JP6554021B2 - Method for producing non-spherical biodegradable polymer powder and cosmetics - Google Patents
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- 239000002994 raw material Substances 0.000 claims description 2
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- 241000195940 Bryophyta Species 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
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- 229920001610 polycaprolactone Polymers 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
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- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
- Biological Depolymerization Polymers (AREA)
- Cosmetics (AREA)
Description
本発明は、非球状生分解性ポリマー粉体の製造方法およびその製造方法によって製造された非球状生分解性ポリマー粉体を含有する化粧料に関するものである。 The present invention relates to a method for producing non-spherical biodegradable polymer powder and a cosmetic containing non-spherical biodegradable polymer powder produced by the method.
化粧料に毛穴ぼかし効果、素肌感・透明感だけでなく塗布時の感触やすべり性を向上させる目的で、架橋シリコーン粉体（例えば特許文献１参照。）、ナイロン粉体（例えば特許文献２参照。）、アクリル粉体（例えば特許文献３参照。）、ポリ乳酸粉体（例えば特許文献４参照。）などの球状ポリマー粉体を配合することがよく知られている。 Crosslinked silicone powder (see, for example, Patent Document 1), nylon powder (see, for example, Patent Document 2) for the purpose of improving the feeling of blurring and the feeling of natural skin and transparency as well as the feel and slipperiness at the time of application. It is well known to blend spherical polymer powders such as acrylic powder (see, for example, Patent Document 3), polylactic acid powder (see, for example, Patent Document 4).
中でも、ポリ乳酸粉体などの生分解性ポリマー粉体は、化粧品として使用された後に自然界に放出されても容易に分解するため、環境への負荷が小さく注目されている。 In particular, biodegradable polymer powders such as polylactic acid powder are attracting attention because they are easily decomposed even when released into nature after being used as cosmetics, and thus have a low environmental impact.
ポリマー粒子の開発が進むにつれ、近年では、光学特性やすべり性などの特性を変化させるために、球状からアスペクト比を変化させた楕円、板状、針状といった非球状ポリマー粒子の開発が盛んに行われるようになってきた。（例えば特許文献５〜７参照。） As the development of polymer particles progresses, in recent years development of non-spherical polymer particles such as oval, plate-like and needle-like with the aspect ratio changed from spherical in order to change the characteristics such as optical characteristics and slip Has come to be done. (For example, refer to Patent Documents 5 to 7.)
しかし、これらは主に石油原料から製造されたものであり、より安全なものを使いたいという消費者のニーズにはこたえられていない。また、これらのポリマー粒子は、自然界では容易に分解せず、化粧品として使用された後に自然界に放出されると、長期間ゴミとして堆積物として存在し、環境への負担が大きい。 However, these are mainly produced from petroleum raw materials and do not meet the consumer's need to use safer ones. In addition, these polymer particles do not easily decompose in the natural world, and when they are used as cosmetics and then released to the natural world, they are present as deposits for a long time as waste and have a large burden on the environment.
本発明は、前述のような問題点に鑑みてなされたもので、環境への負荷が小さく、毛穴ぼかし効果、素肌感・透明感、塗布時の感触やすべり性に加え、付着性を向上させた非球状生分解性ポリマー粉体の製造方法を提供するとともに、この製造方法によって製造された非球状生分解性ポリマー粉体を含有することにより、付着性に優れた化粧料を提供することを目的とするものである。 The present invention has been made in view of the above-mentioned problems, and has a small load on the environment, and in addition to the pore blurring effect, the feeling of bare skin and transparency, the feeling and slipperiness at the time of application, adhesion is improved. It is an object of the present invention to provide a method for producing non-spherical biodegradable polymer powder and providing a cosmetic excellent in adhesion by containing the non-spherical biodegradable polymer powder produced by this production method. It is the purpose.
