JP2016065116A - Aqueous dispersion of cellulose nanofibers, and food products and cosmetics using the same - Google Patents
Aqueous dispersion of cellulose nanofibers, and food products and cosmetics using the same Download PDFInfo
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- JP2016065116A JP2016065116A JP2014193258A JP2014193258A JP2016065116A JP 2016065116 A JP2016065116 A JP 2016065116A JP 2014193258 A JP2014193258 A JP 2014193258A JP 2014193258 A JP2014193258 A JP 2014193258A JP 2016065116 A JP2016065116 A JP 2016065116A
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- Prior art keywords
- fatty acid
- aqueous dispersion
- acid ester
- cellulose nanofiber
- salt type
- Prior art date
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- Granted
Links
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Abstract
Description
本発明は、セルロースナノファイバー水分散体組成物、それを用いた食品および化粧料に関する。 The present invention relates to a cellulose nanofiber aqueous dispersion composition, a food using the same, and a cosmetic.
セルロースナノファイバー水分散体の用途範囲は広く、化粧料や医薬品、医薬部外品、医療分野、更には食品などに幅広く使用されうる（特許文献１、２）。また、通常、密封容器に充填されて販売されている食品においては、製造してから食されるまでの期間、微生物などによる変敗が防止できる様に、殺菌工程を経て流通されているが、食品衛生法で指定された方法で製造、流通したとしても、食品によっては混入する耐熱性芽胞菌や耐熱性カビ等によって変敗を生じることがある。また、一般的な商業的滅菌では耐熱性のある芽胞形成捍菌を完全に殺菌することができず、食品中にこれら耐熱性菌が残存した場合には、高温で長時間保存しているうちに発芽、増殖して内容物を腐敗させることがある。 Cellulose nanofiber aqueous dispersions have a wide range of applications, and can be widely used in cosmetics, pharmaceuticals, quasi drugs, medical fields, and foods (Patent Documents 1 and 2). In addition, the food that is usually sold in a sealed container is distributed through a sterilization process so that it can be prevented from being damaged by microorganisms during the period from manufacture to eating. Even if it is manufactured and distributed by the method specified by the Food Sanitation Law, deterioration may occur due to heat-resistant spore bacteria, heat-resistant molds and the like mixed in depending on the food. In addition, general commercial sterilization cannot completely sterilize heat-resistant spore-forming rods, and if these heat-resistant bacteria remain in food, May germinate and multiply, causing the contents to rot.
天然系抗菌剤として、例えば、エタノール、ポリリジン、リゾチーム、プロタミン、ラクトフェリン、グリシン、キトサン、チモール、オイゲノール、油性甘草エキス、アシタバ抽出エキス、竹抽出エキス、香辛料抽出物が開示されている（特許文献３） As natural antibacterial agents, for example, ethanol, polylysine, lysozyme, protamine, lactoferrin, glycine, chitosan, thymol, eugenol, oily licorice extract, acitaba extract, bamboo extract, spice extract are disclosed (Patent Document 3). )
セルロースナノファイバー水分散体からなる水性ゲル状組成物において、常温保管において経時的に腐敗が進み、例えば、セルロースナノファイバー水分散体を増粘剤とする各種応用用途において、経時的に系の粘度低下を生じたり、異臭を放つ場合や、外観上で有色、或いは異物様物質の発生によって均一性や美観を損ねることで商品価値を著しく低下させる問題があった。また、乳化安定化や分散安定化に係る応用用途においては、その性能が腐敗の進行に伴って大きく損なわれる問題があった。化粧品、医薬品、医療分野、更には食品分野での使用において、安全性の観点から使用可能な防腐剤、殺菌剤、抗菌剤、静菌剤の種類や添加量が限定されるといった問題などがあった。これらを解決する為に、防腐剤や殺菌剤、抗菌剤、静菌剤を添加して、流通させることが想定される。特許文献３記載の天然系抗菌剤は天然系素材であるため安全性は高いが、いずれも抗菌活性の点で満足いくものではなかった。 In an aqueous gel composition composed of an aqueous dispersion of cellulose nanofibers, decay proceeds with time during normal temperature storage.For example, in various application uses where the aqueous dispersion of cellulose nanofibers is a thickener, the viscosity of the system over time There has been a problem in that the product value is remarkably lowered by causing deterioration, giving off a strange odor, or being colored on the appearance, or by deteriorating uniformity and aesthetics due to the generation of foreign substances. Moreover, in the application use which concerns on emulsification stabilization and dispersion stabilization, there existed a problem by which the performance was impaired significantly with the progress of decay. In use in the cosmetics, pharmaceuticals, medical, and food fields, there is a problem that the types and amounts of preservatives, bactericides, antibacterial agents, and bacteriostatic agents that can be used are limited from the viewpoint of safety. It was. In order to solve these problems, it is assumed that preservatives, bactericides, antibacterial agents, and bacteriostatic agents are added and distributed. The natural antibacterial agent described in Patent Document 3 is a natural material and thus has high safety, but none of them is satisfactory in terms of antibacterial activity.
本発明は、上記問題点に鑑みて為されたものであり、安全性が高く、低濃度で効果を発揮する腐敗防止剤を提供することを課題とする。また、化粧料、医薬品、医療分野、更には食品分野での使用に際して、皮膚刺激性や粘膜刺激性、更には刺激臭や不快臭の発生、風味や味の異変、劣化、消失、外観変化、使用感の変化などを抑制することを課題とする。 This invention is made | formed in view of the said problem, and makes it a subject to provide the anti-corruption agent which is highly safe and exhibits an effect at low concentration. In addition, when used in the cosmetics, pharmaceuticals, medical fields, and even in the food field, skin irritation and mucous membrane irritation, further generation of irritating odors and unpleasant odors, flavor and taste abnormalities, deterioration, disappearance, appearance changes, It is an object to suppress changes in the feeling of use.
本発明の発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、特定の界面活性剤を含有するセルロースナノファイバー水分散体組成物を用いることで課題を解決できることを見出し、本発明を完成させるに至った。 The inventors of the present invention have found that the problem can be solved by using a cellulose nanofiber aqueous dispersion composition containing a specific surfactant as a result of intensive studies to solve the above problems. It came to complete.
すなわち、本発明は下記に掲げるに発明に関する。
（１）下記（ａ）および／または（ｂ）を含有するセルロースナノファイバー水分散体組成物。
（ａ）脂肪酸エステル型構造非イオン界面活性剤
（ｂ）四級アンモニウム塩型、ベンザルコニウム塩型およびピリジニウム塩型からなる群より選ばれる１種以上の構造を有するカチオン界面活性剤
（２）前記脂肪酸エステル型構造非イオン界面活性剤が、
ショ糖脂肪酸エステル、糖アルコール脂肪酸エステル、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステルおよびソルビタン脂肪酸エステルからなる群より選ばれる１種以上である（１）記載のセルロースナノファイバー水分散体組成物。
（３）前記カチオン界面活性剤が、塩化ベンザルコニウム、塩化セチルピリジニウム、塩化ジデシルジメチルアンモニウム、塩化セチルトリメチルアンモニウムからなる群より選ばれる１種以上である（１）記載のセルロースナノファイバー水分散体組成物。
（４） （１）または（２）記載のセルロースナノファイバー水分散体組成物を含有する食品。
（５） （１）〜（３）のいずれか記載のセルロースナノファイバー水分散体組成物を含有する化粧料。
（６）下記（ａ）および／または（ｂ）を含有するセルロースナノファイバー水分散体用腐敗防止剤。
（ａ）脂肪酸エステル型構造非イオン界面活性剤
（ｂ）四級アンモニウム塩型、ベンザルコニウム塩型およびピリジニウム塩型からなる群より選ばれる１種以上の構造を有するカチオン界面活性剤
That is, the present invention relates to the invention described below.
(1) A cellulose nanofiber aqueous dispersion composition containing the following (a) and / or (b):
(A) Fatty acid ester type structure nonionic surfactant (b) Cationic surfactant having at least one structure selected from the group consisting of quaternary ammonium salt type, benzalkonium salt type and pyridinium salt type (2) The fatty acid ester type structure nonionic surfactant is
The cellulose nanofiber aqueous dispersion composition according to (1), which is at least one selected from the group consisting of sucrose fatty acid ester, sugar alcohol fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester and sorbitan fatty acid ester.
(3) The cellulose nanofiber aqueous dispersion according to (1), wherein the cationic surfactant is at least one selected from the group consisting of benzalkonium chloride, cetylpyridinium chloride, didecyldimethylammonium chloride, and cetyltrimethylammonium chloride. Body composition.
(4) A food containing the cellulose nanofiber aqueous dispersion composition according to (1) or (2).
(5) A cosmetic comprising the cellulose nanofiber aqueous dispersion composition according to any one of (1) to (3).
(6) An anti-corruption agent for cellulose nanofiber aqueous dispersion, comprising the following (a) and / or (b):
(A) Fatty acid ester type structure nonionic surfactant (b) Cationic surfactant having at least one structure selected from the group consisting of quaternary ammonium salt type, benzalkonium salt type and pyridinium salt type
本発明によれば、安全性が高く、低濃度で効果を発揮する腐敗防止剤を提供することができる。また、皮膚刺激性や粘膜刺激性、更には刺激臭や不快臭の発生、風味や味の異変、劣化、外観変化、使用感の変化などを抑制した化粧料、医薬品、医療分野製品、更には食品を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the anti-corruption agent which exhibits high safety and exhibits an effect at a low concentration can be provided. In addition, skin irritation and mucous membrane irritation, as well as generation of irritating odors and unpleasant odors, changes in flavor and taste, deterioration, changes in appearance, changes in feeling of use, cosmetics, pharmaceuticals, medical products, and more Food can be provided.
