TW202409216A - Oil-in-water emulsion composition - Google Patents
Oil-in-water emulsion composition Download PDFInfo
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- TW202409216A TW202409216A TW112120466A TW112120466A TW202409216A TW 202409216 A TW202409216 A TW 202409216A TW 112120466 A TW112120466 A TW 112120466A TW 112120466 A TW112120466 A TW 112120466A TW 202409216 A TW202409216 A TW 202409216A
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- TW
- Taiwan
- Prior art keywords
- oil
- emulsion composition
- water emulsion
- general formula
- composition according
- Prior art date
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- 239000002562 thickening agent Substances 0.000 description 1
Abstract
本發明為一種水中油型乳化液組成物，其特徵在於含有下述(A)～(C)成分。(A)將下述(A-1)成分與(A-2)成分混合而成的溶液；(A-1)具有下述通式(1)表示的結構單元的有機矽氧烷接枝聚乙烯醇系聚合物；(A-2)揮發性油；(B)從非離子性界面活性劑、陰離子性界面活性劑、陽離子性界面活性劑、及兩離子性界面活性劑之中選出的至少1種界面活性劑；(C)水。藉此，能夠提供一種組成物，其聚乙烯醇系聚合物會保持被膜形成性等特性且與油性成分之間的相溶性良好，故能夠使用來作為水中油型乳化液用的原料，且設為水中油型乳化液組成物即能夠調配在水系配方中。 式(1)中，M 1及M 2為氫原子、乙醯基、或下述通式(2)表示的矽氧烷基； 。 The present invention is an oil-in-water emulsion composition characterized by containing the following components (A) to (C). (A) A solution in which the following component (A-1) and (A-2) are mixed; (A-1) An organosiloxane grafted polymer having a structural unit represented by the following general formula (1) Vinyl alcohol polymer; (A-2) volatile oil; (B) at least one selected from nonionic surfactants, anionic surfactants, cationic surfactants, and diionic surfactants 1 surfactant; (C) water. This makes it possible to provide a composition in which the polyvinyl alcohol-based polymer maintains properties such as film-forming properties and has good compatibility with oily components, so that it can be used as a raw material for an oil-in-water emulsion and is provided. It is an oil-in-water emulsion composition that can be formulated in a water-based formula. In formula (1), M 1 and M 2 are a hydrogen atom, an acetyl group, or a siloxane group represented by the following general formula (2); .
Description
本發明是有關一種水中油型乳化液組成物。The invention relates to an oil-in-water emulsion composition.
聚乙烯醇為具有優異的阻氣性和透明性的熱塑性高分子材料。其玻璃轉移溫度由於為約80度而相對較低而加熱成型性優異，故已廣泛使用來作為薄膜、片材、容器等的原料。此外，已包覆在其它樹脂薄膜和片材而用於改良耐油性和阻氣性。Polyvinyl alcohol is a thermoplastic polymer material with excellent gas barrier properties and transparency. Its glass transition temperature is relatively low at about 80 degrees, and it has excellent thermoforming properties, so it has been widely used as a raw material for films, sheets, containers, etc. In addition, it has been coated on other resin films and sheets to improve oil resistance and gas barrier properties.
此外，在睫毛膏等眼粧、及護膚等化粧料的領域中，為了對化粧料賦予良好的特性，而至今一直進行開發一種技術，其添加具有被膜形成性的樹脂來防止脫粧。聚乙烯醇由於除了被膜形成性以外，還具有透明性、乳化性、低皮膚刺激性、被膜的柔軟度、人體適合性等優異的特性，故已調配在各種化粧料中。然而，聚乙烯醇有下述這樣的問題：缺乏對一般的油性成分的溶解性，而與大量調配在化粧料等中的烴系溶劑和油脂、矽氧系材料等之間的相溶性不良，而在皮膚上使其乾燥時不容易獲得均勻的被膜。In addition, in the field of eye makeup such as mascara and cosmetics such as skin care, a technology has been developed to add a resin with film-forming properties to prevent makeup from coming off in order to give good properties to cosmetics. Polyvinyl alcohol has excellent properties such as transparency, emulsification, low skin irritation, film softness, and human body compatibility in addition to film-forming properties, so it has been formulated in various cosmetics. However, polyvinyl alcohol has the following problems: it lacks solubility in general oily components, and has poor compatibility with hydrocarbon solvents, oils, silicone materials, etc. that are formulated in large quantities in cosmetics, and it is not easy to obtain a uniform film when it is dried on the skin.
聚乙烯醇也缺乏與用以賦予新功能的改質劑的反應性，而難以進行材料改質。因此，先前一直期望一種聚乙烯醇，其一面具有聚乙烯醇特有的性質，一面與油性成分之間的相溶性優異。Polyvinyl alcohol also lacks reactivity with modifiers used to impart new functions, making it difficult to modify materials. Therefore, there has been a demand for a polyvinyl alcohol that has properties unique to polyvinyl alcohol and has excellent compatibility with oily components.
另一方面，在相同的用途中，已大量使用一種矽氧樹脂，其與油性成分具有相溶性且具有被膜形成性。化粧料中一直使用的具有被膜形成性的矽氧樹脂可舉例如：矽氧樹脂(專利文獻1)；有機氫聚矽氧烷與含乙烯基的有機聚矽氧烷進行加成聚合而成的矽氧交聯物(專利文獻2)；丙烯酸-矽氧接枝共聚物(專利文獻3)等，為了進一步提高特性，而正在尋求新材料。On the other hand, for the same purpose, a silicone resin that is compatible with oily components and has film-forming properties has been used in large quantities. Examples of silicone resins with film-forming properties that have been used in cosmetics include silicone resins (Patent Document 1); silicone crosslinked products formed by addition polymerization of organohydropolysiloxane and vinyl-containing organopolysiloxane (Patent Document 2); acrylic-silicone graft copolymers (Patent Document 3), etc. In order to further improve the properties, new materials are being sought.
為了解決此等問題的目的，而專利文獻4中已提出一種聚合物，其側鏈具有烷氧基。然而，一方面能夠改善溶劑溶解性，另一方面已與Si鍵結的側鏈的烷氧基的水解性高，而對安全性產生另外的問題。此外，完全未進行研究關於對安全性高的矽氧油及烴油的溶解性。In order to solve these problems, Patent Document 4 has proposed a polymer having an alkoxy group in its side chain. However, while it can improve solvent solubility, on the other hand, the alkoxy group of the side chain bonded to Si is highly hydrolyzable, causing another problem with safety. In addition, no research has been conducted on the solubility of highly safe silicone oils and hydrocarbon oils.
此外，專利文獻5中已提出一種聚合物，其側鏈具有直鏈的矽氧烷。此聚合物雖對甲苯和二甲苯等芳香族烴類溶劑、N,N-二甲基甲醯胺(DMF)、甲基乙基酮(MEK)等極性溶劑的溶解性會提高，但對安全性高的矽氧油及烴油的溶解性不良，而尚未根本上地解決前述問題。In addition, Patent Document 5 proposes a polymer having a linear siloxane as a side chain. Although the solubility of this polymer in aromatic hydrocarbon solvents such as toluene and xylene, and polar solvents such as N,N-dimethylformamide (DMF) and methyl ethyl ketone (MEK) is improved, the solubility in highly safe silicone oils and hydrocarbon oils is poor, and the above-mentioned problem has not been fundamentally solved.
專利文獻6中已提出一種已被取代的矽烷基烷基胺基甲酸聚乙烯醇，來作為一種材料，其一面保持聚乙烯醇的造膜性、強韌性、優異的阻氣性和透明性等一般特性，一面藉由使具有分枝結構的矽氧改質來兼具對有機溶劑的高溶解性、作為液狀材料的優異的處理性。然而，一般的聚乙烯醇與矽氧改質劑的反應性低，為了獲得高改質率的已被取代的矽烷基烷基胺基甲酸聚乙烯醇，而必須使用過剩量的矽氧改質劑，而經常製造成本提高而不適合目標的使用用途。Patent document 6 proposes a substituted silylalkylcarbamate polyvinyl alcohol as a material which, while maintaining the general properties of polyvinyl alcohol such as film-forming property, strong toughness, excellent gas barrier property and transparency, has high solubility in organic solvents and excellent handling property as a liquid material by modifying it with silicon oxide having a branched structure. However, general polyvinyl alcohol has low reactivity with silicon oxide modifiers, and in order to obtain a substituted silylalkylcarbamate polyvinyl alcohol with a high modification rate, an excess amount of silicon oxide modifier must be used, which often increases the manufacturing cost and is not suitable for the intended use.
專利文獻7中已提出一種材料，其藉由對具有特定結構單元的聚乙烯醇以具有分枝結構的矽氧來進行改質，而兼具聚乙烯醇的被膜形成性和透明性等一般特性、與對有機溶劑的高溶解性、作為液狀材料的優異的處理性。然而，由於對水的溶解性/分散性已降低，故在添加在水系配方中時有下述缺點：因分散性不足而會在配方中分離。 [先前技術文獻] (專利文獻) Patent document 7 has proposed a material which combines the general properties of polyvinyl alcohol such as film formation and transparency with high solubility in organic solvents and excellent handling properties as a liquid material by modifying polyvinyl alcohol having a specific structural unit with silicon oxide having a branched structure. However, since the solubility/dispersibility in water has been reduced, there is the following disadvantage when adding it to a water-based formulation: it will separate in the formulation due to insufficient dispersibility. [Prior technical document] (Patent document)
專利文獻1：日本特表2020-502185號公報 專利文獻2：日本特開平3-115207號公報 專利文獻3：日本特開平2-25411號公報 專利文獻4：日本特公平5-53838號公報 專利文獻5：日本特開平9-40782號公報 專利文獻6：日本特開2011-246642號公報 專利文獻7：日本特開2017-203127號公報 Patent document 1: Japanese Patent Publication No. 2020-502185 Patent document 2: Japanese Patent Publication No. 3-115207 Patent document 3: Japanese Patent Publication No. 2-25411 Patent document 4: Japanese Patent Publication No. 5-53838 Patent document 5: Japanese Patent Publication No. 9-40782 Patent document 6: Japanese Patent Publication No. 2011-246642 Patent document 7: Japanese Patent Publication No. 2017-203127
[發明所欲解決的問題] 本發明是鑒於上述問題而完成，目的在於能夠提供一種組成物，其調配來作為主成分的有機矽氧烷接枝聚乙烯醇系聚合物會保持聚乙烯醇具有的被膜形成性等一般特性且使與油性成分、特別是大量調配在化粧料等中的烴系溶劑和油脂、矽氧系材料等之間的相溶性良好，而在皮膚上使其乾燥時會形成均勻的被膜，除此之外設為溶於揮發性油中而成的溶液即能夠使用來作為水中油型乳化液組成物的原料，並且作為組成物，設為水中油型乳化液組成物即能夠調配在水系配方中。 [解決問題的技術手段] [Problems to be solved by the invention] The present invention was made in view of the above problems, and its purpose is to provide a composition, wherein the organosiloxane grafted polyvinyl alcohol polymer formulated as the main component maintains the general properties of polyvinyl alcohol such as film-forming property and has good compatibility with oily components, especially hydrocarbon solvents and oils and silicone materials formulated in large quantities in cosmetics, etc., and forms a uniform film when dried on the skin. In addition, the solution formed by dissolving in volatile oil can be used as a raw material for an oil-in-water emulsion composition, and as a composition, the oil-in-water emulsion composition can be formulated in a water-based formulation. [Technical means for solving the problem]
為了解決上述所欲解決的問題，而本發明中提供一種水中油型乳化液組成物，其含有下述(A)～(C)成分： (A)將下述(A-1)成分與(A-2)成分混合而成的有機矽氧烷接枝聚乙烯醇系聚合物的溶液：100質量份； (A-1)具有下述通式(1)表示的結構單元的有機矽氧烷接枝聚乙烯醇系聚合物； 式(1)中，M 1及M 2為氫原子、乙醯基、或下述通式(2)表示的矽氧烷基，並且M 1及M 2之中的至少一方為下述通式(2)表示的矽氧烷基；A表示單鍵或連結基； 式(2)中，R 1為碳數1～6的1價有機基，R 2、R 3及R 4分別為碳數1～6的1價有機基或－OSiR 5R 6R 7表示的矽烷氧基，R 5、R 6及R 7分別為碳數1～6的1價有機基；n為1～10的整數，a為0～2的整數； (A-2)揮發性油； (B)從非離子性界面活性劑、陰離子性界面活性劑、陽離子性界面活性劑、及兩離子性界面活性劑之中選出的至少1種界面活性劑；2～30質量份； (C)水：10～2,000質量份。 In order to solve the above-mentioned problems, the present invention provides an oil-in-water emulsion composition, which contains the following components (A) to (C): (A) 100 parts by weight of a solution of an organosiloxane-grafted polyvinyl alcohol polymer prepared by mixing the following components (A-1) and (A-2); (A-1) an organosiloxane-grafted polyvinyl alcohol polymer having a structural unit represented by the following general formula (1); In formula (1), M1 and M2 are hydrogen atoms, acetyl groups, or siloxane groups represented by the following general formula (2), and at least one of M1 and M2 is a siloxane group represented by the following general formula (2); A represents a single bond or a linking group; In formula (2), R1 is a monovalent organic group having 1 to 6 carbon atoms, R2 , R3 and R4 are each a monovalent organic group having 1 to 6 carbon atoms or a silaneoxy group represented by -OSiR5R6R7 , R5 , R6 and R7 are each a monovalent organic group having 1 to 6 carbon atoms; n is an integer from 1 to 10, and a is an integer from 0 to 2; (A-2) a volatile oil; (B) at least one surfactant selected from a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphiphilic surfactant; 2 to 30 parts by weight; (C) water: 10 to 2,000 parts by weight.