本発明者らは鋭意研究を重ねた結果、非水溶性の生分解性ポリマー微粒子が水溶性材料からなるマトリックス中に分散している樹脂組成物を一定形状の孔を有するノズルより溶融吐出し、それを水洗することにより、１．５以上のアスペクト比を有する非球状ポリマー粒子が効率よく製造できることを見出し、その非球状生分解性ポリマー粉体を肌へ塗布した際に、毛穴ぼかし効果、素肌感・透明感、塗布時の感触やすべり性に加え、付着性が向上できることを見出し、本発明を完成させるに至った。 As a result of intensive studies, the present inventors melt and discharge a resin composition in which non-water-soluble biodegradable polymer fine particles are dispersed in a matrix made of a water-soluble material from a nozzle having holes of a predetermined shape. It is found that by washing it with water, non-spherical polymer particles having an aspect ratio of 1.5 or more can be efficiently produced, and when the non-spherical biodegradable polymer powder is applied to the skin, the pore blurring effect, bare skin In addition to feeling, transparency, touch and slipperiness at the time of application, it has been found that adhesion can be improved, and the present invention has been completed.
要するに、前記目的を達成するために、第１発明による非球状生分解性ポリマー粉体の製造方法は、非水溶性の生分解性ポリマーと水溶性材料とを含む樹脂組成物を、直径が０．０５〜２．０ｍｍの範囲で、長さが２０ｍｍ以上である毛管状の細孔を有するノズルから溶融吐出する工程を経ることにより、平均粒子径が０．１〜１００μｍで、平均アスペクト比が１．５以上である非球状生分解性ポリマー粉体を製造することを特徴とするものである。 In short, in order to achieve the above object, the method for producing a non-spherical biodegradable polymer powder according to the first aspect of the present invention provides a resin composition comprising a water-insoluble biodegradable polymer and a water-soluble material having a diameter of 0. The average particle diameter is 0.1 to 100 μm and the average aspect ratio is through a step of melting and discharging from a nozzle having capillary pores having a length of 20 mm or more in a range of 0.05 to 2.0 mm. A non-spherical biodegradable polymer powder having a particle size of 1.5 or more is produced.
次に、第２発明による化粧料は、第１発明に係る非球状生分解性ポリマー粉体の製造方法によって製造された非球状生分解性ポリマー粉体を含有してなることを特徴とするものである。 Next, the cosmetic according to the second invention is characterized by comprising the non-spherical biodegradable polymer powder produced by the method for producing the non-spherical biodegradable polymer powder according to the first invention. It is.
第１発明によれば、非球状生分解性ポリマー粉体は、細孔の直径が０．０５〜２．０ｍｍの範囲であり、かつ細孔の長さが２０ｍｍ以上である毛管状の細孔を有するノズルより溶融吐出する製造工程を経ることで、形状の揃った非球状の粒子を効率よく形成することが可能となり、平均粒子径が０．１〜１００μｍで、平均アスペクト比が１．５以上である非球状生分解性ポリマー粉体を製造することができ、環境への負荷が小さく、肌へ塗布した際に、毛穴ぼかし効果、素肌感・透明感、塗布時の感触やすべり性に加え、付着性に優れた非球状生分解性ポリマー粉体を得ることができる。 According to the first invention, the non-spherical biodegradable polymer powder has capillary pores having a pore diameter in the range of 0.05 to 2.0 mm and a pore length of 20 mm or more. It is possible to efficiently form non-spherical particles having a uniform shape by passing through a manufacturing process of melting and discharging from a nozzle having a mean particle diameter of 0.1 to 100 μm and an average aspect ratio of 1.5. The above non-spherical biodegradable polymer powders can be manufactured, and the impact on the environment is small. When applied to the skin, the effect of blurring pores, feeling of skin / transparency, and touch and slipperiness during application In addition, a non-spherical biodegradable polymer powder having excellent adhesion can be obtained.
