it is made into a fiber structure as compared with the conventional rayon fiber. The product has a gentle texture and can produce a very high-class effect on the product (hereinafter also referred to as the texture effect). In addition, since the fat and oil-containing rayon fiber of the present invention is kneaded with fats and oils in the fiber, the texture effect of the present invention is a so-called post-processing finish that imparts a softener at the final finishing stage of a conventional fiber structure. Compared with outstanding washing durability.

  As the fiber structure of the present invention, for example, in the case of a spun yarn, the above oil-containing rayon fiber alone or other regenerated cellulose fibers, cotton, hemp, wool, acrylic, polyester, polyamide, polyolefin, polyurethane, and other fibers It is preferable to be blended with and mixed with. Such spun yarn can be processed into a woven fabric or a knitted fabric and used for clothing or the like.

  When the fiber structure of the present invention is a woven fabric or a knitted fabric, the structure of the woven fabric or the knitted fabric is not particularly limited. For example, circular knitting, weft knitting, and warp knitting (tricot) are preferable for knitting, and plain weaving, twill weaving, and satin weaving are preferable forms of the fiber structure because the texture effect of the present invention can be exhibited well.

  As the fiber structure of the present invention, for example, when it is a non-woven fabric, the above oil and fat-containing rayon fiber alone or other regenerated cellulose fibers, cotton, hemp, wool, acrylic, polyester, polyamide, polyolefin, polyurethane and other fibers Can be used after blending. Examples of the form of the nonwoven fabric include a wet nonwoven fabric (wet papermaking), an airlaid nonwoven fabric, a hydroentangled nonwoven fabric, and a needle punched nonwoven fabric. Such a nonwoven fabric can be used, for example, for wet tissues, wet sheets such as interpersonal / objective wipers, hydrolytic sheets, and the like. Moreover, it can be used for sanitary sheets such as cosmetic puffs and absorbent bodies.

  In the fiber structure of the present invention, when mixed with other fibers, the oil-and-fat-containing rayon fibers are preferably contained in an amount of 10% by mass or more. More preferably, it is 15 mass% or more, More preferably, it is 20 mass% or more, Most preferably, it is 30 mass% or more. The upper limit of the content of the oil-and-fat-containing rayon fiber when mixed is preferably 90% by mass. When the oil and fat-containing rayon fiber is less than 10% by mass, the above-mentioned soft texture tends to be hardly obtained. In addition, when it exceeds 90% by mass, the ratio of the rayon fiber increases, so in addition to the above-mentioned hand effect, the moisture absorption, moisture release, moisture absorption heat generation, and drape properties are high, but the inherent low strength of rayon fiber. It tends to be low dryness (hard to dry), low heat retention, and low stretchability. To supplement such performance, it is preferably combined with other fibers.

  Other fibers combined with the oil-and-fat-containing rayon fiber can be appropriately selected according to the purpose, and are not particularly limited. For example, in order to improve the strength, it is preferable to combine polyester fibers, the method of blending the fat-containing rayon short fibers and the polyester fibers, or the oil-containing rayon fibers and the polyester fibers are twisted and knitted together with the long fibers. It is preferable to make a composite by interweaving. Moreover, it is preferable to combine a polyester fiber in order to improve the low drying property of sweat or laundry. For improving heat retention, polyacrylic fibers are preferred. For improving the low stretchability, polyurethane elastic fibers are preferred. Polyamide fibers are preferred for improving color development and improving flexural strength. Further, since the hard texture of cotton can be improved and the warmth of wool can be taken into account, it is preferable to combine such fibers in accordance with the application and requirements.

  The fat and oil-containing rayon fiber of the present invention is preferably blended with other fibers at a blending ratio of 20 to 50% by weight, and particularly when processed into a knit (knitted fabric) or woven fabric, the texture is felt in outer clothing. It is good, and the bottom, inner garment, socks, etc. have good moisture retention and texture.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples. In the following, when simply expressed as%, it means mass%.

  First, the measurement method will be described.

<Melting point>
For liquid oils and fats, use a differential scanning calorimeter (DSC), flow nitrogen gas at a rate of 30 ml / min as a flow gas, measure from -68 ° C to 20 ° C at a heating rate of 5 ° C / min, endotherm The temperature of the intersection of the straight line extension line before the start and the straight line extension line during endotherm was determined as the melting point (° C.). In the case of solid oils and fats, use a differential scanning calorimeter (DSC), flow nitrogen gas at a rate of 30 ml / min as a flow gas, and measure from 0 ° C to 90 ° C at a rate of temperature increase of 5 ° C / min. The minimum point of the endothermic peak was determined as the melting point (° C.).