本発明のセルロースナノファイバー水分散体組成物は、下記（ａ）および／または（ｂ）を含有する。
（ａ）脂肪酸エステル型構造非イオン界面活性剤
（ｂ）四級アンモニウム塩型、ベンザルコニウム塩型およびピリジニウム塩型からなる群より選ばれる１種以上の構造を有するカチオン界面活性剤
（ａ）および／または（ｂ）を含有することによって、防腐、殺菌、抗菌、静菌作用を付与するに止まらず、セルロースナノファイバー水分散体の配合安定性や当該配合組成物の経時安定性を損なうことがなく、逆にそれらを大きく改善する効果がある。
The cellulose nanofiber aqueous dispersion composition of the present invention contains the following (a) and / or (b).
(A) Fatty acid ester type structure nonionic surfactant (b) Cationic surfactant having at least one structure selected from the group consisting of quaternary ammonium salt type, benzalkonium salt type and pyridinium salt type (a) And / or (b) not only gives antiseptic, bactericidal, antibacterial and bacteriostatic action, but also impairs the stability of the cellulose nanofiber aqueous dispersion and the stability over time of the composition. On the contrary, it has the effect of greatly improving them.
本発明における（ａ）成分は、脂肪酸エステル型構造非イオン界面活性剤である。脂肪酸エステル型構造非イオン界面活性剤を使用することで、低毒性、低刺激性、高配合安定性、耐塩性、低泡性であり、安全性が高く、一方で、防腐、殺菌、抗菌、静菌作用に優れるという効果を奏する。また、工業用用途に加え、化粧品、医薬品、医療分野で使用可能であり、食品分野においても好適に使用できる。 The component (a) in the present invention is a fatty acid ester structure nonionic surfactant. By using fatty acid ester type structure nonionic surfactant, low toxicity, low irritation, high blending stability, salt resistance, low foaming property, high safety, while antiseptic, sterilizing, antibacterial, It has the effect of being excellent in bacteriostatic action. Moreover, in addition to industrial use, it can be used in the cosmetics, pharmaceuticals, and medical fields, and can also be suitably used in the food field.
本発明における脂肪酸エステル型構造非イオン界面活性剤としては、分子中に脂肪酸エステル型構造を有する非イオン界面活性剤であれば、特に限定されないが、セルロースナノファイバー分散体、或いはセルロースナノファイバー分散体が本質にもつ性状、例えば、低毒性、低刺激性、低浸透性、低泡性を悪化させないことから、ショ糖脂肪酸エステル（ａ１）、糖アルコール脂肪酸エステル（ａ２）、グリセリン脂肪酸エステル（ａ３）、ポリグリセリン脂肪酸エステル（ａ４）およびソルビタン脂肪酸エステル（ａ５）からなる群より選ばれる１種以上であることが好ましい。 The fatty acid ester-type structure nonionic surfactant in the present invention is not particularly limited as long as it is a nonionic surfactant having a fatty acid ester-type structure in the molecule, but the cellulose nanofiber dispersion or the cellulose nanofiber dispersion Sucrose fatty acid ester (a1), sugar alcohol fatty acid ester (a2), glycerin fatty acid ester (a3) It is preferable that it is 1 or more types chosen from the group which consists of polyglyceryl fatty acid ester (a4) and sorbitan fatty acid ester (a5).
本発明におけるショ糖脂肪酸エステル（ａ１）としては、ショ糖と各種脂肪酸とのエステルであれば、特に限定されない。 The sucrose fatty acid ester (a1) in the present invention is not particularly limited as long as it is an ester of sucrose and various fatty acids.
本発明における糖アルコール脂肪酸エステル（ａ２）としては、糖アルコールと各種脂肪酸とのエステルであれば、特に限定されない。前記糖アルコールとしては、エリスリトール、キシリトール、アラビトール、ソルビトール、マンニトールが挙げられる。これらは１種又２種以上を組み合わせて使用することができる。 The sugar alcohol fatty acid ester (a2) in the present invention is not particularly limited as long as it is an ester of a sugar alcohol and various fatty acids. Examples of the sugar alcohol include erythritol, xylitol, arabitol, sorbitol, and mannitol. These can be used alone or in combination of two or more.
前記ショ糖脂肪酸エステル（ａ１）および糖アルコール脂肪酸（ａ２）エステルにおける脂肪酸としては、特に限定されず、飽和脂肪酸、不飽和脂肪酸のいずれもが使用可能である。好ましくは炭素原子数８〜２０、より好ましくは１０〜１８の脂肪酸であり、さらに好ましくは１４〜１８の脂肪酸であり、ミリスチン酸、パルミチン酸、ステアリン酸が特に好ましい。これらは１種又２種以上を組み合わせて使用することができる。 The fatty acids in the sucrose fatty acid ester (a1) and sugar alcohol fatty acid (a2) ester are not particularly limited, and any of saturated fatty acids and unsaturated fatty acids can be used. Preferably it is a C8-C20 fatty acid, More preferably, it is a 10-18 fatty acid, More preferably, it is a 14-18 fatty acid, Myristic acid, a palmitic acid, and a stearic acid are especially preferable. These can be used alone or in combination of two or more.
前記ショ糖脂肪酸エステル（ａ１）および糖アルコール脂肪酸エステル（ａ２）におけるエステルとしては、特に限定されないが、モノエステル、ジエステル、これらの混合物が好ましく、モノエステルがより好ましい。 The ester in the sucrose fatty acid ester (a1) and sugar alcohol fatty acid ester (a2) is not particularly limited, but monoesters, diesters, and mixtures thereof are preferable, and monoesters are more preferable.
本発明におけるグリセリン脂肪酸エステル（ａ３）としては、グリセリンと各種脂肪酸とのエステルであれば、特に限定されない。モノエステル、ジエステル、これらの混合物が好ましく、モノエステルがより好ましい。脂肪酸としては、特に限定されず、飽和脂肪酸、不飽和脂肪酸のいずれもが使用可能である。好ましくは炭素原子数８〜２０、より好ましくは１０〜１８の脂肪酸であり、カプリル酸、カプリン酸、ラウリン酸がさらに好ましい。これらは１種又２種以上を組み合わせて使用することができる。なお好ましいものとして、グリセリンモノカプリル酸エステル、グリセリンモノカプリン酸エステル、グリセリンモノラウリン酸エステルが挙げられる。これらは１種又２種以上を組み合わせて使用することができる。 The glycerin fatty acid ester (a3) in the present invention is not particularly limited as long as it is an ester of glycerin and various fatty acids. Monoesters, diesters, and mixtures thereof are preferred, and monoesters are more preferred. It does not specifically limit as a fatty acid, Both a saturated fatty acid and an unsaturated fatty acid can be used. Preferably it is a C8-C20, more preferably 10-18 fatty acid, and caprylic acid, capric acid and lauric acid are more preferred. These can be used alone or in combination of two or more. Preferable examples include glycerol monocaprylate, glycerol monocaprate, and glycerol monolaurate. These can be used alone or in combination of two or more.
本発明におけるポリグリセリン脂肪酸エステル（ａ４）としては、ポリグリセリンと各種脂肪酸とのエステルであれば、特に限定されない。モノエステル、ジエステル、トリ以上のエステル、および、これらの混合物のいずれであってもよい、ポリグリセリンとしては、重合度２〜１５のポリグリセリンが好ましく、重合度２〜５のポリグリセリンがより好ましく、ジグリセリンがさらに好ましい。脂肪酸としては、炭素原子数６〜１２が好ましく、カプロン酸、カプリル酸、カプリン酸がより好ましい。これらは１種又２種以上を組み合わせて使用することができる。 The polyglycerol fatty acid ester (a4) in the present invention is not particularly limited as long as it is an ester of polyglycerol and various fatty acids. The polyglycerol, which may be any of monoesters, diesters, tri- or higher esters, and mixtures thereof, is preferably polyglycerol having a polymerization degree of 2 to 15, more preferably polyglycerol having a polymerization degree of 2 to 5. Diglycerin is more preferable. As a fatty acid, C6-C12 is preferable and a caproic acid, caprylic acid, and capric acid are more preferable. These can be used alone or in combination of two or more.
本発明におけるソルビタン脂肪酸エステル（ａ５）としては、ソルビタンと各種脂肪酸とのエステルであれば、特に限定されない。モノエステル、ジエステル、これらの混合物が好ましく、モノエステルがより好ましい。脂肪酸としては、特に限定されず、飽和脂肪酸、不飽和脂肪酸のいずれもが使用可能である。好ましくは炭素原子数６〜２０、より好ましくは６〜１２の脂肪酸であり、カプリル酸、カプリン酸がさらに好ましい。これらは１種又２種以上を組み合わせて使用することができる。なお好ましいものとして、ソルビタンモノカプリル酸エステル、ソルビタンモノカプリン酸エステルが挙げられる。これらは１種又２種以上を組み合わせて使用することができる。 The sorbitan fatty acid ester (a5) in the present invention is not particularly limited as long as it is an ester of sorbitan and various fatty acids. Monoesters, diesters, and mixtures thereof are preferred, and monoesters are more preferred. It does not specifically limit as a fatty acid, Both a saturated fatty acid and an unsaturated fatty acid can be used. Preferably it is a C6-C20 fatty acid, More preferably, it is a 6-12 fatty acid, and caprylic acid and capric acid are still more preferable. These can be used alone or in combination of two or more. Preferable examples include sorbitan monocaprylate and sorbitan monocaprate. These can be used alone or in combination of two or more.
本発明におけるセルロースナノファイバー水分散体組成物中の脂肪酸エステル型構造非イオン界面活性剤（ａ）の含有量としては、セルロースナノファイバー水分散体に対して２００〜２０,０００ｐｐｍが好ましく、５００〜１５,０００ｐｐｍがより好ましく、８００〜１０,０００ｐｐｍがさらに好ましい。これらの範囲であれば、外観が白濁、粘度低下、不均一が生じないことから好ましい。 As content of the fatty acid ester type structure nonionic surfactant (a) in the cellulose nanofiber aqueous dispersion composition in the present invention, 200 to 20,000 ppm is preferable with respect to the cellulose nanofiber aqueous dispersion, and 500 to 15,000 ppm is more preferable, and 800 to 10,000 ppm is more preferable. If it is in these ranges, it is preferable because the appearance does not cause cloudiness, a decrease in viscosity, and nonuniformity.