第２発明によれば、第１発明に係る非球状生分解性ポリマー粉体の製造方法によって製造された非球状生分解性ポリマー粉体を含有することにより、毛穴ぼかし効果、素肌感・透明感、塗布時の感触やすべり性に加え、付着性に優れた化粧料を得ることができる。 According to the second invention, by containing the non-spherical biodegradable polymer powder produced by the method for producing the non-spherical biodegradable polymer powder according to the first invention, pore blurring effect, bare skin feeling / transparency In addition to the feel and slipperiness at the time of application, a cosmetic excellent in adhesion can be obtained.
次に、本発明による非球状生分解性ポリマー粉体の製造方法および化粧料の具体的な実施の形態について説明する。 Next, specific embodiments of the method for producing non-spherical biodegradable polymer powder and the cosmetic according to the present invention will be described.
本発明による非球状生分解性ポリマー粉体を作製するには、次の手順が採られる。
１）非水溶性の生分解性ポリマーを水溶性材料に溶融分散させる。
２）上記１）の樹脂組成物を一定形状の細孔を有するノズルより溶融吐出させる。
３）上記２）の樹脂組成物を水洗し、水溶性材料を除去する。
The following procedure is taken to make the non-spherical biodegradable polymer powder according to the present invention.
1) A water-insoluble biodegradable polymer is melt-dispersed in a water-soluble material.
2) The resin composition of the above 1) is melted and discharged from a nozzle having pores of a predetermined shape.
3) Wash the resin composition of 2) above with water to remove the water-soluble material.
非水溶性の生分解性ポリマーとしては、ポリ乳酸、ポリカプロラクトン、ポリエチレンサクシネート、ポリブチレンサクシネート等のポリエステル系樹脂が挙げられ、生分解性のポリエステル系樹脂であれば限定されるものではなく、単独または２種以上を組み合わせて使用することができる。耐熱性と環境負荷の観点から環境循環型材料であるポリ乳酸が好ましく用いられる。 Examples of water-insoluble biodegradable polymers include polyester resins such as polylactic acid, polycaprolactone, polyethylene succinate and polybutylene succinate, and are not limited as long as they are biodegradable polyester resins. These can be used alone or in combination of two or more. From the viewpoint of heat resistance and environmental load, polylactic acid, which is an environmentally circulated material, is preferably used.
本発明の非球状分解性ポリマー粉体において、平均粒子径が１０μｍ以下のものを得たい場合、更にポリグリセリン脂肪酸エステルなどの分散剤を添加することが好ましい。本発明に用いることができるポリグリセリン脂肪酸エステルとしては、例えばモノラウリン酸ポリグリセリル、モノミリスチン酸デカグリセリル、モノステアリン酸ポリグリセリル、モノイソステアリン酸ポリグリセリル、モノオレイン酸ポリグリセリル、ジイソステアリン酸ポリグリセリルからなる群から選択され、これらを単独または２種以上組み合わせて使用することができる。 In order to obtain a non-spherical degradable polymer powder of the present invention having an average particle diameter of 10 μm or less, it is preferable to further add a dispersant such as polyglycerin fatty acid ester. Examples of polyglycerin fatty acid esters that can be used in the present invention are selected from the group consisting of polyglyceryl monolaurate, decaglyceryl monomyristate, polyglyceryl monostearate, polyglyceryl monoisostearate, polyglyceryl monooleate, polyglyceryl diisostearate, These can be used alone or in combination of two or more.
また、本発明におけるポリグリセリン脂肪酸エステルの添加量は、非水溶性の生分解性ポリマーに対し０．５〜５．０ｍａｓｓ％の範囲が好ましく、１．０〜３．０ｍａｓｓ％の範囲がより好ましい。添加量０．５ｍａｓｓ％以下では粒子を小さくする効果は得られず、添加量５．０ｍａｓｓ％以上では５．０ｍａｓｓ％添加した時以上の効果は得られない。 Moreover, the range of 0.5-5.0 mass% is preferable with respect to a non-water-soluble biodegradable polymer, and, as for the addition amount of the polyglyceryl fatty acid ester in this invention, the range of 1.0-3.0 mass% is more preferable. . When the addition amount is 0.5 mass% or less, the effect of reducing the particle size can not be obtained, and when the addition amount is 5.0 mass% or more, the effect more than 5.0 mass% is not obtained.