<Average particle size>
The average particle size of the emulsion was measured using a laser diffraction / scattering particle distribution measuring apparatus LA-950V2 manufactured by Horiba, Ltd.

<Active oxygen method>
The active oxygen method (AOM) promotes oxidation by heating a sample (oil or fat or a mixture of oil and fat and an antioxidant) to 98 ° C and simultaneously blowing air into the sample, and the stability of the oil and fat is improved in a short time. This is a test method to be evaluated. The peroxide value (POV) of the sample was measured at regular intervals to confirm the progress of oxidation. Specifically, POV was measured as follows.
(1) 3 g of a sample was accurately weighed and placed in a stoppered Erlenmeyer flask, and 35 ml of a mixed solution of chloroform and glacial acetic acid (volume ratio 2: 3) was added and dissolved. When it did not dissolve uniformly, a mixture of chloroform and glacial acetic acid (volume ratio 2: 3) was added appropriately.
(2) Next, 1 ml of a saturated potassium iodide solution was added while passing nitrogen gas or carbon dioxide through the air in the flask, immediately plugged and mixed for about 1 minute, and then 0.01 N thiosulfuric acid using starch test solution as an indicator. The solution was titrated with a sodium solution, and the peroxide value (POV) was calculated by the following formula.
Peroxide value (meq / kg) = (a / S) × 10
S: Amount of sample collected (g), a: Titration volume of 0.01N sodium thiosulfate solution (ml)
(3) AOM stability was displayed as the time (hr) required for POV to reach 100 and the time (hr) required for POV to reach 200. It means that oxidation of fats and oils progresses in a short time, so that each numerical value is small. In the following, the time (hr) required for POV to reach 100 is expressed as POV. 100 (hr), and the time (hr) required for POV to reach 200 is POV. 200 (hr).

<Odor intensity>
In the AOM test, the maximum odor intensity of the sample was subjected to sensory evaluation in the following five stages.
1: No unpleasant odor 2: Slightly unpleasant odor 3: Unpleasant odor 4: Slightly unpleasant odor 5: Strong unpleasant odor

<Coloring state>
In the AOM test, the coloration state of the sample was subjected to sensory evaluation in the following five stages.
1: No color 2: Yellowish brown 3: Brown 4: Reddish brown 5: Dark brown

<Viscosity>
The viscosity of the sample after the AOM test was sensory evaluated in the following three stages.
1: No change 2: Thickening 3: Strong thickening

<Iodine number>
The iodine amount reacted per 100 g of absolutely dry cotton was measured as the iodine value [I ₂ (g) / cotton (100 g)] according to the following procedure.
(1) The moisture content of the sample raw cotton is measured.
(2) A raw cotton sample is precisely weighed so that the amount of oil and fat is about 0.1 g, and placed in an Erlenmeyer flask.
(3) Add 20 ml of cyclohexane and stir, and further add 10 ml of Wis reagent (iodine aqueous solution of iodine monochloride) and 20 ml of ion-exchanged water.
(4) Leave at room temperature in a dark place for 30 minutes with occasional stirring.
(5) After adding 20 ml of 10% by mass potassium iodide solution and 20 ml of ion-exchanged water, titration is performed with 0.1 N sodium thiosulfate.
(6) When the color of the solution becomes lighter, the starch indicator is added and the titration is continued, and 0.1N sodium thiosulfate titration when the color of the starch indicator disappears is read as the end point.
(7) Do the same test without putting a sample, and make a blank test.
(8) The iodine value is calculated by the following formula.
Iodine value of fiber [I ₂ (g) / cotton (100 g)] = (blank test titration-titration) × 1.269 / absolute dry cotton mass

<Fine fineness>
The fineness of the fiber was measured according to JIS L 1015.

<Fiber strength and elongation>
The strength (dry strength, wet strength) and elongation (dry elongation and wet elongation) of the fiber were measured according to JIS L 1015.

<Accelerated test>
Fiber properties were measured after standing for 8 days in an environment of 80 ° C, 70% RH (constant temperature and humidity chamber, "IG420" manufactured by Yamato Scientific Co., Ltd.), and fiber aging was promoted by comparing before and after treatment. The state was evaluated.

<Washing durability>
The fiber was washed 10 times each using a neutral detergent (textile product new function evaluation council standard detergent) and an alkaline detergent, and then the iodine value was measured. The washing test was conducted according to JIS L 0217 103 method.