如果為這樣的水中油型乳化液組成物，其含有有機矽氧烷接枝聚乙烯醇系聚合物，則會成為一種材料，其調配來作為主成分的有機矽氧烷接枝聚乙烯醇系聚合物會保持聚乙烯醇具有的被膜形成性等一般特性且與油性成分、特別是烴油及矽氧系材料之間的相溶性優異，並且能夠調配在水系配方中。因此，能夠較合適地使用來作為適合水系的化粧料、黏著劑、塗料等的材料。If such an oil-in-water emulsion composition contains an organosilicone-grafted polyvinyl alcohol polymer, the organosilicone-grafted polyvinyl alcohol polymer formulated as the main component will maintain the general properties of polyvinyl alcohol such as film-forming properties and has excellent compatibility with oily components, especially hydrocarbon oils and silicone materials, and can be formulated in a water-based formulation. Therefore, it can be more appropriately used as a material suitable for water-based cosmetics, adhesives, coatings, etc.
較佳是：前述通式(1)中的A為單鍵。Preferably, A in the aforementioned general formula (1) is a single bond.
較佳是：前述(A-1)成分的有機矽氧烷接枝聚乙烯醇系聚合物進一步具有下述通式(3)表示的結構單元，且以GPC(凝膠滲透層析法)來測定的聚苯乙烯換算的數目平均分子量(Mn)為5,000～500,000； 式(3)中，M 3為氫原子、乙醯基、或前述通式(2)表示的矽氧烷基。 Preferably, the organosiloxane-grafted polyvinyl alcohol polymer of the component (A-1) further has a structural unit represented by the following general formula (3), and has a polystyrene-equivalent number average molecular weight (Mn) of 5,000 to 500,000 as measured by GPC (gel permeation chromatography); In formula (3), M3 is a hydrogen atom, an acetyl group, or a siloxyalkyl group represented by the general formula (2).
如果為這樣的(A-1)成分，則會更確實地成為一種材料，其會保持聚乙烯醇具有的被膜形成性等一般特性且與油性成分、特別是烴油及矽氧系材料之間的相溶性優異。Such a component (A-1) can more reliably be a material which maintains the general properties of polyvinyl alcohol such as film-forming property and has excellent compatibility with oily components, particularly hydrocarbon oil and silicone-based materials.
此外，較佳是：前述通式(2)中，n為3，R 2、R 3及R 4為甲基，a為0。 Furthermore, preferably, in the general formula (2), n is 3, R 2 , R 3 and R 4 are methyl groups, and a is 0.
如果如上所述，前述通式(2)中，n為3，R 2、R 3及R 4為甲基，a為0，則生產性、反應性等會更優異。 If, in the general formula (2), n is 3, R 2 , R 3 and R 4 are methyl groups, and a is 0, productivity, reactivity, etc. will be further improved.
較佳是：前述(A-2)成分的揮發性油為25℃時的黏度為未達6 mm 2/s的矽氧油及/或烴油。 Preferably, the volatile oil of the component (A-2) is silicone oil and/or hydrocarbon oil having a viscosity of less than 6 mm 2 /s at 25°C.
如果為這樣的(A-2)成分，則在塗佈水中油型乳化液組成物時，(A-2)成分能夠迅速揮發而獲得良好的被膜。If it is such a component (A-2), when the oil-in-water emulsion composition is applied, the component (A-2) can quickly volatilize and a good film can be obtained.
較佳是：前述(B)成分包含非離子性界面活性劑。Preferably, the component (B) contains a nonionic surfactant.
此水中油型乳化液組成物如果包含非離子性界面活性劑，則安定性會較優異。If the water-in-oil emulsion composition contains a non-ionic surfactant, the stability will be better.
較佳是：前述非離子性界面活性劑為從聚氧伸烷基烷基醚及聚氧伸乙基山梨糖醇酐脂肪酸酯之中選出的1種以上。Preferably, the nonionic surfactant is at least one selected from polyoxyalkylene alkyl ethers and polyoxyethylene sorbitan fatty acid esters.
如果前述非離子性界面活性劑為上述特定物，則此水中油型乳化液組成物的安定性會更優異。If the nonionic surfactant is the specific substance mentioned above, the stability of the water-oil emulsion composition will be better.
較佳是：前述水中油型乳化液組成物中的乳化粒子的平均粒徑為500 nm以下。Preferably, the average particle diameter of the emulsified particles in the oil-in-water emulsion composition is 500 nm or less.
如果前述乳化粒子的平均粒徑為500 nm以下，則此水中油型乳化液組成物的安定性會更優異。 [功效] If the average particle size of the emulsified particles is less than 500 nm, the stability of the water-oil emulsion composition will be better. [Effects]
本發明的水中油型乳化液組成物會成為一種材料，其會保持聚乙烯醇具有的被膜形成性等一般特性且與油性成分、特別是烴油及矽氧系材料之間的相溶性優異，故設為溶液即能夠作為液狀物質來進行處理，並且設為水中油型乳化液組成物即能夠調配在水系配方中。因此，能夠較合適地使用來作為適合水系的化粧料、黏著劑、塗料等的材料。The oil-in-water emulsion composition of the present invention is a material that maintains the general properties of polyvinyl alcohol such as film-forming properties and has excellent compatibility with oily components, especially hydrocarbon oils and silicone-based materials. Therefore, it can be handled as a liquid substance when it is a solution, and it can be formulated in a water-based formulation when it is a water-based emulsion composition. Therefore, it can be more appropriately used as a material suitable for water-based cosmetics, adhesives, coatings, etc.
如前所述，先前一直尋求一種材料，其一面具有聚乙烯醇特有的性質，一面與油性成分、特別是烴油及矽氧系材料之間的相溶性優異，並且能夠調配在水系配方中。As mentioned above, there has been a demand for a material that has the unique properties of polyvinyl alcohol, has excellent compatibility with oily components, especially hydrocarbon oils and silicone materials, and can be formulated in aqueous formulations.
本發明人針對上述所欲解決的問題反覆致力進行研究後，結果發現下述事實而完成本發明：一種水中油型乳化液組成物，其含有具有前述通式(1)表示的結構單元的特定有機矽氧烷接枝聚乙烯醇系聚合物、界面活性劑及水，而會成為一種材料，其會保持聚乙烯醇具有的被膜形成性等一般特性且與油性成分、特別是烴油及矽氧系材料之間的相溶性優異，並且能夠調配在水系配方中。The inventors of the present invention have made intensive researches on the above-mentioned problems and have discovered the following facts, thereby completing the present invention: an oil-in-water emulsion composition comprising a specific organosiloxane-grafted polyvinyl alcohol polymer having a structural unit represented by the general formula (1), a surfactant and water, which is a material that retains the general properties of polyvinyl alcohol, such as film-forming properties, and has excellent compatibility with oily components, especially hydrocarbon oils and silicone materials, and can be formulated in a water-based formulation.
也就是說，本發明為一種水中油型乳化液組成物，其含有下述(A)～(C)成分： (A)將下述(A-1)成分與(A-2)成分混合而成的有機矽氧烷接枝聚乙烯醇系聚合物的溶液：100質量份； (A-1)具有下述通式(1)表示的結構單元的有機矽氧烷接枝聚乙烯醇系聚合物； 式(1)中，M 1及M 2為氫原子、乙醯基、或下述通式(2)表示的矽氧烷基，並且M 1及M 2之中的至少一方為下述通式(2)表示的矽氧烷基；A表示單鍵或連結基； 式(2)中，R 1為碳數1～6的1價有機基，R 2、R 3及R 4分別為碳數1～6的1價有機基或－OSiR 5R 6R 7表示的矽烷氧基，R 5、R 6及R 7分別為碳數1～6的1價有機基；n為1～10的整數，a為0～2的整數； (A-2)揮發性油； (B)從非離子性界面活性劑、陰離子性界面活性劑、陽離子性界面活性劑、及兩離子性界面活性劑之中選出的至少1種界面活性劑；2～30質量份； (C)水：10～2,000質量份。 That is, the present invention is an oil-in-water emulsion composition containing the following components (A) to (C): (A) The following components (A-1) and (A-2) are mixed. A solution of the organosiloxane-grafted polyvinyl alcohol-based polymer: 100 parts by mass; (A-1) Organosiloxane-grafted polyvinyl alcohol-based polymer having a structural unit represented by the following general formula (1) thing; In the formula (1), M 1 and M 2 are a hydrogen atom, an acetyl group, or a siloxane group represented by the following general formula (2), and at least one of M 1 and M 2 is the following general formula (2) Siloxane group represented; A represents a single bond or connecting group; In the formula (2), R 1 is a monovalent organic group having 1 to 6 carbon atoms, and R 2 , R 3 and R 4 are each a monovalent organic group having 1 to 6 carbon atoms or -OSiR 5 R 6 R 7 Silanoxy group, R 5 , R 6 and R 7 are respectively monovalent organic groups having 1 to 6 carbon atoms; n is an integer from 1 to 10, and a is an integer from 0 to 2; (A-2) Volatile oil; (B) At least one surfactant selected from nonionic surfactants, anionic surfactants, cationic surfactants, and diionic surfactants; 2 to 30 parts by mass; (C) Water: 10 to 2,000 parts by mass.
以下更詳細說明本發明。The present invention is described in more detail below.
[(A)將下述(A-1)成分與(A-2)成分混合而成的有機矽氧烷接枝聚乙烯醇系聚合物的溶液] 本發明中的(A)成分為一種組成物，其是將具有下述通式(1)表示的結構單元的有機矽氧烷接枝聚乙烯醇系聚合物(A-1)與揮發性油(A-2)混合而設為溶液而成。 [(A) Solution of an organic silicone grafted polyvinyl alcohol polymer prepared by mixing the following components (A-1) and (A-2)] The component (A) in the present invention is a composition obtained by mixing an organic silicone grafted polyvinyl alcohol polymer (A-1) having a structural unit represented by the following general formula (1) and a volatile oil (A-2) to form a solution.