本発明における（ｂ）成分は、四級アンモニウム塩型、ベンザルコニウム塩型およびピリジニウム塩型からなる群より選ばれる１種以上の構造を有するカチオン界面活性剤である。前記カチオン界面活性剤は、低添加量で腐敗抑制作用を発揮し、さらに低毒性、低刺激性、配合安定性、耐塩性、低泡性である。また、一般に無色、或いは淡色の市販品が入手可能であり、製品外観上からも好ましい。 The component (b) in the present invention is a cationic surfactant having one or more structures selected from the group consisting of a quaternary ammonium salt type, a benzalkonium salt type and a pyridinium salt type. The cationic surfactant exhibits an anti-corrosion action at a low addition amount, and further has low toxicity, low irritation, compounding stability, salt resistance, and low foaming property. Moreover, generally colorless or light-colored commercial products are available, which is preferable from the viewpoint of product appearance.
本発明における前記カチオン界面活性剤としては、四級アンモニウム塩型、ベンザルコニウム塩型およびピリジニウム塩型であれば特に限定されないが、セ低添加量で腐敗抑制作用を発揮し、また、一般に無色、或いは淡色の市販品が入手可能であり、製品外観上から、塩化ベンザルコニウム、塩化セチルピリジニウム、塩化ジデシルジメチルアンモニウム、塩化セチルトリメチルアンモニウムからなる群より選ばれる１種以上であることが好ましい。 The cationic surfactant in the present invention is not particularly limited as long as it is a quaternary ammonium salt type, a benzalkonium salt type, and a pyridinium salt type. Alternatively, a light-colored commercial product is available, and it is preferably one or more selected from the group consisting of benzalkonium chloride, cetylpyridinium chloride, didecyldimethylammonium chloride, and cetyltrimethylammonium chloride from the viewpoint of product appearance. .
本発明におけるセルロースナノファイバー水分散体組成物中の脂肪酸エステル型構造非イオン界面活性剤（ａ）の含有量としては、セルロースナノファイバー水分散体に対して１０〜５,０００ｐｐｍが好ましく、１００〜３,５００ｐｐｍがより好ましく、３００〜２,５００ｐｐｍがさらに好ましい。これらの範囲であれば、外観が白濁、粘度低下、不均一が生じないことから好ましい。 As content of the fatty acid ester type structure nonionic surfactant (a) in the cellulose nanofiber aqueous dispersion composition in the present invention, 10 to 5,000 ppm is preferable with respect to the cellulose nanofiber aqueous dispersion. 3,500 ppm is more preferable, and 300 to 2500 ppm is even more preferable. If it is in these ranges, it is preferable because the appearance does not cause cloudiness, a decrease in viscosity, and nonuniformity.
本発明のセルロースナノファイバー水分散体組成物は、増粘剤、ゲル化剤、保形安定化剤、弾力補強剤、テキスチャー改良剤、分散安定化剤、乳化安定剤として好適に使用される。また、食品、化粧料、医薬、医薬部外品、医療分野の末端製品として好ましく使用される。食品、化粧品としてより好ましく使用される。牛乳ゲル状飲食物、プリン、ゼリー、ココア飲料、洗口液としてさらに好ましく使用される。 The cellulose nanofiber aqueous dispersion composition of the present invention is suitably used as a thickener, gelling agent, shape retention stabilizer, elasticity reinforcing agent, texture improver, dispersion stabilizer, and emulsion stabilizer. Further, it is preferably used as a terminal product in food, cosmetics, medicine, quasi-drugs and medical fields. More preferably used as food and cosmetics. It is more preferably used as a milk gel food, pudding, jelly, cocoa beverage, or mouthwash.
本発明における前記末端製品中の脂肪酸エステル型構造非イオン界面活性剤（ａ）の含有量としては、製品安定性、使用される末端製品の特性や性状を損なわない範囲で、また、食品用途においては味や風味、食感などを損なわない範囲であれば特に限定されないが、腐敗防止の観点から１０〜１０,０００ｐｐｍが好ましく、１００〜７,０００ｐｐｍがより好ましく、２００〜４,０００ｐｐｍがさらに好ましい。但し、腐敗防止の目的外で所望される場合は、この限りではなく、食品用途では脂肪酸エステル型構造の非イオン界面活性剤、即ち、ショ糖脂肪酸エステル、糖アルコール脂肪酸エステル、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステルおよびソルビタン脂肪酸エステルからなる１種以上の同種の化合物を新たに添加して使用することは本発明では許容される。また、同様に化粧料、医薬、医薬部外品、医療分野においては、前記脂肪酸エステル型構造の非イオン界面活性剤に加えて、ポリオキシアルキレンアルキルエーテル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレン（硬化）ひまし油、ポリオキシエチレンポリオキシプロピレンプロックポリマー（プルロニック型界面活性剤）、ポリオキシエチレンアルキルアミンエーテル、アルキルポリグルコシド、ポリグリセリンアルキルエーテル、アルキルアルカノールアミド等の非イオン界面活性剤、更に、ポリオキシアルキレンアルキルエーテル構造を分子中に有するポリオキシエチレンアルキルエーテル硫酸エステル塩、ポリオキシエチレンアルキルエーテルリン酸エステル塩、ポリオキシエチレンアルキルエーテル酢酸塩、ポリオキシエチレンアルキルエーテルスルホコハク酸塩、更に、アルキルスルホン酸塩、アルキル硫酸塩、アルキルスルホコハク酸塩、高級脂肪酸塩等のアニオン界面活性剤、アルキルベタイン、脂肪酸アミドベタイン、アルキルアミンオキサイド、等の両性界面活性剤も新たに添加して使用することは本発明では許容される。また、カチオン界面活性剤も配合系の配合安定性を悪化させない範囲内で新たに添加して使用することができる。 The content of the fatty acid ester type structure nonionic surfactant (a) in the terminal product in the present invention is within a range that does not impair the product stability, characteristics and properties of the terminal product used, and in food applications. Is not particularly limited as long as it does not impair the taste, flavor, texture, etc., but is preferably 10 to 10,000 ppm, more preferably 100 to 7,000 ppm, and even more preferably 200 to 4,000 ppm from the viewpoint of preventing spoilage. . However, this is not limited to the case where it is desired for the purpose of preventing spoilage. For food use, it is a nonionic surfactant having a fatty acid ester structure, that is, sucrose fatty acid ester, sugar alcohol fatty acid ester, glycerin fatty acid ester, It is permissible in the present invention to newly add and use one or more of the same kind of compounds consisting of glycerin fatty acid ester and sorbitan fatty acid ester. Similarly, in the cosmetics, pharmaceuticals, quasi drugs, and medical fields, in addition to the fatty acid ester type nonionic surfactant, polyoxyalkylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan Nonionics such as fatty acid ester, polyoxyethylene (cured) castor oil, polyoxyethylene polyoxypropylene block polymer (pluronic surfactant), polyoxyethylene alkylamine ether, alkyl polyglucoside, polyglycerin alkyl ether, alkyl alkanolamide Surfactant, polyoxyethylene alkyl ether sulfate ester salt having polyoxyalkylene alkyl ether structure in the molecule, polyoxyethylene alkyl ether phosphate ester salt, Siethylene alkyl ether acetate, polyoxyethylene alkyl ether sulfosuccinate, anionic surfactant such as alkyl sulfonate, alkyl sulfate, alkyl sulfosuccinate, higher fatty acid salt, alkyl betaine, fatty acid amide betaine, alkyl It is permissible in the present invention to newly add and use amphoteric surfactants such as amine oxides. Also, a cationic surfactant can be newly added and used within a range not deteriorating the blending stability of the blending system.
本発明における前記末端製品中の（ｂ）成分の含有量としては、製品安定性、使用される末端製品の特性や性状を損なわない範囲であれば特に限定されないが、腐敗防止の観点から１０〜５,０００ｐｐｍが好ましく、１５〜３,０００ｐｐｍがより好ましく、２０〜１,０００ｐｐｍがさらに好ましい。但し、腐敗防止の目的外で所望される場合は、この限りではなく、四級アンモニウム塩型、ベンザルコニウム塩型およびピリジニウム塩型からなる群より選ばれる１種以上の構造を有するカチオン界面活性剤を新たに添加して使用することは本発明では許容される。また、ショ糖脂肪酸エステル、糖アルコール脂肪酸エステル、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステルおよびソルビタン脂肪酸エステル等の脂肪酸エステル型の非イオン界面活性剤、ポリオキシアルキレンアルキルエーテル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレン（硬化）ひまし油、ポリオキシエチレンポリオキシプロピレンプロックポリマー（プルロニック型界面活性剤）、ポリオキシエチレンアルキルアミンエーテル、アルキルポリグルコシド、ポリグリセリンアルキルエーテル、アルキルアルカノールアミド等の非イオン界面活性剤、等を新たに添加して使用することは本発明では許容される。また、配合系の配合安定性を悪化させない範囲内でアニオン界面活性剤や両性界面活性剤を新たに添加して使用することができる。 The content of the component (b) in the end product in the present invention is not particularly limited as long as it does not impair the product stability and the characteristics and properties of the end product used. 5,000 ppm is preferable, 15-3,000 ppm is more preferable, and 20-1,000 ppm is more preferable. However, this is not limited to the case where it is desired outside of the purpose of preventing corruption, and the cationic surface activity having one or more structures selected from the group consisting of a quaternary ammonium salt type, a benzalkonium salt type and a pyridinium salt type. In the present invention, it is acceptable to add a new agent for use. In addition, fatty acid ester type nonionic surfactants such as sucrose fatty acid ester, sugar alcohol fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester and sorbitan fatty acid ester, polyoxyalkylene alkyl ether, polyoxyethylene fatty acid ester, polyoxy Such as ethylene sorbitan fatty acid ester, polyoxyethylene (cured) castor oil, polyoxyethylene polyoxypropylene block polymer (pluronic surfactant), polyoxyethylene alkylamine ether, alkylpolyglucoside, polyglycerin alkyl ether, alkylalkanolamide, etc. In the present invention, it is acceptable to newly add a nonionic surfactant or the like. Moreover, an anionic surfactant and an amphoteric surfactant can be newly added and used within a range not deteriorating the blending stability of the blending system.