<Average pore size of voids in rayon fiber after deoiling>
The average pore diameter of the voids in the rayon fiber after deoiling treatment was measured using a cross-sectional photograph of the fiber after deoiling treatment (scanning electron micrograph, magnification 3000 times). Specifically, the cross-sectional photograph of the fiber after deoiling treatment (scanning electron micrograph, magnification 3000 times) is magnified to a magnification of 9010 by image processing, and the cross-section of any fiber is sampled from the printed paper, The diameter of the voids on the cross section was measured, and the average diameter of the 100 measured voids was used as the average pore diameter of the voids. In addition, the elliptical space | gap was converted into the perfect circle diameter from the area calculated by measuring the long diameter and the short diameter, and it was set as the diameter of the space | gap part.
[Deoiling treatment]
(I) About 2.3 g of a sample was precisely weighed and packed in a sample tube having a small hole at the bottom.
(II) The bottom hole was closed, 10 ml of methanol was poured into the sample tube as an extraction solvent, allowed to stand for a certain period of time and permeated, and then the methanol treatment liquid was extracted with a press device.
(III) Using the same sample, the extraction by the above operation (II) was repeated 20 times, and then the sample taken out from the sample tube was washed with water, dried at 105 ° C. for 2 hours, and the fiber after the deoiling treatment was performed. Obtained.

(Effect confirmation test 1 of antioxidants for oils and fats)
Purified bran oil (from Goto) having the fatty acid composition shown in Table 1 below as the fat and oil and having a melting point of −11.6 ° C. is used with the antioxidant shown in Table 2 below as the antioxidant, and Table 3 below. Fats and antioxidants are mixed at a blending ratio shown in -4, and the peroxide value (POV) is measured based on the active oxygen method (AOM). The results are shown in Tables 3-4 and FIGS. It was shown to. Further, the odor, appearance and viscosity of the sample in the AOM test were evaluated, and the results are shown in Tables 3 to 4 below.

  As can be seen from the results of FIGS. 1 to 3 and Tables 3 to 4, when the antioxidant was added to the cocoon oil, the AOM stability was remarkably higher than when no antioxidant was added. It was also found that in the AOM stability, the same effect can be achieved with tocotrienol and γ-tocopherol in a small amount as compared with mixed tocopherol. Further, in the appearance, when the addition amount was almost the same, the coloring start time was delayed as compared with the mixed tocopherol. From the viewpoint of compatibility between AOM stability and odor and / or appearance, dl-α-tocopherol, tocotrienol and γ-tocopherol are superior to mixed tocopherol, tocotrienol and γ-tocopherol are superior, and tocotrienol is Excellent in AOM stability and all of odor, appearance and viscosity.

(Effect confirmation test 2 of antioxidants for oils and fats)
Olive oil (Spain) having a fatty acid composition shown in Table 5 below as the fat and oil and having a melting point of 0 to 6 ° C. is used as an antioxidant and the antioxidant shown in Table 2 above. Fats and oils and antioxidants were mixed at the blending ratio shown, and the peroxide value (POV) was measured based on the active oxygen method (AOM). The results are shown in Table 6 and FIG. Further, the odor, appearance and viscosity of the sample in the AOM test were evaluated, and the results are shown in Table 6 below.

  As can be seen from the results in FIG. 4 and Table 6, when an antioxidant containing 55% by mass or more of tocotrienol is added to olive oil, the AOM stability is higher than when no antioxidant is added or when mixed tocopherol is added. In terms of both odor and appearance.

Example 1
<Preparation of emulsion liquid>
Effect of antioxidants on fats and oils Emulsifier is added by adding emulsifier to 30% by weight of fats and oils in a mixture of coconut oil and dl-α-tocopherol blended in the same way as in test number A3 in Test 1 Prepared.

<Preparation of spinning viscose liquid>
The obtained emulsion solution was added to the raw material viscose so that the amount of oil added was 1.5% by mass with respect to cellulose, and stirred and mixed in a mixer to prepare a spinning viscose solution. The temperature was kept at 20 ° C. As the raw material viscose, a viscose stock solution containing 8.5% by mass of cellulose, 5.7% by mass of sodium hydroxide, and 2.7% by mass of carbon disulfide was used.

<Spinning conditions>
The obtained viscose liquid for spinning was spun at a spinning speed of 60 m / min and a draw ratio of 50% by a two-bath tension spinning method to obtain a cocoon oil-containing rayon fiber having a fineness of about 1.4 dtex. As the spinning bath, a Mueller bath (50 ° C.) containing 100 g / L of sulfuric acid, 15 g / L of zinc sulfate, and 350 g / L of sodium sulfate was used. In addition, a circular nozzle having 4000 holes having a hole diameter of 0.06 mm was used as a spinneret for discharging viscose.