(A-1)具有下述通式(1)表示的結構單元的有機矽氧烷接枝聚乙烯醇系聚合物； 式(1)中，M 1及M 2為氫原子、乙醯基、或下述通式(2)表示的矽氧烷基，並且M 1及M 2之中的至少一方為下述通式(2)表示的矽氧烷基；A表示單鍵或連結基； 式(2)中，R 1為碳數1～6的1價有機基，R 2、R 3及R 4分別為碳數1～6的1價有機基或－OSiR 5R 6R 7表示的矽烷氧基，R 5、R 6及R 7分別為碳數1～6的1價有機基；n為1～10的整數，a為0～2的整數； (A-2)揮發性油； (A-1) an organosiloxane-grafted polyvinyl alcohol polymer having a structural unit represented by the following general formula (1); In formula (1), M1 and M2 are hydrogen atoms, acetyl groups, or siloxane groups represented by the following general formula (2), and at least one of M1 and M2 is a siloxane group represented by the following general formula (2); A represents a single bond or a linking group; In formula (2), R1 is a monovalent organic group having 1 to 6 carbon atoms, R2 , R3 and R4 are each a monovalent organic group having 1 to 6 carbon atoms or a silanyl group represented by -OSiR5R6R7 , R5 , R6 and R7 are each a monovalent organic group having 1 to 6 carbon atoms; n is an integer of 1 to 10, and a is an integer of 0 to 2; (A- 2 ) a volatile oil;
[(A-1)成分] 此處，作為表示(A-1)成分的上述通式(1)的化合物的側鏈來存在的上述通式(2)中的R 1、R 2、R 3、R 4、R 5、R 6及R 7為碳數1～6的1價有機基，具體而言可例示如：甲基、乙基、丙基、異丙基、丁基、三級丁基、己基等烷基；環戊基、環己基等環烷基；苯基等芳基；乙烯基、烯丙基、5-己烯基等烯基；氯甲基、3,3,3-三氟丙基等已被取代的烴基等，R 1、R 2、R 3、R 4、R 5、R 6及R 7分別可相同或不同。此外，R 2、R 3及R 4分別可為－OSiR 5R 6R 7表示的矽烷氧基，此矽烷氧基可例示如：三甲基矽烷氧基、乙基二甲基矽烷氧基、苯基二甲基矽烷氧基、乙烯基二甲基矽烷氧基、氯甲基二甲基矽烷氧基、3,3,3-三氟丙基二甲基矽烷氧基等。 [Component (A-1)] Here, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 in the above-mentioned general formula (2) present as a side chain of the compound of the above-mentioned general formula (1) representing the component (A-1) are monovalent organic groups having 1 to 6 carbon atoms, and specific examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl and hexyl ; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl; alkenyl groups such as vinyl, allyl and 5-hexenyl; substituted alkyl groups such as chloromethyl and 3,3,3-trifluoropropyl, etc., and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may be the same or different. Furthermore, R 2 , R 3 and R 4 may each be a silyloxy group represented by -OSiR 5 R 6 R 7. Examples of the silyloxy group include trimethylsilyloxy, ethyldimethylsilyloxy, phenyldimethylsilyloxy, vinyldimethylsilyloxy, chloromethyldimethylsilyloxy and 3,3,3-trifluoropropyldimethylsilyloxy.
上述通式(2)中，a為0～2的整數，較佳是：上述通式(2)中，n為3，R 2、R 3及R 4為甲基，a為0。 In the above general formula (2), a is an integer from 0 to 2. Preferably, in the above general formula (2), n is 3, R 2 , R 3 and R 4 are methyl groups, and a is 0.
此外，較佳是：上述通式(1)中的A為單鍵。如果為這樣的(A-1)成分，則會更確實地成為一種材料，其會保持聚乙烯醇具有的被膜形成性等一般特性且與油性成分、特別是烴油及矽氧系材料之間的相溶性優異。Furthermore, it is preferable that A in the above general formula (1) is a single bond. If it is such a component (A-1), it will more reliably become a material that maintains the general properties of polyvinyl alcohol such as film formation and is compatible with oily components, especially hydrocarbon oils and silicone materials. Excellent compatibility.
此外，較佳是：(A-1)成分的有機矽氧烷接枝聚乙烯醇系聚合物的以GPC來測定的聚苯乙烯換算的數目平均分子量(Mn)為5,000～500,000。Furthermore, it is preferred that the organosiloxane-grafted polyvinyl alcohol polymer of the component (A-1) has a polystyrene-equivalent number average molecular weight (Mn) of 5,000 to 500,000 as measured by GPC.
(A-1)成分的有機矽氧烷接枝聚乙烯醇系聚合物的分子量只要以以四氫呋喃(THF)作為溶劑的GPC來測定的聚苯乙烯換算的數目平均分子量(Mn)在5,000～500,000的範圍內即可，較佳為7,000～300,000，更佳為10,000～100,000。如果數目平均分子量為5,000以上，則在薄膜強度的點上優異，如果數目平均分子量為500,000以下，則在處理性和溶解性的點上良好。The molecular weight of the organosiloxane-grafted polyvinyl alcohol polymer of component (A-1) may be in the range of 5,000 to 500,000, preferably 7,000 to 300,000, and more preferably 10,000 to 100,000, as measured by GPC using tetrahydrofuran (THF) as a solvent, in terms of polystyrene conversion. If the number average molecular weight is 5,000 or more, the film strength is excellent, and if the number average molecular weight is 500,000 or less, the handling property and solubility are good.
此外，也較佳是具有下述通式(3)的結構。如果為這樣的(A-1)成分，則與A為單鍵的情形同樣地，會更確實地成為一種材料，其會保持聚乙烯醇具有的被膜形成性等一般特性且與油性成分、特別是烴油及矽氧系材料之間的相溶性優異。 式(3)中，M 3為氫原子、乙醯基、或前述通式(2)表示的矽氧烷基。 In addition, it is also preferable to have a structure of the following general formula (3). If it is such a component (A-1), as in the case where A is a single bond, it will more reliably become a material that maintains the general properties of polyvinyl alcohol such as film-forming properties and is compatible with oily components, especially It has excellent compatibility between hydrocarbon oil and silicone materials. In formula (3), M 3 is a hydrogen atom, an acetyl group, or a siloxane group represented by the aforementioned general formula (2).
(有機矽氧烷接枝聚乙烯醇系聚合物的製造方法) 此外，(A-1)成分的有機矽氧烷接枝聚乙烯醇系聚合物是使含有下述通式(4)表示的結構單元的聚乙烯醇系樹脂化合物與下述通式(5)表示的含異氰酸基的有機矽氧烷進行反應來獲得。 式(4)中，A表示單鍵或連結基。 式(5)中，R 1為碳數1～6的1價有機基，R 2、R 3及R 4分別為碳數1～6的1價有機基或－OSiR 5R 6R 7表示的矽烷氧基，R 5、R 6及R 7分別為碳數1～6的1價有機基；n為1～10的整數，a為0～2的整數。 (Method for producing organosiloxane-grafted polyvinyl alcohol-based polymer) In addition, the organosiloxane-grafted polyvinyl alcohol-based polymer of component (A-1) is represented by the following general formula (4): The polyvinyl alcohol-based resin compound of the structural unit is obtained by reacting with an isocyanato group-containing organosiloxane represented by the following general formula (5). In formula (4), A represents a single bond or a connecting group. In the formula (5), R 1 is a monovalent organic group having 1 to 6 carbon atoms, and R 2 , R 3 and R 4 are each a monovalent organic group having 1 to 6 carbon atoms or -OSiR 5 R 6 R 7 Silanoxy group, R 5 , R 6 and R 7 are respectively monovalent organic groups having 1 to 6 carbon atoms; n is an integer of 1 to 10, and a is an integer of 0 to 2.
在成為有機矽氧烷接枝聚乙烯醇系聚合物的原料的聚乙烯醇系樹脂化合物中含有上述通式(4)表示的結構單元，而該聚乙烯醇系樹脂化合物的與油性材料之間的相溶性會提高，且能夠使與上述通式(5)表示的含異氰酸基的有機矽氧烷的反應率顯著提高。The polyvinyl alcohol resin compound serving as the raw material of the organosiloxane-grafted polyvinyl alcohol polymer contains the structural unit represented by the above-mentioned general formula (4), and the compatibility of the polyvinyl alcohol resin compound with the oily material is improved, and the reaction rate with the isocyanate group-containing organosiloxane represented by the above-mentioned general formula (5) can be significantly improved.
此外，前述聚乙烯醇系樹脂化合物較佳是使用進一步含有下述式(6)表示的結構單元： 。 In addition, the polyvinyl alcohol-based resin compound is preferably used which further contains a structural unit represented by the following formula (6): .
含有上述通式(4)表示的結構單元及進一步的上述式(6)表示的結構單元的聚乙烯醇系樹脂化合物能夠以例如下述方式獲得：使包含下述通式(7)表示的結構單元及下述式(8)表示的結構單元的聚乙酸乙烯酯系樹脂化合物皂化。 式(7)中，A表示單鍵或連結基。 The polyvinyl alcohol-based resin compound containing the structural unit represented by the above general formula (4) and further the structural unit represented by the above formula (6) can be obtained, for example, by saponifying a polyvinyl acetate-based resin compound containing the structural unit represented by the following general formula (7) and the structural unit represented by the following formula (8). In formula (7), A represents a single bond or a linking group.
再者，有機矽氧烷接枝聚乙烯醇系聚合物的原料也就是聚乙烯醇系樹脂化合物能夠以聚乙酸乙烯酯系化合物皂化的方式獲得，該聚乙烯醇系樹脂化合物也能夠使用一部分已皂化之物。Furthermore, the raw material of the organosiloxane-grafted polyvinyl alcohol polymer, that is, the polyvinyl alcohol resin compound can be obtained by saponifying a polyvinyl acetate compound, and the polyvinyl alcohol resin compound can also be partially saponified.
此外，當使用一部分已皂化的聚乙烯醇系樹脂化合物來合成有機矽氧烷接枝聚乙烯醇系聚合物時，代表性的化合物能夠設為一種有機矽氧烷接枝聚乙烯醇系聚合物，其包含上述通式(7)表示的結構單元及上述式(8)表示的結構單元。In addition, when a partially saponified polyvinyl alcohol-based resin compound is used to synthesize an organosiloxane-grafted polyvinyl alcohol-based polymer, a representative compound can be an organosiloxane-grafted polyvinyl alcohol-based polymer. , which includes the structural unit represented by the above general formula (7) and the structural unit represented by the above formula (8).
含有上述通式(7)表示的結構單元及進一步的上述式(8)表示的結構單元的聚乙酸乙烯酯系樹脂化合物是以下述方式獲得：使下述通式(9)表示的化合物與下述式(10)表示的化合物進行聚合。 式(9)中，A表示單鍵或連結基。 A polyvinyl acetate-based resin compound containing a structural unit represented by the above-mentioned general formula (7) and further a structural unit represented by the above-mentioned formula (8) is obtained by mixing a compound represented by the following general formula (9) with the following The compound represented by the formula (10) is polymerized. In formula (9), A represents a single bond or a connecting group.
上述聚乙烯醇系樹脂化合物的分子量能夠以使本發明的有機矽氧烷接枝聚乙烯醇系聚合物的分子量(也就是以GPC來測定的聚苯乙烯換算的數目平均分子量(Mn))成為5,000～500,000的範圍的方式適當選擇。The molecular weight of the polyvinyl alcohol-based resin compound can be such that the molecular weight of the organosiloxane-grafted polyvinyl alcohol-based polymer of the present invention (that is, the number average molecular weight (Mn) in terms of polystyrene measured by GPC) is Choose an appropriate method within the range of 5,000 to 500,000.
上述聚乙烯醇系樹脂化合物已作為日本合成化學工業的G-Polymer TM製造販賣且能夠取得。具體而言能夠從下述中選擇：AZF8035W、OKS-6026、OKS-1011、OKS-8041、OKS-8049、OKS-1028、OKS-1027、OKS-1109、OKS-1083。 The polyvinyl alcohol resin compound is manufactured and sold as G-Polymer TM of Nippon Synthetic Chemical Industry Co., Ltd. and can be obtained. Specifically, it can be selected from the following: AZF8035W, OKS-6026, OKS-1011, OKS-8041, OKS-8049, OKS-1028, OKS-1027, OKS-1109, OKS-1083.