水溶性材料としてはポリエチレングリコール等のポリアルキレンオキシド、ポリアクリル酸等のポリアルケンカルボン酸が挙げられ、これらは単独重合体もしくは共重合体、さらにはこれらの塩を使用することができ、これらを単独または２種以上組み合わせて使用することができる。 Examples of water-soluble materials include polyalkylene oxides such as polyethylene glycol, and polyalkene carboxylic acids such as polyacrylic acid, which may be homopolymers or copolymers, and further, salts thereof, It can be used alone or in combination of two or more.
本発明の非球状生分解性ポリマー粉体の製造方法において、溶融分散するための装置は特に限定されるものではなく、ロール、バンバリーミキサー、ニーダー、押出機等が用いられる。 In the method for producing the non-spherical biodegradable polymer powder of the present invention, the apparatus for melting and dispersing is not particularly limited, and rolls, Banbury mixers, kneaders, extruders and the like are used.
本発明の非球状生分解性ポリマー粉体の製造方法において、溶融吐出するための装置は、一定形状の細孔を有するノズルを設置することができれば特に限定されるものではなく、射出成型機、溶融プレス機、紡糸機、押出機等が用いられる。中でも溶融分散から溶融吐出までの製造を同時に行える押出機の使用は製造コストの面で望ましい。 In the method for producing non-spherical biodegradable polymer powder of the present invention, the apparatus for melting and discharging is not particularly limited as long as it can install a nozzle having pores of a fixed shape, and an injection molding machine, A melt press, a spinning machine, an extruder or the like is used. In particular, the use of an extruder capable of simultaneously performing the production from melt dispersion to melt discharge is desirable in terms of production cost.
本発明の非球状生分解性ポリマー粉体の製造方法において、溶融吐出する際の一定形状の細孔を有するノズルとは、直径が０．０５〜２．０ｍｍの範囲であり、かつ細孔の長さが２０ｍｍ以上である毛管状の細孔を有するノズルが望ましい。細孔の直径が０．０５ｍｍ以下だと生産能力が極めて劣り、細孔の長さが２０ｍｍに満たないと所望のアスペクト比を有する粒子を効率よく安定して得ることができない。また、孔数は1本以上であれば特に制限はないが、孔数が多いほど生産能力が向上するため、可能な限り多く設けることが製造コストの面で望ましい。 In the method for producing non-spherical biodegradable polymer powder of the present invention, the nozzle having pores of a predetermined shape at the time of melting and discharging has a diameter in the range of 0.05 to 2.0 mm, and A nozzle having capillary pores having a length of 20 mm or more is desirable. If the diameter of the pores is 0.05 mm or less, the production capacity is extremely poor, and if the pore length is less than 20 mm, particles having the desired aspect ratio can not be efficiently and stably obtained. The number of holes is not particularly limited as long as it is one or more. However, since the production capacity improves as the number of holes increases, it is desirable from the viewpoint of manufacturing cost to provide as many holes as possible.
本発明の非球状生分解性ポリマー粉体の製造方法において水溶性材料を除去する方法としては、水洗後に遠心分離およびろ過により分離することができ、分離した非球状生分解性ポリマー粉体は必要に応じて乾燥してから使用する。 In the method for producing the non-spherical biodegradable polymer powder of the present invention, the water-soluble material can be removed by centrifuging and filtering after water washing, and the separated non-spherical biodegradable polymer powder is necessary. Use after drying according to.