<Scouring conditions>
The viscose rayon yarn obtained above was cut into a fiber length of 38 mm and scoured. In the scouring step, after washing with hot water, washing with water, applying an oil agent, dropping excess moisture and oil agent from the fiber with a compression roller, and then performing a drying treatment (60 ° C., 7 hours), the fat and oil of Example 1 A contained rayon fiber was obtained.

(Example 2)
The oil-containing rayon fiber of Example 2 was obtained in the same manner as in Example 1 except that a mixed liquid of coconut oil and tocotrienol having the same composition as test number A5 in the effect confirmation test 1 of the antioxidant against oils and fats was used. .

(Example 3)
The oil and fat-containing rayon fiber of Example 3 is obtained in the same manner as in Example 1 except that a mixed solution of olive oil and tocotrienol having the same composition as test number B4 in the effect confirmation test 2 of fats and oils is used. It was.

(Reference Example 1)
As Reference Example 1, regular rayon (manufactured by Daiwabo Rayon Co., Ltd.) was used.

( Comparative Example 1 )
The fat-and-oil-containing rayon fiber of Comparative Example 1 was obtained in the same manner as in Example 1 except that a mixed liquid of cocoon oil and mixed tocopherol having the same composition as in the above test number A2 was used.

The fineness, dry strength, wet strength, dry elongation and wet elongation of the rayon fibers of Examples 1 to 3 and Reference Example 1 and Comparative Example 1 were measured as described above, and the results are shown in Table 7 below. Further, the iodine values of the rayon fibers of Examples 1 to 3, Reference Example 1 and Comparative Example 1 were measured, and the results are shown in Table 7 below. Table 7 below also shows the results of accelerated tests and washing durability.

  As can be seen from Table 7, the fiber strength reduction rate of the oil-and-fat-containing rayon fiber of the example by the accelerated test was lower than that of the regular rayon. From this result, in the fat and oil-containing rayon fiber of the example, the fat and oil is finely dispersed in the cellulose constituting the rayon fiber with good oxidation stability, and the effect of the antioxidant added to the fat and oil. Thus, it is estimated that the stability of the rayon fiber is improved. Moreover, since the iodine value of the fat-and-oil-containing rayon fiber of an Example does not change substantially also in any washing test at the time of washing 10 times with a neutral detergent and 10 times of washing with an alkaline detergent, It was confirmed that the oil-and-fat-containing rayon fibers of the examples were excellent in washing durability without being dropped off.

  About the rayon fiber of Example 2 and the reference example 1, the hydroentangled nonwoven fabric was produced and the moisture absorption / release characteristic was evaluated with the following method.

[Production of non-woven fabric]
The fiber of Example 2 and the fiber of Reference Example 1 were prepared. 100% by mass of each fiber was defibrated with a semi-random card to prepare a card web having a basis weight of about 100 g / m ² . Next, from a nozzle in which orifices having a nozzle hole diameter of 0.13 mm are arranged at intervals of 1 mm, a water flow is jetted with a water pressure of 3 MPa from the web surface and 5 MPa from the web surface, and 5 MPa from the web back surface, and then naturally dried to produce a hydroentangled nonwoven fabric. .

[Moisture absorption / release test method]
(1) The hydroentangled nonwoven fabric was cut to about 2 g, and the mass (W0) of the test piece that had been completely dried using a constant temperature dryer (105 ° C., 2 hr) was measured.
(2) The sample was allowed to cool in a desiccator.
(3) When measuring the moisture content at the time of moisture absorption, the sample was folded in a petri dish of about 92 mmφ, and left in a constant temperature and humidity machine adjusted to 40 ° C. and 90% RH for 24 hours. (W1) was measured.
(4) When measuring moisture content during moisture release, fold the sample into a petri dish of about 92 mmφ, leave it in a constant temperature and humidity chamber adjusted to 20 ° C. and 60% RH for 24 hours, and leave the sample Mass (W2) was measured.
(5) The moisture content of the sample at the time of moisture absorption and moisture release was calculated by the following equation.
Moisture content during moisture absorption (%) = (W1-W0) / W1 × 100
Moisture content during moisture release (%) = (W2−W0) / W2 × 100
(6) From the above test results, the moisture absorption / release parameter ΔMR was calculated by the following equation to evaluate the moisture absorption / release effect. ΔMR indicates that the larger the value, the higher the moisture absorption / release effect.
ΔMR (%) = moisture content during moisture absorption-moisture content during moisture release

 As a result of comparing the moisture absorption / release characteristics of the oil-and-fat-containing rayon fiber (Example 2) of the present invention and the regular rayon fiber (Reference Example 1), no influence on the moisture absorption / release characteristics due to the incorporation of the oil / fat was observed. The moisture absorption / release characteristics were confirmed to be as good as regular rayon.