(A-1)成分的有機矽氧烷接枝聚乙烯醇系聚合物的製造方法是如上所述藉由使聚乙烯醇系樹脂化合物的羥基與含異氰酸基的有機矽氧烷進行反應來進行，此含異氰酸基的有機矽氧烷特佳是使用：參(三甲基矽烷氧基)矽烷基丙基異氰酸酯(也就是在上述通式(5)中n為3且R 2、R 3及R 4為甲基且a為0之物)。只要使參(三甲基矽烷氧基)矽烷基丙基異氰酸酯與聚乙烯醇系樹脂化合物進行反應，則能夠獲得參(三甲基矽烷氧基)矽烷基丙基胺基甲酸聚乙烯醇系聚合物。其具有下述通式(11)表示的結構單元。 式(11)中，L 1及L 2為氫原子、乙醯基、或下述通式(12)表示的矽氧烷基，並且L 1及L 2之中的至少一方為下述通式(12)表示的矽氧烷基；A表示單鍵或連結基； 。 The method for producing the organosiloxane-grafted polyvinyl alcohol-based polymer of the component (A-1) is by reacting the hydroxyl group of the polyvinyl alcohol-based resin compound with the isocyanate group-containing organosiloxane as described above. To carry out, this isocyanato group-containing organosiloxane is particularly preferably used: (trimethylsilyloxy)silylpropyl isocyanate (that is, in the above general formula (5), n is 3 and R 2 , R 3 and R 4 are methyl and a is 0). By reacting ginseng (trimethylsiloxy)silylpropyl isocyanate with a polyvinyl alcohol-based resin compound, ginseng (trimethylsiloxy)silylpropylcarbamate polyvinyl alcohol-based polymerization can be obtained things. It has a structural unit represented by the following general formula (11). In the formula (11), L 1 and L 2 are a hydrogen atom, an acetyl group, or a siloxane group represented by the following general formula (12), and at least one of L 1 and L 2 is the following general formula (12) represents a siloxane group; A represents a single bond or connecting group; .
此外，(A-1)成分的有機矽氧烷接枝聚乙烯醇系聚合物的製造方法是如上所述藉由使聚乙烯醇系樹脂化合物的羥基與含異氰酸基的有機矽氧烷進行反應來進行，此聚乙烯醇系樹脂化合物較佳是包含聚丁烯二醇結構(也就是在上述通式(4)中A為單鍵之物)。如果包含聚丁烯二醇結構，則能夠效率良好地獲得一種有機矽氧烷接枝聚乙烯醇系聚合物，其對有機溶劑的溶解性高且具有高改質率。其具有下述通式(13)表示的結構單元。 式(13)中，L 1及L 2與上述相同。 In addition, the method for producing the organosiloxane-grafted polyvinyl alcohol polymer of the component (A-1) is carried out by reacting the hydroxyl group of the polyvinyl alcohol resin compound with the organosiloxane containing an isocyanate group as described above, and the polyvinyl alcohol resin compound preferably contains a polybutylene glycol structure (that is, A is a single bond in the above general formula (4)). If the polybutylene glycol structure is contained, an organosiloxane-grafted polyvinyl alcohol polymer can be obtained efficiently, which has high solubility in organic solvents and a high modification rate. It has a structural unit represented by the following general formula (13). In formula (13), L1 and L2 are the same as described above.
再者，(A-1)成分的有機矽氧烷接枝聚乙烯醇系聚合物的製造方法由於為藉由聚乙烯醇系樹脂化合物的羥基與含異氰酸基的有機矽氧烷的胺酯鍵產生反應來進行的製造方法，故無須使用特別的反應條件和反應裝置，為了聚乙烯醇系樹脂化合物的羥基與含異氰酸基的有機矽氧烷的混合、反應效率、反應控制，而較佳是使用溶劑。此溶劑可例示如：乙酸甲酯、乙酸乙酯、乙酸丁酯等酯類；丙酮、甲基乙基酮、環己酮等酮類；甲苯、二甲苯等芳香族烴類；二***、四氫呋喃等醚類；N,N-二甲基甲醯胺、N-甲基吡咯啶酮等醯胺類；二甲基亞碸等亞碸類，此等可使用單獨1種、或混合使用2種以上。Furthermore, the method for producing the organosiloxane-grafted polyvinyl alcohol-based polymer of the component (A-1) involves the use of the hydroxyl group of the polyvinyl alcohol-based resin compound and the amine of the isocyanate-containing organosiloxane. The manufacturing method is carried out by reaction of ester bond, so there is no need to use special reaction conditions and reaction equipment. In order to mix, react efficiently and control the reaction between the hydroxyl group of the polyvinyl alcohol resin compound and the isocyanate group-containing organosiloxane, Preferably, a solvent is used. Examples of this solvent include: esters such as methyl acetate, ethyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; diethyl ether, and tetrahydrofuran. ethers; amides such as N,N-dimethylformamide and N-methylpyrrolidone; styrenes such as dimethylsulfoxide. These can be used individually or in combination. above.
此外，雖會因此處使用的溶劑的種類而不同，但此反應通常只要設為在20～150℃1～24小時即可，此時，可添加像下述這樣的在形成胺酯鍵時使用的公知觸媒來作為觸媒：三乙胺、三伸乙二胺、N-甲基嗎啉等胺類；二月桂酸二正丁錫、油酸亞錫等有機金屬化合物。反應結束後，只要洗淨、乾燥，則能夠獲得目標的有機矽氧烷接枝聚乙烯醇系聚合物。In addition, although it will differ depending on the type of solvent used here, this reaction usually only needs to be carried out at 20 to 150°C for 1 to 24 hours. In this case, the following solvents used when forming an amine ester bond can be added. Well-known catalysts are used as catalysts: amines such as triethylamine, triethylenediamine, and N-methylmorpholine; organometallic compounds such as di-n-butyltin dilaurate and stannous oleate. After the reaction is completed, the target organosiloxane-grafted polyvinyl alcohol-based polymer can be obtained by simply washing and drying.
[(A-2)成分] 揮發性油可舉例如：25℃時的黏度為未達6 mm 2/s的矽氧油；己烷、辛烷、異十二烷、α-烯烴寡聚物、輕質異構烷烴、輕質流動異構烷烴、流動石蠟、流動異構烷烴等烴油；甲基乙基酮、甲基異丁基酮等酮系化合物；乙酸乙酯、乙酸異丁酯等酯系化合物；甲醇、乙醇、異丙醇、丁醇、異丁醇、三級丁醇等醇類；甲苯、二甲苯等芳香族烴類等，能夠從在常壓/25℃時沸點顯示260℃以下之物中適當選擇使用，能夠使用單獨1種或適當組合使用2種以上。化粧料中能夠使用的揮發性油可舉例如：矽氧油、烴油、酮系化合物、酯系化合物、醇類。從安全性及泛用性的觀點來看，較佳為矽氧油及烴油、酯系化合物。再更佳為矽氧油及烴油。 [(A-2) Component] Examples of volatile oils include silicone oil with a viscosity of less than 6 mm 2 /s at 25°C; hexane, octane, isododecane, and α-olefin oligomers , light isoparaffin, light mobile isoparaffin, mobile paraffin, mobile isoparaffin and other hydrocarbon oils; methyl ethyl ketone, methyl isobutyl ketone and other ketone compounds; ethyl acetate, isobutyl acetate Ester compounds such as methanol, ethanol, isopropanol, butanol, isobutanol, tertiary butanol and other alcohols; aromatic hydrocarbons such as toluene and xylene, etc., can be displayed from the boiling point at normal pressure/25℃ Those having a temperature of 260°C or lower can be appropriately selected and used, and one type can be used alone or two or more types can be used in an appropriate combination. Examples of volatile oils that can be used in cosmetics include silicone oils, hydrocarbon oils, ketone compounds, ester compounds, and alcohols. From the viewpoint of safety and versatility, silicone oil, hydrocarbon oil, and ester compounds are preferred. Even better are silicone oil and hydrocarbon oil.
矽氧油是使用25℃時的黏度為未達6 mm 2/s的矽氧油。再者，此黏度為運動黏度，並且為由奧氏(Ostwald)黏度計所得的25℃時的測定值(以下相同)。如果黏度為未達6 mm 2/s，則在25℃時具有揮發性而矽氧油也不會殘留在被膜中，且在將水中油型乳化液組成物調配在化粧料等中時也不會顯現沾黏感。矽氧油的25℃時的黏度的下限無特別限定，能夠設為例如0.65 mm 2/s。矽氧油可舉例如下述通式表示的矽氧油。 式中，b為1～3的整數，R 8為相同或不同種的碳數1～10的1價有機基，c為4～6的整數。 Silicone oil is used with a viscosity of less than 6 mm 2 /s at 25°C. In addition, this viscosity is a kinematic viscosity, and is the measured value at 25°C obtained by an Ostwald viscometer (the same applies below). If the viscosity is less than 6 mm 2 /s, it is volatile at 25°C and the silicone oil will not remain in the film, and it will not remain in the oil-in-water emulsion composition when it is formulated in cosmetics, etc. A sticky feeling will appear. The lower limit of the viscosity of the silicone oil at 25° C. is not particularly limited, but can be, for example, 0.65 mm 2 /s. Examples of silicone oil include silicone oil represented by the following general formula. In the formula, b is an integer of 1 to 3, R 8 is the same or different monovalent organic group having 1 to 10 carbon atoms, and c is an integer of 4 to 6.
烴油可舉例如：直鏈狀或分枝狀且揮發性的烴油等。其具體例可舉例如：異十二烷、α-烯烴寡聚物、輕質異構烷烴、輕質流動異構烷烴、流動石蠟、流動異構烷烴等。雖只要依要求的使用感等來適當選擇即可，但從泛用性的觀點來看，較佳為異十二烷、異構烷烴(isoparaffin)等。Examples of the hydrocarbon oil include linear or branched and volatile hydrocarbon oils. Specific examples thereof include isododecane, α-olefin oligomer, light isoparaffin, light flowing isoparaffin, flowing paraffin, and flowing isoparaffin. It is sufficient to select appropriately according to the required feeling of use, etc., but from the viewpoint of versatility, isododecane, isoparaffin (isoparaffin), etc. are preferred.
酯系化合物可舉例如：乙酸乙酯、乙酸丁酯、乙酸異丙酯等。Examples of the ester compound include ethyl acetate, butyl acetate, isopropyl acetate, and the like.
(A-1)有機矽氧烷接枝聚乙烯醇系聚合物與(A-2)揮發性油的質量比無特別限制，較佳為(A-1)/(A-2)＝10/90～90/10，更佳為15/85～80/20，再更佳為20/80～75/25。如果揮發性油(A-2)的比例較10/90更少，則在將包含水中油型乳化液組成物的化粧料塗佈時，揮發性油(A-2)會迅速揮發，而不會阻礙化粧料的特性，也無對皮膚造成刺激的疑慮。另一方面，如果揮發性油(A-2)較90/10更多，則能夠將作為(A)成分的黏度抑制在較低，而處理性不會惡化。The mass ratio of (A-1) organosiloxane-grafted polyvinyl alcohol-based polymer and (A-2) volatile oil is not particularly limited, but is preferably (A-1)/(A-2)=10/ 90～90/10, more preferably 15/85～80/20, still more preferably 20/80～75/25. If the proportion of volatile oil (A-2) is less than 10/90, when a cosmetic containing an oil-in-water emulsion composition is applied, the volatile oil (A-2) will volatilize quickly without It will hinder the properties of cosmetics and cause irritation to the skin. On the other hand, if the volatile oil (A-2) is more than 90/10, the viscosity of the component (A) can be kept low without deteriorating the handleability.