本発明のセルロースナノファイバー水分散体用腐敗防止剤は、下記（ａ）および／または（ｂ）を含有する。
（ａ）脂肪酸エステル型構造非イオン界面活性剤
（ｂ）四級アンモニウム塩型、ベンザルコニウム塩型およびピリジニウム塩型からなる群より選ばれる１種以上の構造を有するカチオン界面活性剤
The antiseptic agent for cellulose nanofiber aqueous dispersion of the present invention contains the following (a) and / or (b).
(A) Fatty acid ester type structure nonionic surfactant (b) Cationic surfactant having at least one structure selected from the group consisting of quaternary ammonium salt type, benzalkonium salt type and pyridinium salt type
本発明において腐敗防止剤とは、防腐作用、及び／又は、殺菌作用、及び／又は、抗菌作用、及び／又は、静菌作用を有する化学物質が、その単独、或いは複合的な作用をもってセルロースナノファイバー水分散体の腐敗を抑制する、或いは、セルロースナノファイバー水分散水体組成物の腐敗を抑制することを特徴とする薬剤である。 In the present invention, the anti-corruption agent refers to a chemical compound having antiseptic action and / or bactericidal action and / or antibacterial action and / or bacteriostatic action. It is an agent characterized by suppressing the decay of the fiber aqueous dispersion or suppressing the decay of the cellulose nanofiber aqueous dispersion composition.
本発明におけるセルロースナノファイバーは、数平均繊維径が２ｎｍ以上２００ｎｍ以下の状態まで解繊されていることが好ましい。 The cellulose nanofibers in the present invention are preferably defibrated to a state where the number average fiber diameter is 2 nm or more and 200 nm or less.
本発明におけるセルロースとしては、特に限定されないが、例えば、天然セルロースが用いることができる。前記天然セルロースとしては、例えば、植物，動物，バクテリア産生ゲル等のセルロースの生合成系から単離した精製セルロースである。例えば、針葉樹系パルプ、広葉樹系パルプ、コットンリンター、コットンリント等の綿系パルプ、麦わらパルプ、バガスパルプ等の非木材系パルプ、バクテリアセルロース（ＢＣ）、ホヤから単離されるセルロース、海草から単離されるセルロース等が挙げられる。これらは単独でもしくは二種以上併せて用いることができる。これらのなかでも、針葉樹系パルプ、広葉樹系パルプ、コットンリンター、コットンリント等の綿系パルプ、麦わらパルプ，バガスパルプ等の非木材系パルプが好ましい。上記天然セルロースは、セルロースナノファイバー水分散体を調製する目的において、天然由来でありながら、その成分組成が比較的安定している点、また、原料として商業生産品が入手可能である点、更に、本発明の用途分野において、商品価値の低下や物性の低下を生じる可能性のある成分や不純物を除去した高純度品が入手可能性である点から好ましい。 Although it does not specifically limit as a cellulose in this invention, For example, a natural cellulose can be used. Examples of the natural cellulose include purified cellulose isolated from cellulose biosynthetic systems such as plants, animals, and bacteria-producing gels. For example, cotton pulp such as softwood pulp, hardwood pulp, cotton linter and cotton lint, non-wood pulp such as straw pulp and bagasse pulp, bacterial cellulose (BC), cellulose isolated from sea squirt, and seaweed A cellulose etc. are mentioned. These can be used alone or in combination of two or more. Among these, soft wood pulp, hardwood pulp, cotton pulp such as cotton linter and cotton lint, and non-wood pulp such as straw pulp and bagasse pulp are preferable. For the purpose of preparing an aqueous dispersion of cellulose nanofiber, the natural cellulose is derived from nature, but its component composition is relatively stable, and commercial products are available as raw materials. In the field of application of the present invention, a high-purity product from which components or impurities that may cause a drop in commercial value or physical properties is removed is preferable from the viewpoint of availability.
以下、実施例及び比較例に基づいて、本発明について詳細に説明するが、本発明はもちろんこれらに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, of course this invention is not limited to these.
（実施例A）
まず、針葉樹パルプを乾燥重量２００ｇに、水１５L、臭化ナトリウム２５ｇ、ＴＥＭＰＯ ２．５ｇを加え、充分撹拌して分散させた後、１３重量％の次亜塩素酸ナトリウム水溶液（共酸化剤）を、次亜塩素酸ナトリウムとして６．５ｍｍｏｌ／ｇとなるように加え、反応を開始した。反応の進行に伴いｐＨが低下するため、ｐＨを１０〜１１に保持するように０．５Ｎ水酸化ナトリウム水溶液を滴下しながら、ｐＨの変化が見られなくなるまで反応させた。反応終了後、０．１Ｎ塩酸を添加してｐＨを７．０に調整し、ろ過と水洗を繰り返して精製し、カルボキシル基量 １．８３ｍｍｏｌ／ｇである繊維表面が酸化されたセルロース繊維を得た。
次いで、上記セルロース繊維を、固形分濃度が１重量％となるように純水で希釈し、超高圧ホモジナイザーにより、液温２０℃から１４０ＭＰａの圧力で３回処理して、最大繊維径１０ｎｍ、数平均繊維径６ｎｍ、固形分１重量％のセルロースナノファイバー水分散液（A）を調製した。
(Example A)
First, add 15 L of water, 25 g of sodium bromide, and 2.5 g of TEMPO to 200 g of dry weight of softwood pulp, disperse it with sufficient stirring, and then add 13 wt% aqueous sodium hypochlorite solution (co-oxidant). Then, sodium hypochlorite was added to 6.5 mmol / g to initiate the reaction. Since the pH decreased with the progress of the reaction, the reaction was continued until no change in pH was observed while adding a 0.5N aqueous sodium hydroxide solution dropwise so that the pH was maintained at 10-11. After completion of the reaction, 0.1N hydrochloric acid was added to adjust the pH to 7.0, and filtration and washing were repeated and purified to obtain a cellulose fiber having an oxidized fiber surface with a carboxyl group amount of 1.83 mmol / g. It was.
Next, the cellulose fiber is diluted with pure water so that the solid content concentration becomes 1% by weight, and is treated three times with a super high pressure homogenizer at a liquid temperature of 20 ° C. to 140 MPa, and the maximum fiber diameter is 10 nm. A cellulose nanofiber aqueous dispersion (A) having an average fiber diameter of 6 nm and a solid content of 1% by weight was prepared.
なお、前記カルボキシル基量は以下の操作にて測定を行った。セルロースナノファイバー重量として０．２５ｇ相当のセルロースナノファイバー水分散体を秤取し、０．１Ｍの塩酸水溶液によってｐＨを約２．５とした後、０．０５Ｍの水酸化ナトリウム水溶液を滴下して、電気伝導度測定を行った。測定はｐＨが約１１になるまで続けた。電気伝導度の変化が緩やかな弱酸の中和段階において消費された水酸化ナトリウム量（Ｖ）から、下式にてカルボキシル基量を求めた。
カルボキシル基量 [mmol/g]＝Ｖ[ml]×〔０．０５／セルロース重量〕
The amount of the carboxyl group was measured by the following operation. Cellulose nanofiber aqueous dispersion equivalent to 0.25 g as the weight of cellulose nanofiber was weighed and adjusted to pH about 2.5 with 0.1 M hydrochloric acid aqueous solution, and then 0.05 M sodium hydroxide aqueous solution was added dropwise. The electrical conductivity was measured. The measurement was continued until the pH was about 11. From the amount (V) of sodium hydroxide consumed in the neutralization step of the weak acid where the change in electrical conductivity is gradual, the amount of carboxyl groups was determined by the following equation.
Amount of carboxyl group [mmol / g] = V [ml] × [0.05 / cellulose weight]
（実施例B）
撹拌機に広葉樹パルプを乾燥重量で２００ｇ、水酸化ナトリウムを８８ｇ加え、パルプ固形濃度が１５％になるように水を加えた。その後、３０℃で３０分攪拌した後に７０℃まで昇温し、モノクロロ酢酸ナトリウムを１１７ｇ（有効成分換算）添加した。１時間反応した後に、反応物を取り出して中和、洗浄して、グルコース単位当たりのカルボキシメチル置換度０．０５のアニオン変性されたセルロースを得た。その後、アニオン変性したパルプを固形濃度１％とし、超高圧ホモジナイザーにより、液温２０℃から冷却操作を伴いながら１４０ＭＰａの圧力で５回処理して固形分１重量％のセルロースナノファイバー水分散液（B-1）を調製した。
(Example B)
200 g by dry weight of hardwood pulp and 88 g of sodium hydroxide were added to the stirrer, and water was added so that the pulp solid concentration was 15%. Then, after stirring for 30 minutes at 30 ° C., the temperature was raised to 70 ° C., and 117 g of sodium monochloroacetate (in terms of active ingredient) was added. After reacting for 1 hour, the reaction product was taken out, neutralized, and washed to obtain anion-modified cellulose having a carboxymethyl substitution degree of 0.05 per glucose unit. Thereafter, the anion-modified pulp was adjusted to a solid concentration of 1%, and treated with an ultra-high pressure homogenizer five times at a pressure of 140 MPa while being cooled from a liquid temperature of 20 ° C., and a cellulose nanofiber aqueous dispersion having a solid content of 1% by weight ( B-1) was prepared.
また、水酸化ナトリウムを２６４ｇ、モノクロロ酢酸ナトリウムを３５１ｇ（有効成分換算）に変更した以外、前記操作と同様にしてセルロースナノファイバー水分散液（B-2）を得た。なお、得られたセルロースのグルコース単位当たりのカルボキシメチル置換度は０．１５であった。 Moreover, the cellulose nanofiber aqueous dispersion (B-2) was obtained like the said operation except having changed into sodium hydroxide 264g and sodium monochloroacetate 351g (active ingredient conversion). In addition, the carboxymethyl substitution degree per glucose unit of the obtained cellulose was 0.15.