本発明の非球状生分解性ポリマー粉体の製造方法によって得られる非球状生分解性ポリマー粉体は、平均粒子径が０．１〜１００μｍで、平均アスペクト比が１．５以上であることを特徴とするものである。平均粒子径が０．１μｍより小さい場合には、生産効率が悪くなるためコストがかかるという懸念がある。一方、平均粒子径が１００μｍより大きい場合には、肌への付着性が悪くなるという懸念がある。
また、平均アスペクト比が１．５より小さい場合には、球状または略球状であり非球状とは言えない。平均アスペクト比が１．５以上であれば付着性に優れた粉体を得られるが、平均アスペクト比が２５より大きい場合には粒子同士の絡み合いによる凝集物を形成する恐れがあるため、平均アスペクト比は１．５〜２５がより好ましい。
The non-spherical biodegradable polymer powder obtained by the method for producing the non-spherical biodegradable polymer powder of the present invention has an average particle diameter of 0.1 to 100 μm and an average aspect ratio of 1.5 or more. It is a feature. If the average particle size is smaller than 0.1 μm, there is a concern that the production efficiency will deteriorate and the cost will increase. On the other hand, when the average particle size is larger than 100 μm, there is a concern that the adhesion to the skin may be deteriorated.
On the other hand, when the average aspect ratio is less than 1.5, it is spherical or substantially spherical and cannot be said to be non-spherical. If the average aspect ratio is 1.5 or more, a powder having excellent adhesion can be obtained. However, if the average aspect ratio is greater than 25, aggregates due to entanglement between particles may be formed. The ratio is more preferably 1.5-25.
本発明において、非球状生分解性ポリマー粉体の粒子径の測定方法としては、電子顕微鏡により観察した写真から画像的に抽出、判定する方法と、レーザー回折・散乱式粒度分布計などの粒度分布測定装置を用いて測定する方法などが挙げられるが、レーザー回折・散乱式粒度分布計による測定方法を用いるのが好ましい。 In the present invention, as a method of measuring the particle diameter of the non-spherical biodegradable polymer powder, a method of imagewise extraction and determination from a photograph observed with an electron microscope, and particle size distribution such as laser diffraction / scattering type particle size distribution analyzer Although the method etc. which measure using a measuring apparatus are mentioned, It is preferable to use the measuring method by a laser diffraction and scattering type particle size distribution meter.
本発明において、非球状生分解性ポリマー粉体のアスペクト比の測定方法としては、電子顕微鏡により観察した写真から画像的に抽出、判定する方法を用いるのが好ましい。 In the present invention, as a method of measuring the aspect ratio of the nonspherical biodegradable polymer powder, it is preferable to use a method of extracting and judging an image from a photograph observed by an electron microscope.
本発明の非球状生分解性ポリマー粉体には、それ自体従来公知の各種の表面処理を施すことができる。この表面処理の例としては、以下の処理が挙げられ、これらの処理を複数組み合わせて用いることも可能であるが、環境負荷の観点から天然素材を用いるのが好ましい。
ａ）フッ素化合物処理・・・パーフルオロアルキルリン酸エステル処理やパーフルオロアルキルシラン処理、パーフルオロポリエーテル処理、フルオロシリコーン処理、フッ素化シリコーン樹脂処理など
ｂ）シリコーン処理・・・メチルハイドロジェンポリシロキサン処理、ジメチルポリシロキサン処理、気相法テトラメチルテトラハイドロジェンシクロテトラシロキサン処理など
ｃ）ペンダント処理・・・気相法シリコーン処理後にアルキル鎖などを付加する処理
ｄ）シランカップリング剤処理
ｅ）チタンカップリング剤処理
ｆ）アルミニウムカップリング剤処理
ｇ）油剤処理
ｈ）Ｎ−アシル化リジン処理
ｉ）ポリアクリル酸処理
ｊ）金属石鹸処理・・・ステアリン酸塩処理やミリスチン酸塩処理など
ｋ）アクリル樹脂処理
ｌ）金属酸化物処理
The non-spherical biodegradable polymer powder of the present invention can be subjected to various surface treatments conventionally known per se. Examples of this surface treatment include the following treatments. A plurality of these treatments can be used in combination, but it is preferable to use natural materials from the viewpoint of environmental impact.