(A)成分的有機矽氧烷接枝聚乙烯醇系聚合物的溶液的黏度無特別限制，較佳為1～100,000 mm 2/s，更佳為2～50,000 mm 2/s，再更佳為5～30,000 mm 2/s，特佳為10～10,000 mm 2/s。如果黏度為1 mm 2/s以上，則容易使用均質機和均質分散機(homodisper)等一般的攪拌機來乳化，且水中油型乳化液組成物的乳化粒子會變細，故保存安定性不會降低，且無會經時發生濃淡分離的疑慮。此外，如果黏度為100,000 mm 2/s以下，則處理性不會惡化。 The viscosity of the solution of the organosiloxane-grafted polyvinyl alcohol polymer as component (A) is not particularly limited, but is preferably 1 to 100,000 mm 2 /s, more preferably 2 to 50,000 mm 2 /s, and still more preferably It is 5～30,000 mm 2 /s, and the best one is 10～10,000 mm 2 /s. If the viscosity is 1 mm 2 /s or more, it is easy to emulsify using a general mixer such as a homogenizer and a homodisperse, and the emulsified particles of the oil-in-water emulsion composition become finer, so the storage stability is affected. Reduces the risk of light and shade separation over time. In addition, if the viscosity is 100,000 mm 2 /s or less, the handleability will not be deteriorated.
[(B)成分] (B)成分的界面活性劑只要能夠使(A)成分乳化分散在水中，則無特別限制，較佳是包含非離子性界面活性劑。可舉例如：聚氧伸乙基烷基醚、聚氧伸乙基氧伸丙基烷基醚等聚氧伸烷基烷基醚；山梨糖醇酐脂肪酸酯、聚氧伸乙基山梨糖醇酐脂肪酸酯、聚氧伸乙基脂肪酸酯等，從水中油型乳化液組成物的安定性的觀點及安全性的觀點來看，特佳為聚氧伸烷基烷基醚、聚氧伸乙基山梨糖醇酐脂肪酸酯。 [Component (B)] The surfactant of component (B) is not particularly limited as long as it can emulsify and disperse component (A) in water. It is preferably a non-ionic surfactant. Examples include polyoxyalkyl alkyl ethers such as polyoxyethyl alkyl ether and polyoxyethyl oxypropyl alkyl ether; sorbitan fatty acid esters, polyoxyethyl sorbitan fatty acid esters, polyoxyethyl fatty acid esters, etc. From the perspective of the stability and safety of the water-in-oil emulsion composition, polyoxyalkyl alkyl ethers and polyoxyethyl sorbitan fatty acid esters are particularly preferred.
此等的具體例可舉例如：聚氧伸乙基辛基醚、聚氧伸乙基壬基醚、聚氧伸乙基癸基醚、聚氧伸乙基氧伸丙基癸基醚、聚氧伸乙基月桂基醚、聚氧伸乙基氧伸丙基月桂基醚、聚氧伸乙基十三烷基醚、聚氧伸乙基氧伸丙基十三烷基醚、聚氧伸乙基鯨蠟基醚、聚氧伸乙基硬脂基醚、聚氧伸乙基油基醚、聚氧伸乙基山梨糖醇酐單月桂酸酯、聚氧伸乙基山梨糖醇酐單棕櫚酸酯、聚氧伸乙基山梨糖醇酐單硬脂酸酯、聚氧伸乙基山梨糖醇酐參硬脂酸酯、聚氧伸乙基山梨糖醇酐單油酸酯、聚氧伸乙基山梨糖醇酐參油酸酯。(B)成分能夠將此等非離子性界面活性劑單獨使用或併用2種以上。Specific examples of these include polyoxyethyl octyl ether, polyoxyethyl nonyl ether, polyoxyethyl decyl ether, polyoxyethyl oxypropyl decyl ether, polyoxyethyl lauryl ether, polyoxyethyl oxypropyl lauryl ether, polyoxyethyl tridecyl ether, polyoxyethyl oxypropyl tridecyl ether, polyoxyethyl cetyl ether, polyoxyethyl stearyl ether, polyoxyethyl oleyl ether, polyoxyethyl sorbitan monolaurate, polyoxyethyl sorbitan monopalmitate, polyoxyethyl sorbitan monostearate, polyoxyethyl sorbitan ginstearate, polyoxyethyl sorbitan monooleate, and polyoxyethyl sorbitan ginsoleate. Component (B) may be composed of these nonionic surfactants alone or in combination of two or more.
此外，也能夠使用：烷基硫酸鹽、烷基苯磺酸鹽、烷基磺基琥珀酸鹽、聚氧伸乙基烷基醚硫酸鹽、聚氧伸乙基烷基苯基醚硫酸鹽等陰離子性界面活性劑；四級銨鹽、烷基胺乙酸鹽等陽離子性界面活性劑；及烷基甜菜鹼、烷基咪唑啉等兩離子性界面活性劑等。In addition, alkyl sulfates, alkyl benzene sulfonates, alkyl sulfosuccinates, polyoxyethylidene alkyl ether sulfates, polyoxyethylidene alkylphenyl ether sulfates, etc. can also be used. Anionic surfactants; cationic surfactants such as quaternary ammonium salts and alkylamine acetates; and two-ionic surfactants such as alkyl betaines and alkyl imidazolines.
相對於(A)成分的量100質量份，(B)成分的添加量為2～30質量份。前述添加量較佳為2.5～25質量份，更佳為3～20質量份，再更佳為4～15質量份。如果前述添加量為未達2質量份，則水中油型乳化液組成物的安定性惡化，如果前述添加量超過30質量份，則由水中油型乳化液組成物所形成的膜的被膜特性惡化。The amount of component (B) added is 2 to 30 parts by mass relative to 100 parts by mass of component (A). The amount added is preferably 2.5 to 25 parts by mass, more preferably 3 to 20 parts by mass, and even more preferably 4 to 15 parts by mass. If the amount added is less than 2 parts by mass, the stability of the oil-in-water emulsion composition deteriorates, and if the amount added exceeds 30 parts by mass, the film properties of the film formed by the oil-in-water emulsion composition deteriorate.
上述界面活性劑較佳是具有HLB(親水親油平衡)值3.0～19.0。當併用2種以上時，宜HLB值的加權平均成為7.0～17.0。The above surfactants preferably have an HLB (hydrophile-lipophile balance) value of 3.0 to 19.0. When two or more surfactants are used in combination, the weighted average of the HLB values is preferably 7.0 to 17.0.
[(C)成分] 本發明的水中油型乳化液組成物能夠藉由下述方式來調製：將(C)成分也就是水與上述的(A)成分及(B)成分混合並依照慣用方法來使其乳化分散。(C)水宜較佳為離子交換水。相對於(A)成分的量100質量份，(C)水的含量為10～2,000質量份，較佳為50～1,000質量份。藉由將上述(A)～(C)成分混合並使其乳化分散，即能夠獲得水中油型乳化液組成物。雖通常會成為白色乳濁液，但當乳化粒子的平均粒徑為20 nm以下時，也有時會成為外觀為藍白色或透明的微乳化液。此外，能夠在使用時在所得的水中油型乳化液組成物中進一步加入水來稀釋後使用。用以稀釋的水的量並無特別限制，只要因應用途來適當調整即可。 [(C)Component] The oil-in-water emulsion composition of the present invention can be prepared by mixing component (C), that is, water, and the above-mentioned components (A) and (B), and emulsifying and dispersing them according to a conventional method. (C) Water is preferably ion exchange water. The content of (C) water is 10 to 2,000 parts by mass, preferably 50 to 1,000 parts by mass relative to 100 parts by mass of the component (A). By mixing the above components (A) to (C) and emulsifying and dispersing them, an oil-in-water emulsion composition can be obtained. Although it usually turns into a white emulsion, when the average particle size of the emulsified particles is 20 nm or less, it may turn into a microemulsion with a blue-white or transparent appearance. In addition, water can be further added to the obtained oil-in-water emulsion composition during use to dilute it before use. The amount of water used for dilution is not particularly limited, as long as it can be adjusted appropriately according to the purpose.
乳化溫度無特別限定，設為本發明的水中油型乳化液組成物的起火點以下即可。較佳為0～80℃，更佳為0～40℃。設為0～80℃，而容易乳化，且乳化組成物更安定。攪拌速度較佳為100～10,000 rpm，更佳為500～5,000 rpm。乳化時間無特別限定，當使用批次式的乳化機來製造時，較佳為1～240分鐘，當使用連續式的乳化機來製造時，較佳為1分鐘以下。乳化時的壓力不只常壓，也可為減壓或加壓。當在減壓或加壓下攪拌時，有時氣泡不容易混入而能夠有效地乳化。當設為減壓時，壓力較原料的蒸氣壓更加提高，而防止原料揮發。The emulsification temperature is not particularly limited, and it can be set below the ignition point of the water-oil emulsion composition of the present invention. It is preferably 0 to 80°C, and more preferably 0 to 40°C. When it is set to 0 to 80°C, it is easy to emulsify and the emulsified composition is more stable. The stirring speed is preferably 100 to 10,000 rpm, and more preferably 500 to 5,000 rpm. The emulsification time is not particularly limited. When a batch emulsifier is used for production, it is preferably 1 to 240 minutes, and when a continuous emulsifier is used for production, it is preferably less than 1 minute. The pressure during emulsification is not only normal pressure, but also reduced pressure or pressurized pressure. When stirring under reduced pressure or pressurized pressure, bubbles are sometimes not easily mixed in and effective emulsification can be achieved. When set to decompression, the pressure is higher than the vapor pressure of the raw material to prevent the raw material from volatilizing.
乳化機能夠使用例如：均勻混合機(PRIMIX公司)、均質分散機(PRIMIX公司)、AGI HOMO MIXER(PRIMIX公司)、將均勻混合機與均質分散機與anchor mixer組合而成的三軸型分散揉合機也就是COMBI MIX(PRIMIX公司)、具有由轉子及攪拌器所構成的攪拌部的膠體研磨機(IKA公司、PUC公司、日本精機製作所公司、IWAKI公司)、High Shear Mixers(silverson公司、PRIMIX公司)及藉由2片刀片的公轉運動及自轉運動及齒形的葉片的高速旋轉的攪拌機也就是HIVIS DISPER MIX 3D-5型(PRIMIX公司)等。Examples of emulsifiers that can be used include homomixers (PRIMIX), homodispersers (PRIMIX), AGI HOMO MIXER (PRIMIX), and triaxial dispersing kneaders that combine a homomixer, a homogeneous disperser, and an anchor mixer. The combined machines include COMBI MIX (PRIMIX company), colloid grinders with a stirring section composed of a rotor and a stirrer (IKA company, PUC company, Nippon Seiki Manufacturing Co., Ltd., IWAKI company), High Shear Mixers (silverson company, PRIMIX company) Company) and a mixer that utilizes the revolution and rotation of two blades and the high-speed rotation of toothed blades, namely HIVIS DISPER MIX 3D-5 (PRIMIX Company), etc.
水中油型乳化液組成物的黏度無特別指定，較佳為5～20,000 mPa・s，更佳為10～5,000 mPa・s，再更佳為20～2,000 mPa・s。如果絕對黏度為5 mPa・s以上，則無保存安定性降低的疑慮和被膜產生縮孔(cissing)的疑慮。另一方面，如果絕對黏度為20,000 mPa・s以下，則容易進行處理。再者，水中油型乳化組成物的絕對黏度為使用BM型旋轉黏度計來測得的25℃時的值。The viscosity of the oil-in-water emulsion composition is not particularly specified, but it is preferably 5 to 20,000 mPa·s, more preferably 10 to 5,000 mPa·s, and still more preferably 20 to 2,000 mPa·s. If the absolute viscosity is 5 mPa·s or more, there is no concern about the decrease in storage stability or the possibility of cissing in the film. On the other hand, if the absolute viscosity is 20,000 mPa·s or less, handling is easy. In addition, the absolute viscosity of the oil-in-water emulsion composition is the value measured at 25°C using a BM-type rotational viscometer.