また、水酸化ナトリウムを440ｇ、モノクロロ酢酸ナトリウムを585ｇ（有効成分換算）に変更した以外、前記操作と同様にしてセルロースナノファイバー水分散液（B-3）を得た。なお、得られたセルロースのグルコース単位当たりのカルボキシメチル置換度は０．25であった。 Further, a cellulose nanofiber aqueous dispersion (B-3) was obtained in the same manner as in the above operation except that sodium hydroxide was changed to 440 g and sodium monochloroacetate was changed to 585 g (converted to active ingredient). In addition, the carboxymethyl substitution degree per glucose unit of the obtained cellulose was 0.25.
なお、前記水分散体（B-1）〜（B-3）について、グルコース単位当たりのカルボキシメチル置換度は、実施例１に記載の方法でカルボキシル基量を測定し、更に下式を用いて算出した。ここで言う置換度とは、無水グルコース単位１モル当たりの置換基のモル数の平均値を示す。
カルボキシメチル置換度＝（１６２×Ｃ）／（１−５８×Ｃ）
Ｃ：カルボキシル基量 ［mol/g］
In addition, about the said water dispersion (B-1)-(B-3), the carboxymethyl substitution degree per glucose unit measures the amount of carboxyl groups by the method as described in Example 1, and also uses the following Formula. Calculated. The degree of substitution here refers to the average value of the number of moles of substituents per mole of anhydroglucose unit.
Carboxymethyl substitution degree = (162 × C) / (1-58 × C)
C: Amount of carboxyl group [mol / g]
≪粘度測定≫
実施例、並びに比較例で得られた調製直後のセルロースナノファイバー水分散体（固形分１重量％）を２００ｍのマヨネーズ瓶に移し、脱気後、２５℃で２４時間静置したサンプルについて、ＢＨ型粘度計（８００００ｍＰａ・ｓ未満：ローターＮｏ．４、回転数２．５ｒｐｍ、３分、２５℃、８００００ｍＰａ・ｓ以上：ローターＮｏ．５、回転数２．５ｒｐｍ、３分、２５℃）を用いて粘度を測定した。
≪Measurement of viscosity≫
About the sample which transferred the cellulose nanofiber aqueous dispersion (1 weight% of solid content) immediately after preparation obtained in the Example and the comparative example to a 200-m mayonnaise bottle, and left still at 25 degreeC for 24 hours about BH. Using a viscometer (less than 80000 mPa · s: rotor No. 4, rotation speed 2.5 rpm, 3 minutes, 25 ° C., 80000 mPa · s or more: rotor No. 5, rotation speed 2.5 rpm, 3 minutes, 25 ° C.) The viscosity was measured.
≪一般細菌数試験法≫ ※JP 2009-144091 A参照
一般細菌数については以下の方法に従って測定した。
１．一般細菌用寒天培地（標準寒天培地）を下記手順により調製した。
（１）１０００ｍＬビーカーに標準寒天培地２３．５ｇを取り純水１０００ｍＬを加え撹拌溶解し、更に、ビーカーを熱湯に漬け加熱撹拌溶解した。
（２）５００ｍＬ三角フラスコ２個に分取した後、フラスコにシリコン栓で栓をし、更にアルミホイルで包み込み、滅菌用カゴに入れオートクレーブで１２１℃×２０分間滅菌した。
（３）オートクレーブ釜内圧が低下後、脱気バルプを開け作業当日まで放置した。
（４）作業当日に脱気バルプを閉め、１２１℃×５分間滅菌した。
（５）釜内圧が低下後、脱気バルプを開け、フラスコを取り出し、予め用意した５０℃湯バスに浸して保温した。
２．生理食塩水を下記手順により調製した。
（１）食塩を８．５ｇ取り、１０００ｇになるように純水を加え撹拌、溶解して０．８５重量％の生理食塩水を調整した。
（２）５０ｍＬメスシリンダーを用いて、５０ｍＬを１００ｍＬ三角フラスコに取り、シリコン栓で栓をし、アルミホイルで包み込み、オートクレーブで１２１℃×２０分間滅菌した。
（３）オートクレーブ釜内圧が低下後、脱気バルプを開けた。
３．サンプル検体調製は下記手順により行った。
（１）予め無菌ブース内で紫外線殺菌した上皿天秤、分銅を用意した。
（２）滅菌した１００ｍＬサンプル瓶に滅菌済みスパチュラで約２０ｇのサンプリングを分注した。
（３）殺菌した１００ｍＬ三角フラスコと栓、スパチュラ、殺菌済み０．８５％生理食塩水（１００ｍＬフラスコ）、供試サンプルを無菌ブース内に準備した。
（４）上皿天秤で殺菌済み１００ｍＬ三角フラスコにサンプル０．５ｇ（菌数によっては適宜希釈して供試）秤取した。
（５）サンプルを含む１００ｍＬ三角フラスコに滅菌済み０．８５％生理食塩水を加え、手で振り、振とう機に１時間かけて供試検体を調製した。
（６）滅菌済みシャーレ３枚に滅菌済み１０ｍＬメスピペットで供試検体から各１ｍＬずつ検体を採取した。
４．培養、及び、菌数測定
（１）３枚のシャーレに予め溶解殺菌、保温した標準寒天培地を約２０ｍＬずつ素早く流し込み、サンプルと培地とを混合した。
（２）寒天培地が固まるまで静置した。
（３）シャーレを倒置して、３７℃のふ卵器で４８時間±３時間培養後、コロニーをカウントした。
（４）菌数／ｇは、（３枚のシャーレに発生した菌数／３）×１００にて算出した。
<General Bacteria Count Test Method> * See JP 2009-144091 A General bacterial count was measured according to the following method.
1. A general agar medium (standard agar medium) was prepared by the following procedure.
(1) 23.5 g of standard agar medium was taken into a 1000 mL beaker, 1000 mL of pure water was added and dissolved by stirring, and the beaker was immersed in hot water and dissolved by stirring.
(2) After separating into two 500 mL Erlenmeyer flasks, the flask was stoppered with a silicon stopper, wrapped in aluminum foil, placed in a sterilization basket, and sterilized in an autoclave at 121 ° C. for 20 minutes.
(3) After the pressure inside the autoclave decreased, the deaeration valve was opened and left until the day of the work.
(4) The degassing valve was closed on the day of work and sterilized at 121 ° C. for 5 minutes.
(5) After the pressure in the kettle decreased, the deaeration valve was opened, the flask was taken out, and kept warm by being immersed in a 50 ° C. hot water bath prepared in advance.
2. Saline was prepared by the following procedure.
(1) Take 8.5 g of salt, add pure water to 1000 g, stir and dissolve to prepare 0.85 wt% physiological saline.
(2) Using a 50 mL graduated cylinder, 50 mL was taken into a 100 mL Erlenmeyer flask, sealed with a silicon stopper, wrapped in aluminum foil, and sterilized in an autoclave at 121 ° C. for 20 minutes.
(3) The deaeration valve was opened after the internal pressure of the autoclave decreased.
3. Sample specimen preparation was performed according to the following procedure.
(1) An upper pan balance and a weight that were previously sterilized with ultraviolet rays in a sterile booth were prepared.
(2) About 20 g of sampling was dispensed with a sterilized spatula into a sterilized 100 mL sample bottle.
(3) A sterilized 100 mL Erlenmeyer flask and stopper, spatula, sterilized 0.85% physiological saline (100 mL flask), and a test sample were prepared in a sterile booth.
(4) A 0.5 g sample (tested by appropriately diluting depending on the number of bacteria) was weighed in a 100 mL Erlenmeyer flask sterilized with an upper pan balance.
(5) Sterilized 0.85% physiological saline was added to a 100 mL Erlenmeyer flask containing the sample, shaken by hand, and a test specimen was prepared for 1 hour on a shaker.
(6) 1 mL of each sample was collected from the test sample with a sterilized 10 mL measuring pipette on three petri dishes.
4). Cultivation and count of bacteria (1) About 20 mL of standard agar medium previously dissolved and sterilized and kept warm was poured into three petri dishes, and the sample and the medium were mixed.
(2) The mixture was allowed to stand until the agar medium hardened.
(3) The petri dish was inverted and cultured in a 37 ° C. incubator for 48 hours ± 3 hours, and colonies were counted.
(4) The number of bacteria / g was calculated by (number of bacteria generated in 3 petri dishes / 3) × 100.
≪臭気測定≫
臭気（異臭の有無）については、以下の方法に従って判定を行った。
社内パネラー５人（パネラーA〜E： ３０代男性、３０代男性、２０代男性、４０代女性、２０代女性）によって、各サンプルについて異臭の有無についてサンプル名を隠したブラインド評価を実施して臭気の判定を行った。
［判定］
３ … 鼻をつく刺激臭あり
２ … 不快臭あり
１ … わずかな異臭或いは不快臭あり
０ … 不快臭を感じない
≪Odor measurement≫
Odor (presence / absence of off-flavor) was determined according to the following method.
In-house panelists (panelists A to E: Males in their 30s, males in their 30s, males in their 20s, females in their 40s, females in their 20s) Odor was determined.
[Judgment]
3 ... Stimulating odor with nose 2 ... Unpleasant odor 1 ... Slight odor or unpleasant odor 0 ... No unpleasant odor
更に、実施例、並びに比較例で得られた調製直後のセルロースナノファイバー水分散体（固形分１重量％）を２００ｍのマヨネーズ瓶に取り分け、フタをしてそれぞれ２５℃、４０℃にて３０日間放置した後、各サンプルについて、上記操作に従って同様にセルロースナノファイバー水分散体の粘度測定、一般細菌数測定、臭気判定を行った。それら評価結果を以下の表1に示す。 Furthermore, the cellulose nanofiber aqueous dispersions (1% by weight solid content) immediately after preparation obtained in Examples and Comparative Examples were separated into 200 m mayonnaise bottles, capped, and 30 days at 25 ° C. and 40 ° C., respectively. After leaving, the viscosity of the cellulose nanofiber aqueous dispersion, the number of general bacteria, and the odor determination were performed on each sample in the same manner as described above. The evaluation results are shown in Table 1 below.