a) Fluorine compound treatment: perfluoroalkyl phosphate treatment, perfluoroalkylsilane treatment, perfluoropolyether treatment, fluorosilicone treatment, fluorinated silicone resin treatment, etc. b) Silicone treatment: methyl hydrogen polysiloxane Treatment, dimethylpolysiloxane treatment, vapor phase tetramethyltetrahydrogencyclotetrasiloxane treatment, etc. c) pendant treatment: treatment to add alkyl chain after vapor phase silicone treatment d) silane coupling agent treatment e) titanium Treatment with coupling agent f) Treatment with aluminum coupling agent g) Treatment with oil agent h) Treatment with N-acylated lysine i) Treatment with polyacrylic acid j) Treatment with metal soap ... Treatment with stearate or myristate k) Acrylic Resin treatment l) Metal oxide Management
本発明の非球状生分解性ポリマー粉体の製造方法によって製造された非球状生分解性ポリマー粉体は、化粧料に配合することにより、毛穴ぼかし効果、素肌感・透明感、塗布時の感触やすべり性に加え、付着性に優れた化粧料を得ることができる。この場合、配合量としては、０．１〜９９質量％が好ましく、より好ましくは０．５〜６０質量％である。化粧料の剤型としては、二層状、油中水型エマルジョン、水中油型エマルジョン、ジェル状、スプレー、ムース状、油性、固形状等の従来公知の剤型を使用することができる。勿論、本発明の化粧料を得るのに、他の公知の着色顔料、体質顔料、樹脂粉体、光輝性粉体、又はそれらの粉体の表面処理粉体と、界面活性剤、油剤を組み合わせることができるのは言うまでもない。 The non-spherical biodegradable polymer powder produced by the method for producing the non-spherical biodegradable polymer powder of the present invention is capable of blurring the pores, feeling of bare skin and transparency, and feeling at the time of application by being incorporated into cosmetics. In addition to slipperiness, a cosmetic with excellent adhesion can be obtained. In this case, the blending amount is preferably 0.1 to 99% by mass, and more preferably 0.5 to 60% by mass. As the dosage form of the cosmetic, conventionally known dosage forms such as bilayer, water-in-oil emulsion, oil-in-water emulsion, gel, spray, mousse, oil, solid and the like can be used. Of course, in order to obtain the cosmetic composition of the present invention, other known color pigments, extender pigments, resin powders, glitter powders, or surface-treated powders thereof are combined with a surfactant and an oil agent. It goes without saying that you can.
次に、本発明による非球状生分解性ポリマー粉体の製造方法および化粧料の具体的な実施例について、図面を参照しつつ説明する。なお、本発明は、以下に述べる実施例に限定されるものではない。 Next, specific examples of the method for producing the non-spherical biodegradable polymer powder and the cosmetic according to the present invention will be described with reference to the drawings. In addition, this invention is not limited to the Example described below.