水中油型乳化液組成物中的乳化粒子的平均粒徑較佳為500 nm以下，更佳為400 nm以下。如果平均粒徑為500 nm以下，則不會迅速發生分離。再者，平均粒徑的下限無特別限定，通常能夠設為100 nm以上、特別是150 nm以上。再者，平均粒徑的測定能夠以動態光散射法或雷射繞射法來進行測定，在本發明中為藉由雷射繞射法來進行的體積平均粒徑(累積平均直徑D50(中位徑))。動態光散射法的裝置可舉例如：N4PLUS(BECKMAN COULTER公司)、DelsaMax CORE(BECKMAN COULTER公司)、DelsaMax PRO(BECKMAN COULTER公司)等，雷射繞射法的裝置可舉例如：LA-920(堀場製作所公司製)、LA-960(堀場製作所公司製)、Partica LA-960V2(堀場製作所公司製)等。The average particle size of the emulsified particles in the water-oil emulsion composition is preferably 500 nm or less, more preferably 400 nm or less. If the average particle size is 500 nm or less, separation will not occur quickly. In addition, the lower limit of the average particle size is not particularly limited, and can usually be set to 100 nm or more, especially 150 nm or more. In addition, the average particle size can be measured by dynamic light scattering or laser diffraction. In the present invention, it is a volume average particle size (cumulative average diameter D50 (median diameter)) performed by laser diffraction. Examples of devices for the dynamic light scattering method include N4PLUS (Beckman Coulter), DelsaMax CORE (Beckman Coulter), and DelsaMax PRO (Beckman Coulter). Examples of devices for the laser diffraction method include LA-920 (Horiba, Ltd.), LA-960 (Horiba, Ltd.), and Partica LA-960V2 (Horiba, Ltd.).
[其它添加劑] 本發明的乳化液撥水劑組成物中，除了上述(A)～(C)成分以外，還能夠因應需要來調配各種添加劑。可包含例如：增稠劑、防凍劑、防腐劑、防鏽劑、抗氧化劑、及紫外線吸收劑等。 [實施例] [Other additives] In the emulsion water-repellent composition of the present invention, in addition to the above-mentioned components (A) to (C), various additives can be blended as needed. It may include, for example, thickeners, antifreezes, preservatives, anti-rust agents, antioxidants, and ultraviolet absorbers. [Example]
以下列舉實施例及比較例來更詳細說明本發明，但本發明並不受下述實施例所限制。再者，下述例中，份表示質量份，％表示質量％。平均粒徑為體積平均粒徑(累積平均直徑D50(中位徑))，並且為使用堀場製作所股份有限公司製雷射繞射/散射式粒徑分布測定裝置LA-960來測得的值。黏度為使用B型旋轉黏度計來在25℃測定的絕對黏度，並且為使用東機產業公司製的TVB-10型黏度計來測得的值。The following examples and comparative examples are given to illustrate the present invention in more detail, but the present invention is not limited by the following examples. In addition, in the following examples, part means mass part, and % means mass %. The average particle diameter is a volume average particle diameter (cumulative average diameter D50 (median diameter)), and is a value measured using a laser diffraction/scattering particle size distribution measuring device LA-960 manufactured by Horiba Manufacturing Co., Ltd. The viscosity is the absolute viscosity measured at 25°C using a B-type rotational viscometer, and is a value measured using a TVB-10 type viscometer manufactured by Toki Sangyo Co., Ltd.
以下說明實施例及比較例中所使用的(A)成分、(B)成分。 ＜(A-1)有機矽氧烷接枝聚乙烯醇系聚合物＞ ・(A-1[I]) 在具備滴液漏斗、冷卻管、溫度計及攪拌裝置的燒瓶中，饋入作為含有上述通式(4)表示的結構單元的聚乙烯醇系樹脂化合物的從日本合成化學工業公司取得的G-Polymer(OKS-1011；聚合度300，皂化率98.5％) 20 g、N-甲基吡咯啶酮180 g、三乙胺0.6 g、參(三甲基矽烷氧基)矽烷基丙基異氰酸酯52.5 g，並在90℃進行反應4小時。反應結束後，在水與甲醇的混合液中使產物析出，並進一步以水與甲醇混合液來反覆洗淨後，在70℃進行減壓乾燥24小時，而獲得58.0 g的固體的聚合物。藉由以THF作為溶劑的GPC來測得的數目平均分子量(Mn)以聚苯乙烯換算為26,000，分子量分布為1.61。 The (A) component and (B) component used in Examples and Comparative Examples are described below. <(A-1) Organosiloxane-grafted polyvinyl alcohol-based polymer> ・(A-1[I]) Into a flask equipped with a dropping funnel, a cooling tube, a thermometer, and a stirring device, G-Polymer obtained from Nippon Synthetic Chemical Industry Co., Ltd. as a polyvinyl alcohol-based resin compound containing the structural unit represented by the above general formula (4) was charged. (OKS-1011; degree of polymerization 300, saponification rate 98.5%) 20 g, N-methylpyrrolidone 180 g, triethylamine 0.6 g, ginseng(trimethylsilyloxy)silylpropyl isocyanate 52.5 g, And the reaction was carried out at 90°C for 4 hours. After the reaction, the product was precipitated in a mixture of water and methanol, washed repeatedly with a mixture of water and methanol, and then dried under reduced pressure at 70° C. for 24 hours to obtain 58.0 g of a solid polymer. The number average molecular weight (Mn) measured by GPC using THF as a solvent was 26,000 in polystyrene conversion, and the molecular weight distribution was 1.61.
・(A-1[II]) 使用與(A-1[I])相同的裝置，饋入作為含有上述通式(4)表示的結構單元的聚乙烯醇系樹脂化合物的從日本合成化學工業公司取得的G-Polymer(OKS-1083；聚合度1,900，皂化率99.8％) 20 g、N-甲基吡咯啶酮180 g、三乙胺0.6 g、參(三甲基矽烷氧基)矽烷基丙基異氰酸酯52.5 g，並在90℃進行反應4小時。反應結束後，在水與甲醇的混合液中使產物析出，並進一步以水與甲醇混合液來反覆洗淨後，在70℃進行減壓乾燥24小時，而獲得65.5 g的固體的聚合物。藉由以THF作為溶劑的GPC來測得的數目平均分子量(Mn)以聚苯乙烯換算為68,000，分子量分布為1.23。 ・(A-1[II]) Using the same apparatus as (A-1[I]), 20 g of G-Polymer (OKS-1083; polymerization degree 1,900, saponification rate 99.8%) obtained from Nippon Synthetic Chemical Industry Co., Ltd., which is a polyvinyl alcohol-based resin compound containing a structural unit represented by the above general formula (4), 180 g of N-methylpyrrolidone, 0.6 g of triethylamine, and 52.5 g of tris(trimethylsilyloxy)silylpropyl isocyanate were fed and reacted at 90°C for 4 hours. After the reaction was completed, the product was precipitated in a mixed solution of water and methanol, and after further repeated washing with a mixed solution of water and methanol, it was dried under reduced pressure at 70°C for 24 hours to obtain 65.5 g of a solid polymer. The number average molecular weight (Mn) measured by GPC using THF as a solvent was 68,000 in terms of polystyrene, and the molecular weight distribution was 1.23.
＜(A-2)揮發性油＞ ・(A-2[I])：異十二烷(黏度1.4 mm 2/s) ・(A-2[II])：十甲基環五矽氧烷(黏度4 mm 2/s) ・(A-2[III])：二甲基聚矽氧烷(黏度6 mm 2/s)[比較例] 再者，(A-2[III])：二甲基聚矽氧烷由於為非揮發性，故不包含在揮發性油內。 ＜(A-2) Volatile oil＞ ・(A-2[I]): Isododecane (viscosity 1.4 mm 2 /s) ・(A-2[II]): Decamethylcyclopentasiloxane (Viscosity 4 mm 2 /s) ・(A-2[III]): Dimethylpolysiloxane (viscosity 6 mm 2 /s) [Comparative Example] Furthermore, (A-2[III]): 2 Methyl polysiloxane is not included in volatile oils because it is non-volatile.
＜(A)有機矽氧烷接枝聚乙烯醇系聚合物的溶液＞ ・(A[I])：(A-1[I])/(A-2[I])＝25/75，黏度：12 mm 2/s ・(A[II])：(A-1[I])/(A-2[II])＝25/75，黏度：600 mm 2/s ・(A[III])：(A-1[II])/(A-2[I])＝30/70，黏度：2,700 mm 2/s ・(A[IV])：(A-1[I])/(A-2[III])＝25/75，黏度：1,100 mm 2/s[比較例] <(A) Solutions of organosiloxane-grafted polyvinyl alcohol polymers> ・(A[I]): (A-1[I])/(A-2[I])=25/75, viscosity: 12 mm 2 /s ・(A[II]): (A-1[I])/(A-2[II])=25/75, viscosity: 600 mm 2 /s ・(A[III]): (A-1[II])/(A-2[I])=30/70, viscosity: 2,700 mm 2 /s ・(A[IV]): (A-1[I])/(A-2[III])=25/75, viscosity: 1,100 mm 2 /s [Comparative Example]
＜(B)界面活性劑＞ ・(B[I])：EMULGEN 104P(聚氧伸乙基[4]月桂基醚)，HLB＝9.7，花王公司製 ・(B[II])：EMULGEN 123P(聚氧伸乙基[23]月桂基醚)，HLB＝16.9，花王公司製 ・(B[III])：RHEODOL TW-O106V(聚氧伸乙基[6]山梨糖醇酐單油酸酯)，HLB＝10.0，花王公司製 ・(B[IV])：NONION ST-60(聚氧伸乙基[20]山梨糖醇酐單硬脂酸酯)，HLB＝14.9，日油公司製 ＜(B) Surfactant＞ ・(B[I]): EMULGEN 104P (polyoxyethylidene[4]lauryl ether), HLB=9.7, manufactured by Kao Corporation ・(B[II]): EMULGEN 123P (polyoxyethylidene[23]lauryl ether), HLB=16.9, manufactured by Kao Corporation ・(B[III]): RHEODOL TW-O106V (polyoxyethylene [6] sorbitan monooleate), HLB = 10.0, manufactured by Kao Corporation ・(B[IV]): NONION ST-60 (polyoxyethylene [20] sorbitan monostearate), HLB = 14.9, manufactured by NOF Corporation
[實施例1] 調配有機矽氧烷接枝聚乙烯醇系聚合物的溶液(A[I])66.0 g、聚氧伸乙基[4]月桂基醚(B[I])1.65 g、聚氧伸乙基[23]月桂基醚(B[II])4.95 g、及(C)離子交換水19.8 g，並以T.K.均勻混合機(PRIMIX公司)3,000 rpm來攪拌3分鐘而使其乳化，並以T.K.均質分散機(PRIMIX公司)1,500 rpm來攪拌15分鐘。然後，加入(C)水56.55 g、作為防腐劑的苯甲酸鈉0.75 g、檸檬酸0.3 g，並以T.K.均勻混合機以1,500 rpm來攪拌3分鐘，而獲得水中油型乳化液組成物(1)。乳化液組成物(1)的乳化粒子的平均粒徑為350 nm，黏度為330 mPa・s。 [Example 1] 66.0 g of a solution of organosiloxane-grafted polyvinyl alcohol polymer (A[I]), 1.65 g of polyoxyethylidene[4]lauryl ether (B[I]), and polyoxyethylidene[4] were prepared. 23] 4.95 g of lauryl ether (B[II]) and 19.8 g of (C) ion-exchange water were stirred for 3 minutes with a T.K. homomixer (PRIMIX company) at 3,000 rpm to emulsify, and homogeneously dispersed with a T.K. machine (PRIMIX Inc.) at 1,500 rpm for 15 minutes. Then, 56.55 g of (C) water, 0.75 g of sodium benzoate as a preservative, and 0.3 g of citric acid were added, and stirred for 3 minutes with a T.K. homomixer at 1,500 rpm to obtain an oil-in-water emulsion composition (1) . The average particle size of the emulsified particles of the emulsion composition (1) is 350 nm, and the viscosity is 330 mPa·s.