表1に記載の結果から、セルロースナノファイバー水分散体の調製工程で殺菌や菌数低減の手段を講じず、また、腐敗防止剤を意図的添加しない場合には、常温から夏期気温程度の温度条件下で長期間放置すると一般細菌の大幅な増加とそれに伴い、セルロースナノファイバー水分散体の臭気の悪化が著しいことが分かる。水分散体粘度は菌数増加や臭気の悪化と連動して水分散体直後の粘度に比較して低下傾向にあることが分かる。
また、水分散体（A）と水分散体（B-1）〜（B-3）の比較では、相対的に水分散体（A）の方が、菌数、並びに臭気の悪化の点でその腐敗が抑制されている傾向が読み取れる。これはセルロースナノファイバー水分散体調製過程における使用原料種、並びに、ｐＨ変動幅などによる両者の差異が影響しているものと思われる。
From the results shown in Table 1, the temperature of the room temperature to the summer temperature can be obtained if no measures for sterilization or bacterial count reduction are taken in the preparation process of the cellulose nanofiber aqueous dispersion and no anti-corrosive agent is added. It can be seen that, when left under conditions for a long period of time, the number of general bacteria is greatly increased, and the odor of the cellulose nanofiber aqueous dispersion is greatly deteriorated. It can be seen that the viscosity of the aqueous dispersion tends to be lower than the viscosity immediately after the aqueous dispersion in conjunction with the increase in the number of bacteria and the deterioration of odor.
Moreover, in the comparison of the water dispersion (A) and the water dispersions (B-1) to (B-3), the water dispersion (A) is relatively more in terms of the number of bacteria and the deterioration of odor. The tendency that the corruption is suppressed can be read. This is considered to be due to the difference between the raw materials used in the process of preparing the cellulose nanofiber aqueous dispersion and the pH fluctuation range.
次に、前記方法によって調製したセルロースナノファイバー水分散体（A）並びに、（B-1）〜（B-3）について、表２および３に示す配合処方にて、本発明の腐敗防止剤を水、或いは適宜温水を選択して、溶解、或いは均一分散させて所定量を配合してセルロースナノファイバー水分散体組成物を調製し、前記表１に準じて腐敗防止効果を評価した。それら評価結果を以下の表４、５、６に示す。
なお、表２および３の配合成分において、特に特記していない限りは、個々成分の固形分（有効成分）濃度は１００％である。また、固形分濃度は重量％である。また、個々の配合部数は有姿での重量部数である。
Next, for the cellulose nanofiber aqueous dispersion (A) prepared by the above method and (B-1) to (B-3), the anti-corruption agent of the present invention was used in the formulation shown in Tables 2 and 3. Water or appropriate warm water was selected and dissolved or uniformly dispersed, and a predetermined amount was blended to prepare a cellulose nanofiber aqueous dispersion composition. The anti-corruption effect was evaluated according to Table 1 above. The evaluation results are shown in Tables 4, 5, and 6 below.
In the blending components in Tables 2 and 3, unless otherwise specified, the solid content (active ingredient) concentration of each component is 100%. Moreover, solid content concentration is weight%. Moreover, each compounding part number is a weight part number with a solid.
前記、セルロースナノファイバー水分散体（A）並びに、（B-1）〜（B-3）に対する本発明で限定した腐敗防止剤の添加効果について、表４において、非イオン系、カチオン系腐敗防止剤の添加系は、ともにその添加効果は明白であり、腐敗防止剤の無添加系とは有意差が認められる（実施例１、２）。
また、表５において、腐敗の進行懸念が高い水分散体（B-1）の系において、本発明で限定した腐敗防止剤の添加効果は明白である。また、水分散体調製直後と25℃、30日保管後の粘度低下幅について、本発明で限定した腐敗防止剤の添加により、その粘度低下幅が縮小していることが分かる（実施例３、４、１３）。
更に、表６において、その他の系の評価結果を示しているが、本発明で限定した腐敗防止剤の添加効果は明白であり（実施例５〜１６）、本発明で限定した条件を外れた場合には、25℃、30日保管後の品質悪化が明らかである（比較例１〜２）。
Regarding the effect of addition of the antiseptic agent limited in the present invention to the cellulose nanofiber aqueous dispersion (A) and (B-1) to (B-3), in Table 4, nonionic and cationic antiseptics Both the additive-added systems have a clear effect of addition, and a significant difference is observed from the additive-free system of the antiseptic agent (Examples 1 and 2).
Further, in Table 5, the effect of adding the anti-corruption agent limited in the present invention is obvious in the system of the aqueous dispersion (B-1) in which the concern about the progress of rotting is high. Moreover, it can be seen that the viscosity reduction range immediately after the preparation of the aqueous dispersion and after the storage at 25 ° C. for 30 days is reduced by the addition of the antiseptic agent limited in the present invention (Example 3, 4, 13).
Furthermore, in Table 6, although the evaluation result of the other system is shown, the addition effect of the anti-corruption agent limited in the present invention is clear (Examples 5 to 16), and the conditions limited in the present invention were excluded. In this case, quality deterioration after storage at 25 ° C. for 30 days is apparent (Comparative Examples 1-2).
［応用例］
次に、腐敗防止剤を含むセルロースナノファイバー水分散体組成物を用いて以下の応用試験を実施した。該応用試験に際して、実施例Bに準じてカルボキシメチル置換度０．０５、固形分濃度３％のセルロースナノファイバー水分散液（B-4）を調製し、以下の表７に記載の配合にて本発明の腐敗防止剤を溶解、均一分散させて実施例Ｘ、Ｙを得て、更に該水分散体組成物を25℃で３０日間恒温保管してセルロースナノファイバー水分散液（W-30D）、（Ｘ-30Ｄ）、（Ｙ-30Ｄ）、（Ｚ-30Ｄ）を得た。
なお、セルロースナノファイバー水分散液（W-30D）、（Ｘ-30Ｄ）、（Ｙ-30Ｄ）、（Ｚ-30Ｄ）について、社内パネラー５人による臭気評価を以下表８に示した。
以下表７の配合成分において、特に特記していない限りは、個々成分の固形分（有効成分）濃度は１００％である。また、固形分濃度は重量％である。また、個々の配合部数は有姿での重量部数である。
[Application example]
Next, the following application test was implemented using the cellulose nanofiber aqueous dispersion composition containing an anti-corruption agent. In the application test, a cellulose nanofiber aqueous dispersion (B-4) having a carboxymethyl substitution degree of 0.05 and a solid content concentration of 3% was prepared according to Example B, and the formulation shown in Table 7 below was used. Examples X and Y were obtained by dissolving and uniformly dispersing the anti-corrosion agent of the present invention, and the aqueous dispersion composition was stored at 25 ° C. for 30 days at a constant temperature for cellulose nanofiber aqueous dispersion (W-30D). , (X-30D), (Y-30D), (Z-30D) were obtained.
Table 8 below shows the odor evaluation by in-house panelists for cellulose nanofiber aqueous dispersions (W-30D), (X-30D), (Y-30D), and (Z-30D).
In the following blending components in Table 7, unless otherwise specified, the solid content (active ingredient) concentration of each component is 100%. Moreover, solid content concentration is weight%. Moreover, each compounding part number is a weight part number with a solid.
なお、以下の応用処方において、各配合成分は特に特記していない限りは、個々成分の固形分（有効成分）濃度は１００％であり、固形分濃度は重量％である。また、個々成分の配合部数は有姿での重量部数である。 In the following application formulas, unless otherwise specified, each component has a solid content (active ingredient) concentration of 100% and a solid content concentration of% by weight. Moreover, the number of blended parts of each component is the number of parts by weight in solid form.
＜応用例（１） 牛乳ゲル状飲食物＞
水性飲食物として、前記操作で得たセルロースナノファイバー水分散体組成物（Ｘ-30Ｄ）、（Ｙ-30Ｄ）、（Ｚ-30Ｄ）を用いて、下記処方にて配合して、高圧ホモジナイザー（４４ＭＰａ）にて３回パスさせても目的の牛乳ゲル状飲食物を得た。この調製物について、目視判断にてゲル化の有無、社内パネラー５人（パネラーＦ〜Ｊ： ３０代男性、２０代男性、３０代女性、２０代女性、20代女性）にて、以下評価基準に従って風香味の評価を行った。評価結果は表８の通り。
<Application example (1) Milk gel food and drink>
As aqueous foods and drinks, cellulose nanofiber aqueous dispersion compositions (X-30D), (Y-30D), and (Z-30D) obtained by the above-described operations were blended according to the following formulation, and a high-pressure homogenizer ( 44 MPa), the desired milk gel food / drink was obtained even after 3 passes. With regard to this preparation, the presence or absence of gelation by visual judgment, the following evaluation criteria in 5 in-house panelists (panelists FJ: 30s male, 20s male, 30s female, 20s female, 20s female) The flavor was evaluated according to the above. The evaluation results are shown in Table 8.
［風香味］
３ … 商品価値がない（鼻をつく刺激臭あり、食すには適さない）
２ … 風香味が悪い（異臭、不快臭あり、味に違和感がある）
１ … わずかな異臭或いは不快臭あり、味に僅かに違和感がある
０ … 風香味が良い（不快臭を感じない、味わいがよい）
[Flavored]
3 ... Not worth the product (no irritating odor that makes you nose, not suitable for eating)
2 ... Bad flavor (there is a strange odor, an unpleasant odor, and the taste is uncomfortable)
1… Slight off-flavor or unpleasant odor, slightly uncomfortable taste 0… Good flavor (no unpleasant odor, good taste)
表１０より、実施例１７、１８は、ゲル形成能、風香味ともに良好な結果であった。 From Table 10, Examples 17 and 18 were good results in both gel forming ability and flavor.