  Moreover, when the texture of the fat and oil-containing rayon fibers of Examples 1 to 3 was evaluated by a sensory (tactile feeling) test, the texture was soft and soft.

  The oil and fat-containing rayon fiber of the present invention can be used for fiber structures such as spun yarn, knitted fabric, woven fabric, non-woven fabric, tow, filament, batting (padded cotton), paper and the like. Further, the fiber structure of the present invention can be used for clothes, cosmetic puffs, hygiene materials such as absorbent bodies, wet tissues, wet sheets such as interpersonal / objective wipers, water-degradable sheets, dry wipers, filters, and the like.

Claims (10)

It is a fat and oil-containing rayon fiber containing fat and antioxidant in the rayon fiber,
The cellulose and the fat / oil in the rayon fiber are in an incompatible state, and the fat / oil is finely dispersed in the cellulose,
The fats and oils include at least one fatty acid component selected from fatty acids and glycerin esters thereof,
The antioxidant includes an antioxidant containing 80% by mass or more of α-type tocopherol and tocotrienol as essential components, an antioxidant containing 80% by mass or more of γ-type tocopherol and tocotrienol as an essential component, α-type tocopherol, γ-type tocopherol and Antioxidant containing 80% by mass or more of tocotrienol as an essential component, antioxidant containing 80% by mass or more of α-type tocopherol as an essential component, antioxidant containing 80% by mass or more of γ-type tocopherol as an essential component, or essential tocotrienol An oil-containing rayon fiber characterized by being an antioxidant containing 55% by mass or more as a component .   The fat-and-oil-containing rayon fiber according to claim 1, wherein the antioxidant is an antioxidant containing 60% by mass or more of tocotrienol.   The fat-and-oil-containing rayon fiber according to claim 1 or 2, wherein the fat is one or more selected from the group consisting of camellia oil and olive oil.   The fat and oil-containing rayon fiber according to any one of claims 1 to 3, wherein a blending amount of the fat is in a range of 0.5 to 15% by mass with respect to cellulose.   The fat and oil-containing rayon fiber according to any one of claims 1 to 4, wherein a blending amount of the antioxidant is in a range of 0.03 to 15 mass% with respect to the fat and oil. It is a manufacturing method of oil and fat content rayon fiber given in any 1 paragraph of Claims 1-5,
Prepare an emulsion liquid by mixing oils and fats, antioxidants and emulsifiers,
A viscose solution for spinning is prepared by mixing the emulsion solution with a viscose stock solution containing cellulose,
The spinning viscose liquid is extruded from a nozzle and spun, and coagulated and regenerated to obtain a fat-containing rayon fiber.
The fats and oils include at least one fatty acid component selected from fatty acids and glycerin esters thereof,
The antioxidant includes an antioxidant containing 80% by mass or more of α-type tocopherol and tocotrienol as essential components, an antioxidant containing 80% by mass or more of γ-type tocopherol and tocotrienol as essential components, α-type tocopherol, γ-type tocopherol and Antioxidant containing 80% by mass or more of tocotrienol as an essential component, Antioxidant containing 80% by mass or more of α-type tocopherol as an essential component, Antioxidant containing 80% by mass or more of γ-type tocopherol as an essential component, or essential tocotrienol The manufacturing method of the fat-and-oil containing rayon fiber characterized by being an antioxidant containing 55 mass% or more as a component .   In the said emulsion liquid, the compounding quantity of the said antioxidant is the range of 0.03-15 mass% with respect to fats and oils, The manufacturing method of the fats and oils containing rayon fiber of Claim 6.   The fiber structure containing the fat-and-oils containing rayon fiber of any one of Claims 1-5. Containing 10 to 90% by mass of the oil-containing rayon fiber,
The fiber structure according to claim 8 , wherein at least one fiber selected from the group consisting of polyester fiber, polyacrylic fiber, polyamide fiber, polyurethane elastic fiber, cotton and wool is compounded as the other fiber.   The fiber structure according to claim 8 or 9, wherein the fiber structure has a form selected from the group consisting of spun yarn, knitted fabric, woven fabric, and nonwoven fabric.

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