[實施例2] 調配有機矽氧烷接枝聚乙烯醇系聚合物的溶液(A[I])66.0 g、聚氧伸乙基[23]月桂基醚(B[II])4.95 g、聚氧伸乙基[6]山梨糖醇酐單油酸酯(B[III])1.65 g、及(C)離子交換水19.8 g，並以T.K.均勻混合機(PRIMIX公司)3,000 rpm來攪拌3分鐘而使其乳化，並以T.K.均質分散機(PRIMIX公司)1,500 rpm來攪拌15分鐘。然後，加入(C)水56.55 g、作為防腐劑的苯甲酸鈉0.75 g、檸檬酸0.3 g，並以T.K.均勻混合機以1,500 rpm來攪拌3分鐘，而獲得水中油型乳化液組成物(2)。乳化液組成物(2)的乳化粒子的平均粒徑為300 nm，黏度為170 mPa・s。 [Example 2] 66.0 g of a solution of an organosiloxane-grafted polyvinyl alcohol polymer (A[I]), 4.95 g of polyoxyethylene[23]lauryl ether (B[II]), 1.65 g of polyoxyethylene[6]sorbitan monooleate (B[III]), and (C) 19.8 g of ion-exchanged water were prepared, and the mixture was emulsified by stirring at 3,000 rpm for 3 minutes using a T.K. homomixer (PRIMIX), and then stirred at 1,500 rpm for 15 minutes using a T.K. homodispersor (PRIMIX). Then, (C) 56.55 g of water, 0.75 g of sodium benzoate as a preservative, and 0.3 g of citric acid were added, and stirred at 1,500 rpm for 3 minutes using a T.K. homomixer to obtain a water-oil emulsion composition (2). The average particle size of the emulsified particles of the emulsion composition (2) was 300 nm, and the viscosity was 170 mPa・s.
[實施例3] 調配有機矽氧烷接枝聚乙烯醇系聚合物的溶液(A[II])75.0 g、聚氧伸乙基[20]山梨糖醇酐單硬脂酸酯(B[IV])7.5 g、及(C)離子交換水22.5 g，並以T.K.均勻混合機(PRIMIX公司)3,000 rpm來攪拌3分鐘而使其乳化，並以T.K.均質分散機(PRIMIX公司)1,500 rpm來攪拌15分鐘。然後，加入(C)水43.95 g、作為防腐劑的苯甲酸鈉0.75 g、檸檬酸0.3 g，並以T.K.均勻混合機以1,500 rpm來攪拌3分鐘，而獲得水中油型乳化液組成物(3)。乳化液組成物(3)的乳化粒子的平均粒徑為450 nm，黏度為150 mPa・s。 [Example 3] 75.0 g of a solution of an organosiloxane-grafted polyvinyl alcohol polymer (A[II]), 7.5 g of polyoxyethylene[20] sorbitan monostearate (B[IV]), and 22.5 g of (C) ion-exchanged water were prepared, and stirred at 3,000 rpm for 3 minutes with a T.K. homomixer (PRIMIX) to emulsify the mixture, and stirred at 1,500 rpm with a T.K. homodispersor (PRIMIX) for 15 minutes. Then, 43.95 g of (C) water, 0.75 g of sodium benzoate as a preservative, and 0.3 g of citric acid were added, and stirred at 1,500 rpm with a T.K. homomixer for 3 minutes to obtain an oil-in-water emulsion composition (3). The average particle size of the emulsified particles of the emulsion composition (3) is 450 nm and the viscosity is 150 mPa・s.
[實施例4] 調配有機矽氧烷接枝聚乙烯醇系聚合物的溶液(A[III])66.0 g、聚氧伸乙基[4]月桂基醚(B[I])0.825 g、聚氧伸乙基[23]月桂基醚(B[II])5.775 g、及(C)離子交換水19.8 g，並以T.K.均勻混合機(PRIMIX公司)3,000 rpm來攪拌3分鐘而使其乳化，並以T.K.均質分散機(PRIMIX公司)1,500 rpm來攪拌15分鐘。然後，加入(C)水56.55 g、作為防腐劑的苯甲酸鈉0.75 g、檸檬酸0.3 g，並以T.K.均勻混合機以1,500 rpm來攪拌3分鐘，而獲得水中油型乳化液組成物(4)。乳化液組成物(4)的乳化粒子的平均粒徑為280 nm，黏度為200 mPa・s。 [Example 4] 66.0 g of a solution of organosiloxane-grafted polyvinyl alcohol polymer (A[III]), 0.825 g of polyoxyethylidene[4]lauryl ether (B[I]), and polyoxyethylidene[4] were prepared. 23] 5.775 g of lauryl ether (B[II]) and 19.8 g of (C) ion-exchange water were stirred for 3 minutes with a T.K. homomixer (PRIMIX company) at 3,000 rpm to emulsify, and homogeneously dispersed with a T.K. machine (PRIMIX Inc.) at 1,500 rpm for 15 minutes. Then, 56.55 g of (C) water, 0.75 g of sodium benzoate as a preservative, and 0.3 g of citric acid were added, and stirred for 3 minutes with a T.K. homomixer at 1,500 rpm to obtain an oil-in-water emulsion composition (4) . The average particle diameter of the emulsified particles of the emulsion composition (4) is 280 nm, and the viscosity is 200 mPa·s.
[實施例5] 調配有機矽氧烷接枝聚乙烯醇系聚合物的溶液(A[I])66.0 g、聚氧伸乙基[4]月桂基醚(B[I])3.3 g、聚氧伸乙基[23]月桂基醚(B[II])9.9 g、及(C)離子交換水23.1 g，並以T.K.均勻混合機(PRIMIX公司)3,000 rpm來攪拌3分鐘而使其乳化，並以T.K.均質分散機(PRIMIX公司)1,500 rpm來攪拌15分鐘。然後，加入(C)水46.65 g、作為防腐劑的苯甲酸鈉0.75 g、檸檬酸0.3 g，並以T.K.均勻混合機以1,500 rpm來攪拌3分鐘，而獲得水中油型乳化液組成物(5)。乳化液組成物(5)的乳化粒子的平均粒徑為210 nm，黏度為620 mPa・s。 [Example 5] 66.0 g of a solution of organosiloxane-grafted polyvinyl alcohol polymer (A[I]), 3.3 g of polyoxyethylidene[4]lauryl ether (B[I]), and polyoxyethylidene[4] were prepared. 23] 9.9 g of lauryl ether (B[II]) and 23.1 g of (C) ion-exchange water were emulsified by stirring for 3 minutes with a T.K. homomixer (PRIMIX company) at 3,000 rpm, and homogeneously dispersed with a T.K. machine (PRIMIX Inc.) at 1,500 rpm for 15 minutes. Then, 46.65 g of (C) water, 0.75 g of sodium benzoate as a preservative, and 0.3 g of citric acid were added, and stirred for 3 minutes with a T.K. homomixer at 1,500 rpm to obtain an oil-in-water emulsion composition (5) . The average particle size of the emulsified particles of the emulsion composition (5) is 210 nm, and the viscosity is 620 mPa·s.
[實施例6] 調配有機矽氧烷接枝聚乙烯醇系聚合物的溶液(A[I])66.0 g、聚氧伸乙基[4]月桂基醚(B[I])1.32 g、聚氧伸乙基[23]月桂基醚(B[II])1.98 g、及(C)離子交換水16.5 g，並以T.K.均勻混合機(PRIMIX公司)3,000 rpm來攪拌3分鐘而使其乳化，並以T.K.均質分散機(PRIMIX公司)1,500 rpm來攪拌15分鐘。然後，加入(C)水63.15 g、作為防腐劑的苯甲酸鈉0.75 g、檸檬酸0.3 g，並以T.K.均勻混合機以1,500 rpm來攪拌3分鐘，而獲得水中油型乳化液組成物(6)。乳化液組成物(6)的乳化粒子的平均粒徑為420 nm，黏度為170 mPa・s。 [Example 6] 66.0 g of a solution of organosiloxane-grafted polyvinyl alcohol polymer (A[I]), 1.32 g of polyoxyethylidene[4]lauryl ether (B[I]), and polyoxyethylidene[4] were prepared. 23] 1.98 g of lauryl ether (B[II]) and 16.5 g of (C) ion-exchange water were stirred for 3 minutes with a T.K. homomixer (PRIMIX company) at 3,000 rpm to emulsify them, and homogeneously dispersed with a T.K. machine (PRIMIX Inc.) at 1,500 rpm for 15 minutes. Then, 63.15 g of (C) water, 0.75 g of sodium benzoate as a preservative, and 0.3 g of citric acid were added, and stirred for 3 minutes with a T.K. homomixer at 1,500 rpm to obtain an oil-in-water emulsion composition (6) . The average particle size of the emulsified particles of the emulsion composition (6) is 420 nm, and the viscosity is 170 mPa·s.
[比較例1] 調配有機矽氧烷接枝聚乙烯醇系聚合物的溶液(A[IV])66.0 g、聚氧伸乙基[4]月桂基醚(B[I])1.65 g、聚氧伸乙基[23]月桂基醚(B[II])4.95 g、及(C)離子交換水19.8 g，並以T.K.均勻混合機(PRIMIX公司)3,000 rpm來攪拌3分鐘而使其乳化，並以T.K.均質分散機(PRIMIX公司)1,500 rpm來攪拌15分鐘。然後，加入(C)水56.55 g、作為防腐劑的苯甲酸鈉0.75 g、檸檬酸0.3 g，並以T.K.均勻混合機以1,500 rpm來攪拌3分鐘，而獲得水中油型乳化液組成物(7)。乳化液組成物(7)的乳化粒子的平均粒徑為430 nm，黏度為270 mPa・s。 [Comparative example 1] 66.0 g of a solution of organosiloxane-grafted polyvinyl alcohol polymer (A[IV]), 1.65 g of polyoxyethylidene[4]lauryl ether (B[I]), and polyoxyethylidene[4] were prepared. 23] 4.95 g of lauryl ether (B[II]) and 19.8 g of (C) ion-exchange water were stirred for 3 minutes with a T.K. homomixer (PRIMIX company) at 3,000 rpm to emulsify, and homogeneously dispersed with a T.K. machine (PRIMIX Inc.) at 1,500 rpm for 15 minutes. Then, 56.55 g of (C) water, 0.75 g of sodium benzoate as a preservative, and 0.3 g of citric acid were added, and stirred for 3 minutes with a T.K. homomixer at 1,500 rpm to obtain an oil-in-water emulsion composition (7) . The average particle size of the emulsified particles of the emulsion composition (7) is 430 nm, and the viscosity is 270 mPa·s.
[比較例2] 調配有機矽氧烷接枝聚乙烯醇系聚合物的溶液(A[I])66.0 g、聚氧伸乙基[4]月桂基醚(B[I])0.231 g、聚氧伸乙基[23]月桂基醚(B[II])0.693 g、及(C)離子交換水13.2 g，並以T.K.均勻混合機(PRIMIX公司)3,000 rpm來攪拌3分鐘而使其乳化，並以T.K.均質分散機(PRIMIX公司)1,500 rpm來攪拌15分鐘。然後，加入(C)水63.15 g、作為防腐劑的苯甲酸鈉0.75 g、檸檬酸0.3 g，並以T.K.均勻混合機以1,500 rpm來攪拌3分鐘，而獲得水中油型乳化液組成物(8)。乳化液組成物(8)的乳化粒子的平均粒徑為630 nm，黏度為120 mPa・s。 [Comparative Example 2] 66.0 g of a solution of an organosiloxane-grafted polyvinyl alcohol polymer (A[I]), 0.231 g of polyoxyethylene[4]lauryl ether (B[I]), 0.693 g of polyoxyethylene[23]lauryl ether (B[II]), and 13.2 g of (C) ion-exchanged water were prepared and stirred at 3,000 rpm for 3 minutes with a T.K. homomixer (PRIMIX) to emulsify the mixture, and then stirred at 1,500 rpm with a T.K. homodispersor (PRIMIX) for 15 minutes. Then, (C) 63.15 g of water, 0.75 g of sodium benzoate as a preservative, and 0.3 g of citric acid were added, and stirred at 1,500 rpm for 3 minutes using a T.K. homomixer to obtain a water-oil emulsion composition (8). The average particle size of the emulsified particles of the emulsion composition (8) was 630 nm, and the viscosity was 120 mPa・s.
[比較例3] 將有機矽氧烷接枝聚乙烯醇系聚合物的溶液(A[I])直接用於評估。 [Comparative Example 3] The solution of organosiloxane grafted polyvinyl alcohol polymer (A[I]) was used directly for evaluation.