＜応用例（２） プリン＞
保形性を必要とする加工食品として、前記操作で得たセルロースナノファイバー水分散体組成物（Ｘ-30Ｄ）、（Ｙ-30Ｄ）、（Ｚ-30Ｄ）を用いて、下記処方に従って、水にセルロースナノファイバー水分散体に加え、次いで、生クリームを加えて攪拌しながら、プリンフレーバー以外の原料を粉体混合物として添加し、８０℃１０分間、攪拌溶解した後、プリンフレーバーを添加し、容器充填後、冷却してプリンを調製した。その後、容器から取り出した際の保形性（（良）○〜（悪）×）、食感（社内パネラーによる評価 、（良）○〜（悪）×）、風香味を評価した結果を表１２に示した。なお、風香味の評価は、応用例１記載の方法にて実施した。
<Application example (2) Pudding>
Using the cellulose nanofiber aqueous dispersion composition (X-30D), (Y-30D), (Z-30D) obtained by the above operation as a processed food requiring shape retention, In addition to the cellulose nanofiber aqueous dispersion, the raw material other than pudding flavor was added as a powder mixture while stirring with the addition of fresh cream. After stirring and dissolving at 80 ° C. for 10 minutes, the pudding flavor was added, After filling the container, the pudding was prepared by cooling. After that, when the shape is taken out from the container ((good) ○ ~ (bad) ×), texture (evaluation by in-house panelists, (good) ○ ~ (bad) ×), the evaluation results of flavor This is shown in FIG. The evaluation of the flavor was carried out by the method described in Application Example 1.
表１２より、汎用される水溶性増粘剤（カルボキシメチルセルロースＮａ塩）の代わりにセルロースナノファイバー水分散体を用いた実施例１９、２０は、保形性、食感、風香味ともに良好な結果であった。 From Table 12, Examples 19 and 20 using a cellulose nanofiber aqueous dispersion instead of a commonly used water-soluble thickener (carboxymethylcellulose Na salt) showed good results in shape retention, texture and flavor. Met.
＜応用例（３） ゼリー＞
保形性を必要とする加工食品として、前記操作で得たセルロースナノファイバー水分散体組成物（Ｘ-30Ｄ）、（Ｙ-30Ｄ）、（Ｚ-30Ｄ）を用いて、下記処方に従って、水にセルロースナノファイバー水分散体を加え、攪拌しながら、砂糖、クエン酸三ナトリウム及び乳酸カルシウムの粉体混合物を加え、８０℃１０分間、加熱攪拌、溶解後、クエン酸（無水）を添加し、攪拌混合、全量を水にて調整し、容器充填し、８５℃３０分間殺菌して、水冷固化し、ゼリーを調製した。その後、容器から取り出した際の保形性（（良）○〜（悪）×）、食感（社内パネラーによる評価 、（良）○〜（悪）×）、風香味を評価した結果を表１４に示した。なお、風香味の評価は、応用例１記載の方法にて実施した。
<Application example (3) Jelly>
Using the cellulose nanofiber aqueous dispersion composition (X-30D), (Y-30D), (Z-30D) obtained by the above operation as a processed food requiring shape retention, Add the cellulose nanofiber aqueous dispersion to the mixture, add a powder mixture of sugar, trisodium citrate and calcium lactate with stirring, heat and stir at 80 ° C. for 10 minutes, add citric acid (anhydrous), Stir and mix, adjust the whole amount with water, fill the container, sterilize at 85 ° C. for 30 minutes, solidify with water, and prepare a jelly. After that, when the shape is taken out from the container ((good) ○ ~ (bad) ×), texture (evaluation by in-house panelists, (good) ○ ~ (bad) ×), the evaluation results of flavor 14 shows. The evaluation of the flavor was carried out by the method described in Application Example 1.
表１４より、汎用される水溶性増粘剤（カルボキシメチルセルロースＮａ塩）の代わりにセルロースナノファイバー水分散体を用いた実施例２１、２２は、保形性、食感、風香味ともに良好な結果であった。比較例５は保形性、食感、風香味において何れも相対的に劣る結果であった。 From Table 14, Examples 21 and 22 using a cellulose nanofiber aqueous dispersion instead of a commonly used water-soluble thickener (carboxymethylcellulose Na salt) showed good results in shape retention, texture and flavor. Met. The comparative example 5 was a result in which all are relatively inferior in shape retention property, food texture, and flavor.
＜応用例（４） ココア飲料＞
分散安定性を必要とする飲料組成物として、前記操作で得たセルロースナノファイバー水分散体組成物（Ｘ-30Ｄ）、（Ｙ-30Ｄ）、（Ｚ-30Ｄ）を用いて、下記処方に従って、水にセルロースナノファイバー水分散体を加え、更に攪拌しながら、分散安定化剤、砂糖、異性化液糖、粉乳、生乳を加え、次いで、７０℃に加温した。この分散液にココアパウダーを加えながら、ホモミキサーにて撹拌混合した。これを一次圧１５ＭＰａ、二次圧５ＭＰａの処理条件にてモジナイザーで均質化し、容器に充填後、１２０℃、２０分間オートクレーブにより殺菌を行ない、ココア飲料を調製した。その後、調製したココア飲料を５℃及び５５℃恒温槽にて１ケ月保存した時のオイルリングとココア粉末の沈殿の様子を観察した。その結果を表１６に示した。なお、風香味の評価は、応用例１記載の方法にて実施した。
オイルリング、ココア粉末の沈殿の様態評価は、以下の評価基準に従って実施した。
<Application example (4) Cocoa beverage>
Using the cellulose nanofiber aqueous dispersion composition (X-30D), (Y-30D), (Z-30D) obtained by the above operation as a beverage composition that requires dispersion stability, A cellulose nanofiber aqueous dispersion was added to water, and further, a dispersion stabilizer, sugar, isomerized liquid sugar, powdered milk and raw milk were added with stirring, and then heated to 70 ° C. While adding cocoa powder to this dispersion, the mixture was stirred and mixed with a homomixer. This was homogenized with a modifier under the treatment conditions of a primary pressure of 15 MPa and a secondary pressure of 5 MPa, filled in a container, and then sterilized by autoclaving at 120 ° C. for 20 minutes to prepare a cocoa beverage. Then, the state of precipitation of the oil ring and the cocoa powder when the prepared cocoa beverage was stored in a thermostatic bath at 5 ° C. and 55 ° C. for one month was observed. The results are shown in Table 16. The evaluation of the flavor was carried out by the method described in Application Example 1.
Evaluation of the state of oil ring and cocoa powder precipitation was carried out according to the following evaluation criteria.
［オイリング］
○ … 軽い振とうで容易に再分散する。
× … 長時間強く振とうしないと再分散しない。
［ココア粉末の沈殿］
○ … 軽い振とうで容易に再分散する。
× … 長時間強く振とうしないと再分散しない。
[Euling]
○… Re-dispersed easily with light shaking.
×… Does not re-disperse unless shaken strongly for a long time.
[Precipitation of cocoa powder]
○… Re-dispersed easily with light shaking.
×… Does not re-disperse unless shaken strongly for a long time.
（＊２）旭化成（株）製アビセルＲＣ-３０
表１６より、実施例２３、２４は、オイリング、ココア粉末の再分散、風香味ともに良好な結果であった。比較例６はオイリング、ココア粉末の再分散、風香味において何れも相対的に劣る結果であった。 From Table 16, Examples 23 and 24 were good results in oiling, re-dispersion of cocoa powder, and flavor. In Comparative Example 6, the results were relatively inferior in oiling, re-dispersion of cocoa powder, and flavor.
＜応用例（５） 洗口液＞
カチオン系腐敗防止剤を含有するセルロースナノファイバー水分散体組成物の応用例として、前記操作で得たセルロースナノファイバー水分散体組成物（W-30Ｄ）、（Ｚ-30Ｄ）を用いて、下記処方に従って、各成分を順に加え、攪拌しながら、均一化して洗口液を調製した。該洗口液について、唾液中のＳ．ｍｕｔａｎｓに対する抗菌持続性評価試験、並びに、洗口液を吐き出した後の後味について評価し、その結果を表１８に示した。
なお、抗菌持続性評価試験、並びに、洗口液を吐き出した後の後味の評価は、社内パネラー５人（パネラーＦ〜Ｊ： ３０代男性、２０代男性、３０代女性、２０代女性、20代女性）にて、以下評価基準にて評価実施した。
<Application example (5) Mouthwash>
As an application example of the cellulose nanofiber aqueous dispersion composition containing a cationic anticorrosive agent, the cellulose nanofiber aqueous dispersion composition (W-30D) and (Z-30D) obtained by the above-described operation are used. According to the prescription, each component was added in order, and uniformed with stirring to prepare a mouthwash. About the mouthwash, S. The antibacterial sustainability evaluation test against mutans and the aftertaste after spouting the mouthwash were evaluated, and the results are shown in Table 18.
In addition, the antibacterial durability evaluation test and the evaluation of aftertaste after spitting out the mouthwash were performed by 5 in-house panelists (panelists FJ: 30s male, 20s male, 30s female, 20s female, 20 Evaluation was performed according to the following evaluation criteria.
≪抗菌持続性評価試験≫
実施例および比較例で得られた洗口液を対象として、唾液中のＳ．ｍｕｔａｎｓの菌数を測定する検査キット「Ｄｅｎｔｏｃｕｌｔ ＳＭ（株式会社オーラルケア製）」を用いて、社内パネラー５名による抗菌持続性評価試験を行った。試験方法としては、洗口液ですすぐ直前（イニシャル）、洗口液１０ｍＬで２０秒間口腔内をすすいで吐き出した直後と３時間後にそれぞれ口腔中の唾液を採取して、コロニーの有無を下記の基準に従い、３段階で評価し、その平均値を算出した。
［判定基準］
３ … 非常に多くの菌が存在する（１０6／ｍｌ以上）
２ … 菌が存在する（１０5／ｍｌ以上、１０6／ｍｌ未満）
１ … わずかに菌が存在する（１０5／ｍｌ未満）
≪Antimicrobial sustainability evaluation test≫
In the mouthwash obtained in Examples and Comparative Examples, S. Using a test kit “Dentocult SM (manufactured by Oral Care Co., Ltd.)” for measuring the number of mutans bacteria, an antibacterial sustainability evaluation test was conducted by five in-house panelists. As test methods, immediately before rinsing with mouthwash (initial), immediately after spitting out the mouth with 10 mL of mouthwash for 20 seconds, and after 3 hours, saliva in the mouth was collected, and the presence or absence of colonies was determined as follows. According to the standard, it was evaluated in three stages, and the average value was calculated.
[Criteria]
3 ... There are very many bacteria (10 6 / ml or more)
2 ... Bacteria are present (10 5 / ml or more and less than 10 6 / ml)
1 ... Slight bacteria (less than 10 5 / ml)
また、算出したすすぎ直後と３時間後の評価の平均値から下記の式に従い、菌の抑制率を算出した。
菌の抑制率（％） ＝ １００ − （各時間の平均値 ／イニシャルの平均値）×１００
算出した菌の抑制率を下記の基準に従い、４段階で評価した。
［判定基準］
◎ … ８０％〜１００％
○ … ４０％〜７９％
△ … ２１％〜３９％
× … ０％〜２０％
Moreover, according to the following formula | equation, the suppression rate of the microbe was computed from the average value of the evaluation immediately after the calculated rinse and 3 hours after.
Bacterial inhibition rate (%) = 100− (average value of each time / average value of initials) × 100
The calculated inhibition rate of the bacteria was evaluated in four stages according to the following criteria.
[Criteria]
◎ ... 80% ~ 100%
○ ... 40% to 79%
△ 21% -39%
×… 0% ~ 20%
洗口液を吐き出した後の後味の評価
［後味］
○ … 後味がない、或いは、僅かな苦味を感じ
△ … 僅かな苦味がしばらく継続する
× … 強い苦味やえぐ味を感じる
Evaluation of aftertaste after spouting mouthwash [aftertaste]
○… No aftertaste or a slight bitterness △… Slight bitterness continues for a while ×… A strong bitterness or a bitter taste
表１８より、実施例２５は、Ｓ．ｍｕｔａｎｓに対する長時間の菌抑制効果、洗口液の後味低減において良好な結果であった。実施例２５の洗口液の後味低減はセルロースナノファイバーと塩化セチルピリジニウムとの強い親和性に起因するものと推察される。比較例７は洗口液の後味が悪化する傾向が確認された。 From Table 18, Example 25 shows S.I. It was a favorable result in the long-term bacteria inhibitory effect with respect to mutans and the aftertaste reduction of the mouthwash. The aftertaste reduction of the mouthwash of Example 25 is presumed to be due to the strong affinity between cellulose nanofibers and cetylpyridinium chloride. In Comparative Example 7, the tendency for the aftertaste of the mouthwash to deteriorate was confirmed.
本発明のセルロースナノファイバー水分散体は、主に、増粘剤、ゲル化剤として用いられるものであり、例えば、クリーム状、ゲル状、乳液状あるいは液体状の剤型を有する各種製品（化粧料、医薬品、農薬、トイレタリー用品、スプレー剤、塗料等）の増粘剤等として好適に用いることができる。具体的には、化粧水、乳液、コールドクリーム、バニシングクリーム、マッサージクリーム、エモリエントクリーム、クレンジングクリーム、美容液、パック、ファンデーション、サンスクリーン化粧料、サンタン化粧料、モイスチャークリーム、ハンドクリーム、美白乳液、各種ローション等の皮膚用化粧料、シャンプー、リンス、ヘアコンディショナー、リンスインシャンプー、ヘアスタイリング剤（ヘアフォーム，ジェル状整髪料等）、ヘアトリートメント剤（ヘアクリーム，トリートメントローション等）、染毛剤やローションタイプの育毛剤あるいは養毛剤等の毛髪用化粧料、さらにはハンドクリーナーのような洗浄剤、プレシェーブローション、アフターシェーブローション、自動車用や室内用の芳香剤、脱臭剤、歯磨剤、軟膏、貼布剤、農薬、スプレー剤、塗料等の用途に用いることができる。
また、食品用では、具体例として以下が挙げられる。うどん、そば、焼きそば等の麺類、卵サンド、ハムサンド等のサンドイッチ類、赤飯むすび、鮭おむすび、梅入りおむすび等のおむすび類、レトルト米飯、粥などの穀類、もち類葛きり、はるさめ等の澱粉類、小豆あん、うずら豆あん、あずき餡、月餅等の餡類、豆腐、厚揚げ、いなり等の豆腐加工食品類、おでん、野菜の煮物等の煮物類、柴漬け、梅干し、たくあん、浅漬け、キムチ等の漬物類；イチゴジャム、マーマレード等のジャム類、イカ佃煮、のり佃煮等の佃煮類、みりん干し、一夜干し等の水産加工品、蒲鉾、竹輪、はんぺん等の水産練り製品、プロセスチーズ、ホイップクリーム、コーヒーホワイトナー等の乳類、ファットスプレッド、マーガリン等の油脂類、ういろう、カステラ、草もち、タルト、あんまん、せんべい、スポンジケーキ、マドレーヌ、蒸しパン、あんパン、クリームパン、ホットケーキ、ドーナツ、パイ、シュークリーム等の菓子類、アイスクリーム、プリン、ババロア、ヨーグルト、フルーツゼリー、杏仁豆腐などのデザート類、無糖コーヒー、ミルクコーヒー、カフェオレ、コーヒー牛乳などのコーヒー飲料、ミルクティー、紅茶、ストレートティー、レモンティー等の紅茶飲料、緑茶、ウーロン茶、ブレンド茶などの茶系飲料、牛乳、ミルクセーキ等の乳飲料、ココア、ホットチョコレート等のカカオ飲料、しるこ、甘酒、飴湯、しょうが湯の飲料などのｐＨが５以上の中性飲料、果汁飲料、炭酸飲料、酸性乳飲料などのｐＨが５未満の酸性飲料、コーンポタージュやポテトスープ等のスープ類、調味みそ、ごまだれ、ドレッシング、ソース、ホワイトソース、マヨネーズ、たれ等の調味料類、しゅうまい、ぎょうざ、えびフライ、コロッケ等の調理加工食品類が挙げられる。
The aqueous dispersion of cellulose nanofibers of the present invention is mainly used as a thickener and a gelling agent. For example, various products having a cream, gel, emulsion or liquid dosage form (makeup) It can be suitably used as a thickener for materials, pharmaceuticals, agricultural chemicals, toiletries, sprays, paints and the like. Specifically, lotion, emulsion, cold cream, burnishing cream, massage cream, emollient cream, cleansing cream, essence, pack, foundation, sunscreen cosmetic, suntan cosmetic, moisture cream, hand cream, whitening milk, Cosmetics for skin such as various lotions, shampoos, rinses, hair conditioners, rinse-in shampoos, hair styling agents (hair foam, gel-like hair conditioners, etc.), hair treatment agents (hair creams, treatment lotions, etc.), hair dyes and lotions Hair cosmetics such as types of hair restorers or hair nourishing agents, as well as detergents such as hand cleaners, pre-shave lotions, after-shave lotions, automotive and indoor fragrances, deodorants, dentifrices, ointments Plasters, pesticides, sprays, can be used in applications of the paint, or the like.
Moreover, the following is mentioned as a specific example for foodstuffs. Noodles such as udon, buckwheat noodles, fried noodles, sandwiches such as egg sand and ham sand, red rice musubi, rice bran rice cake, cereal such as retort rice, rice cakes such as rice cakes, starches such as rice bran , Azuki Beans, Uzura Beans, Azuki Beans, Mooncakes, etc., Tofu, Deep Fried, Inari and other Tofu Processed Foods, Oden, Vegetable Stewed Boiled Foods, Shiba Pickled, Plum Dried, Takuan, Shallow Pickled, Pickles such as kimchi; jams such as strawberry jam and marmalade; boiled squid such as squid boiled and simmered in sea bream; marine products such as mirin dried and dried overnight; marine products such as strawberries, bamboo rings and hampen; process cheese and whipped Milk such as cream, coffee whitener, fat spread, fats and oils such as margarine, Uiro, Castella, grassy mochi, tart, bun, rice cracker, sushi Desserts such as ice cream, pudding, bavaroa, yogurt, fruit jelly, apricot tofu, sugar-free coffee, milk Coffee drinks such as coffee, cafe au lait, coffee milk, tea drinks such as milk tea, tea, straight tea, lemon tea, tea drinks such as green tea, oolong tea, blended tea, milk drinks such as milk, milkshake, cocoa, hot Neutral beverages such as cocoa beverages such as chocolate, shirako, amazake, suiyu, ginger bath, etc., neutral beverages such as fruit juice beverages, carbonated beverages, acidic milk beverages, etc. Soups such as potato soup, seasoning miso, dish, dressing, saw , Seasonings such as white sauce, mayonnaise, sauce, steamed meat dumpling, dumplings, fried shrimp, cooked processed foods such as croquettes and the like.
Claims (6)
（ａ）脂肪酸エステル型構造非イオン界面活性剤
（ｂ）四級アンモニウム塩型、ベンザルコニウム塩型およびピリジニウム塩型からなる群より選ばれる１種以上の構造を有するカチオン界面活性剤 The cellulose nanofiber aqueous dispersion composition containing the following (a) and / or (b).
(A) Fatty acid ester type structure nonionic surfactant (b) Cationic surfactant having at least one structure selected from the group consisting of quaternary ammonium salt type, benzalkonium salt type and pyridinium salt type
ショ糖脂肪酸エステル、糖アルコール脂肪酸エステル、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステルおよびソルビタン脂肪酸エステルからなる群より選ばれる１種以上である請求項１記載のセルロースナノファイバー水分散体組成物。 The fatty acid ester type structure nonionic surfactant is
The cellulose nanofiber aqueous dispersion composition according to claim 1, which is at least one selected from the group consisting of sucrose fatty acid ester, sugar alcohol fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester and sorbitan fatty acid ester.
（ａ）脂肪酸エステル型構造非イオン界面活性剤
（ｂ）四級アンモニウム塩型、ベンザルコニウム塩型およびピリジニウム塩型からなる群より選ばれる１種以上の構造を有するカチオン界面活性剤 The antiseptic | prevention agent for cellulose nanofiber aqueous dispersions containing the following (a) and / or (b).
(A) Fatty acid ester type structure nonionic surfactant (b) Cationic surfactant having at least one structure selected from the group consisting of quaternary ammonium salt type, benzalkonium salt type and pyridinium salt type
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