上述例中所得的水中油型乳化液組成物(1～8)及有機矽氧烷接枝聚乙烯醇系聚合物的溶液(A[I])的調配組成(％)、平均粒徑、黏度、離心安定性、水分散性、塗佈性、乾燥性、及龜裂性的評估結果是如下述表所示。平均粒徑為體積平均粒徑(累積平均直徑D50(中位徑))，並且為使用堀場製作所股份有限公司製雷射繞射/散射式粒徑分布測定裝置LA-960來測得的值。黏度為使用B型旋轉黏度計來在25℃測定的絕對黏度，並且為使用東機產業公司製的TVB-10型黏度計來測得的值。The prepared composition (%), average particle size, and viscosity of the oil-in-water emulsion compositions (1 to 8) and the solution (A[I]) of the organosiloxane-grafted polyvinyl alcohol-based polymer obtained in the above example , centrifugal stability, water dispersibility, coating properties, drying properties, and cracking properties are evaluated as shown in the table below. The average particle diameter is a volume average particle diameter (cumulative average diameter D50 (median diameter)), and is a value measured using a laser diffraction/scattering particle size distribution measuring device LA-960 manufactured by Horiba Manufacturing Co., Ltd. The viscosity is the absolute viscosity measured at 25°C using a B-type rotational viscometer, and is a value measured using a TVB-10 type viscometer manufactured by Toki Sangyo Co., Ltd.
[離心安定性] 在離心管中加入水中油型乳化液組成物(1～8)25 g，並使用離心機H-19FM(KOKUSAN公司製)來進行3,000 rpm×50分鐘離心後，測定上層部及下層部的非揮發成分(105℃×3小時)。結果表示將上層部的非揮發成分除以下層部的非揮發成分而得的值。如果上層部的非揮發成分除以下層部的非揮發成分而得的值在0.95～1.05的範圍內，則設為合格。此值為越遠離1的值，則顯示越有會經時分離的可能性。 [Centrifugal stability] 25 g of the water-in-oil emulsion composition (1 to 8) was added to the centrifuge tube and centrifuged at 3,000 rpm for 50 minutes using a centrifuge H-19FM (manufactured by KOKUSAN Co., Ltd.), and the non-volatile components of the upper and lower layers were measured (105°C for 3 hours). The result is the value obtained by dividing the non-volatile components of the upper layer by the non-volatile components of the lower layer. If the value obtained by dividing the non-volatile components of the upper layer by the non-volatile components of the lower layer is within the range of 0.95 to 1.05, it is considered to be acceptable. The farther this value is from 1, the more likely it is to separate over time.
[水分散性] 對在離子交換水90 g中添加水中油型乳化液組成物(1～8)及有機矽氧烷接枝聚乙烯醇系聚合物的溶液(A[I])10 g並以玻璃棒來攪拌時的分散液的狀態，以肉眼來進行評估。 ＜水分散性判定基準＞ ○：均勻分散 ×：分離成兩層 [Water dispersibility] Add 10 g of the oil-in-water emulsion composition (1 to 8) and the organosiloxane-grafted polyvinyl alcohol polymer solution (A[I]) to 90 g of ion-exchange water and stir with a glass rod. The state of the dispersion is evaluated with the naked eye. ＜Water dispersibility judgment criteria＞ ○: Evenly dispersed ×: Separated into two layers
[塗佈性] 對以No.13的棒塗佈器來將水中油型乳化液組成物(1～8)塗佈(膜厚約20 μm)於未進行表面塗佈的板紙(15 cm×7 cm)後以30小時×36℃來使其乾燥而得的被膜的縮孔，以肉眼來進行評估。 ＜塗佈性判定基準＞ ○：無縮孔～塗佈面整體的未達3成有縮孔 △：塗佈面整體的3成以上且未達5成有縮孔 ×：塗佈面整體的5成以上有縮孔 將「○」或「△」設為合格。 [Coatability] Use a No. 13 rod coater to apply the oil-in-water emulsion compositions (1 to 8) (film thickness: about 20 μm) on uncoated cardboard (15 cm × 7 cm). The shrinkage cavities of the film dried at 36° C. for 30 hours were evaluated with the naked eye. ＜Coatability Judgment Criteria＞ ○: No shrinkage cavities - less than 30% of the entire coated surface has shrinkage cavities △: More than 30% but less than 50% of the entire coated surface has shrinkage cavities. ×: More than 50% of the entire coated surface has shrinkage cavities Set "○" or "△" as passed.
[乾燥性] 對以手指來觸摸在塗佈性中進行評估後的板紙的表面時的沾黏感(黏膩感)的有無或手指的痕跡的有無，進行評估。 ＜乾燥性判定基準＞ ○：無沾黏感及手指的痕跡 ×：有沾黏感或手指的痕跡 [Dryness] The presence or absence of a sticky feeling (sticky feeling) or the presence or absence of finger marks when the surface of the cardboard evaluated for coating properties is touched with a finger was evaluated. ＜Dryness Judgment Criteria＞ ○: No sticky feeling or finger marks ×: Sticky feeling or finger marks
[裂痕性] 將在塗佈性中進行評估後的板紙捲繞成直徑3.5 cm的筒後，以肉眼來評估裂痕。 ＜裂痕性判定基準＞ ○：無裂痕 ×：有裂痕 [crack property] The board paper evaluated for coatability was rolled into a cylinder with a diameter of 3.5 cm, and cracks were visually evaluated. <Criteria for Crackability Judgment> ○: No cracks ×: There are cracks
[表1] [Table 1]
[表2] [Table 2]
由表1表示可知，在實施例1～6中獲得安定性及水分散性良好的水中油型乳化液組成物，且所得的組成物的塗佈性、乾燥性、及裂痕性良好。As shown in Table 1, it can be seen that in Examples 1 to 6, oil-in-water emulsion compositions with good stability and water dispersibility were obtained, and the obtained compositions had good coating properties, drying properties, and cracking properties.
另一方面，比較例1將二甲基聚矽氧烷(黏度6 mm 2/s)用於(A-2)成分，結果乾燥性不良而被膜產生沾黏感。此外，比較例2的(B)成分的添加量為1.4質量份，結果平均粒徑大且離心安定性不良。比較例3不含(B)成分及(C)成分，結果水分散性不良。 On the other hand, in Comparative Example 1, dimethylpolysiloxane (viscosity 6 mm 2 /s) was used as the component (A-2). As a result, the drying properties were poor and the film had a sticky feeling. Furthermore, in Comparative Example 2, the addition amount of component (B) was 1.4 parts by mass. As a result, the average particle size was large and the centrifugation stability was poor. Comparative Example 3 does not contain the component (B) and the component (C), and as a result, the water dispersibility was poor.
本說明書包含下述態樣。 [1]：一種水中油型乳化液組成物，其特徵在於含有下述(A)～(C)成分： (A)將下述(A-1)成分與(A-2)成分混合而成的有機矽氧烷接枝聚乙烯醇系聚合物的溶液：100質量份； (A-1)具有下述通式(1)表示的結構單元的有機矽氧烷接枝聚乙烯醇系聚合物； 式(1)中，M 1及M 2為氫原子、乙醯基、或下述通式(2)表示的矽氧烷基，並且M 1及M 2之中的至少一方為下述通式(2)表示的矽氧烷基；A表示單鍵或連結基； 式(1)中，R 1為碳數1～6的1價有機基，R 2、R 3及R 4分別為碳數1～6的1價有機基或－OSiR 5R 6R 7表示的矽烷氧基，R 5、R 6及R 7分別為碳數1～6的1價有機基；n為1～10的整數，a為0～2的整數； (A-2)揮發性油； (B)從非離子性界面活性劑、陰離子性界面活性劑、陽離子性界面活性劑、及兩離子性界面活性劑之中選出的至少1種界面活性劑；2～30質量份； (C)水：10～2,000質量份。 [2]：如上述[1]的水中油型乳化液組成物，其中，前述通式(1)中的A為單鍵。 [3]：如上述[1]或上述[2]中任一項的水中油型乳化液組成物，其中，前述(A-1)成分的有機矽氧烷接枝聚乙烯醇系聚合物進一步具有下述通式(3)表示的結構單元，且以GPC來測定的聚苯乙烯換算的數目平均分子量(Mn)為5,000～500,000； 式(3)中，M 3為氫原子、乙醯基、或前述通式(2)表示的矽氧烷基。 [4]：如上述[1]至上述[3]中任一項的水中油型乳化液組成物，其中，前述通式(2)中，n為3，R 2、R 3及R 4為甲基，a為0。 [5]：如上述[1]至上述[4]中任一項的水中油型乳化液組成物，其中，前述(A-2)成分的揮發性油為25℃時的黏度為未達6 mm 2/s的矽氧油及/或烴油。 [6]：如上述[1]至上述[5]中任一項的水中油型乳化液組成物，其中，前述(B)成分包含非離子性界面活性劑。 [7]：如上述[6]的水中油型乳化液組成物，其中，前述非離子性界面活性劑為從聚氧伸烷基烷基醚及聚氧伸乙基山梨糖醇酐脂肪酸酯之中選出的1種以上。 [8]：如上述[1]至上述[7]中任一項的水中油型乳化液組成物，其中，前述水中油型乳化液組成物中的乳化粒子的平均粒徑為500 nm以下。 The present specification includes the following aspects. [1]: A water-in-oil emulsion composition characterized by containing the following components (A) to (C): (A) 100 parts by weight of a solution of an organic silicone grafted polyvinyl alcohol polymer obtained by mixing the following components (A-1) and (A-2); (A-1) an organic silicone grafted polyvinyl alcohol polymer having a structural unit represented by the following general formula (1); In formula (1), M1 and M2 are hydrogen atoms, acetyl groups, or siloxane groups represented by the following general formula (2), and at least one of M1 and M2 is a siloxane group represented by the following general formula (2); A represents a single bond or a linking group; In formula (1), R1 is a monovalent organic group having 1 to 6 carbon atoms, R2 , R3 and R4 are each a monovalent organic group having 1 to 6 carbon atoms or a silaneoxy group represented by -OSiR5R6R7 , R5 , R6 and R7 are each a monovalent organic group having 1 to 6 carbon atoms; n is an integer from 1 to 10, and a is an integer from 0 to 2; (A-2) a volatile oil; (B) at least one surfactant selected from a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphiphilic surfactant; 2 to 30 parts by weight; (C) water: 10 to 2,000 parts by weight. [2]: The oil-in-water emulsion composition of [1] above, wherein A in the general formula (1) is a single bond. [3]: The oil-in-water emulsion composition of any one of [1] or [2] above, wherein the organosiloxane-grafted polyvinyl alcohol polymer of component (A-1) further has a structural unit represented by the following general formula (3), and has a polystyrene-equivalent number average molecular weight (Mn) of 5,000 to 500,000 as measured by GPC; In formula (3), M3 is a hydrogen atom, an acetyl group, or a siloxyalkyl group represented by the general formula (2). [4]: The oil-in-water emulsion composition as described in any one of [1] to [3] above, wherein in the general formula (2), n is 3, R2 , R3 and R4 are methyl groups, and a is 0. [5]: The oil-in-water emulsion composition as described in any one of [1] to [4] above, wherein the volatile oil of the component (A-2) is a silicone oil and/or hydrocarbon oil having a viscosity of less than 6 mm2 /s at 25°C. [6]: The oil-in-water emulsion composition as described in any one of [1] to [5] above, wherein the component (B) contains a non-ionic surfactant. [7]: The oil-in-water emulsion composition of [6], wherein the non-ionic surfactant is one or more selected from polyoxyalkylene alkyl ethers and polyoxyethylene sorbitan fatty acid esters. [8]: The oil-in-water emulsion composition of any one of [1] to [7], wherein the average particle size of the emulsified particles in the oil-in-water emulsion composition is 500 nm or less.
再者，本發明並不受上述實施形態所限定。上述實施形態只是例示，只要具有與本發明的申請專利範圍中所記載的技術思想實質上相同的構成且產生相同的作用效果，無論是何種，都包含在本發明的技術範圍內。In addition, the present invention is not limited to the above-described embodiment. The above-described embodiments are only examples, and any embodiments that have substantially the same configuration as the technical ideas described in the claimed scope of the present invention and produce the same effects are included in the technical scope of the present invention.
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