（製造実施例１：平均粒子径６．０μｍ、平均アスペクト比１．６の楕円状生分解性ポリマー粉体の製造例）
非水溶性の生分解性ポリマーとしてポリ乳酸（ユニチカ製 テラマックＴＰ−４０００ＣＮ）３３質量部に、ポリアクリル酸（東亞合成製 ジュリマーＡＣ−１０Ｐ）６７質量部を加え、よく混合した後、０．５ｋｇ／ｈの速度にて同方向回転２軸押出機（東洋精機製作所製 プラストミル二軸セグメント押出機２Ｄ２５Ｗ）の供給口に供給した。同押出機のシリンダー温度を１８０℃として溶融分散を行い、直径１ｍｍかつ長さ４０ｍｍの２４本の細孔を有するノズルから樹脂組成物を押出して冷却固化した。その後、得られた樹脂組成物に対して１０倍の質量の水を用いて当該ポリアクリル酸を水洗除去し、ポリ乳酸の楕円状生分解性ポリマー粉体の縣濁液を得た。この縣濁液をろ過したうえで乾燥して、目的の楕円状生分解性ポリマー粉体を得た。（図１〜２参照。）
(Production Example 1: Production example of elliptical biodegradable polymer powder having an average particle diameter of 6.0 μm and an average aspect ratio of 1.6)
As a water-insoluble biodegradable polymer, 67 parts by mass of polyacrylic acid (Durimer AC-10P manufactured by Toagosei Co., Ltd.) is added to 33 parts by mass of polylactic acid (Terramac TP-4000CN manufactured by Unitika), and 0.5 kg after mixing well. The solution was supplied to the feed port of a co-rotating twin-screw extruder (Plastmill twin-screw segment extruder 2D25W, manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a speed of 1 / h. Melt dispersion was performed with the cylinder temperature of the extruder set to 180 ° C., and the resin composition was extruded from a nozzle having 24 pores with a diameter of 1 mm and a length of 40 mm, and cooled and solidified. Thereafter, the polyacrylic acid was removed by water washing using 10 times the mass of water with respect to the obtained resin composition, to obtain a suspension of polylactic acid elliptic biodegradable polymer powder. The suspension was filtered and dried to obtain the desired elliptical biodegradable polymer powder. (See FIGS. 1-2.)
（製造実施例２：平均粒子径６．１μｍ、平均アスペクト比２０．８の針状生分解性ポリマー粉体の製造例）
非水溶性の生分解性ポリマーとしてポリ乳酸（ユニチカ製 テラマックＴＰ−４０００ＣＮ）３３質量部に、ポリアクリル酸（東亞合成製 ジュリマーＡＣ−１０Ｐ）６７質量部を加え、よく混合した後、１．０ｋｇ／ｈの速度にて同方向回転２軸押出機（東洋精機製作所製 プラストミル二軸セグメント押出機２Ｄ２５Ｗ）の供給口に供給した。同押出機のシリンダー温度を１８０℃として溶融分散を行い、直径１ｍｍかつ長さ４０ｍｍの２４本の細孔を有するノズルから樹脂組成物を押出して冷却固化した。その後、得られた樹脂組成物に対して１０倍の質量の水を用いて当該ポリアクリル酸を水洗除去し、ポリ乳酸の針状生分解性ポリマー粉体の縣濁液を得た。この縣濁液をろ過したうえで乾燥して、目的の針状生分解性ポリマー粉体を得た。（図３〜４参照。）
(Production Example 2: Production example of acicular biodegradable polymer powder having an average particle diameter of 6.1 μm and an average aspect ratio of 20.8)
As a water-insoluble biodegradable polymer, 67 parts by mass of polyacrylic acid (Durimer AC-10P, manufactured by Toagosei Co., Ltd.) is added to 33 parts by mass of polylactic acid (Terramac TP-4000CN manufactured by Unitika), and 1.0 kg after mixing well. The solution was supplied to the feed port of a co-rotating twin-screw extruder (Plastmill twin-screw segment extruder 2D25W, manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a speed of 1 / h. Melt dispersion was performed with the cylinder temperature of the extruder set to 180 ° C., and the resin composition was extruded from a nozzle having 24 pores with a diameter of 1 mm and a length of 40 mm, and cooled and solidified. Thereafter, the polyacrylic acid was removed by water washing using 10 times the mass of water with respect to the obtained resin composition, to obtain a suspension of needle-like biodegradable polymer powder of polylactic acid. The suspension was filtered and dried to obtain the desired acicular biodegradable polymer powder. (See FIGS. 3-4.)
（製造比較例：平均粒子径６．２μｍ、平均アスペクト比１．１の真球状生分解性ポリマー粉体の製造例）
非水溶性の生分解性ポリマーとしてポリ乳酸（ユニチカ製 テラマックＴＰ−４０００ＣＮ）３３質量部に、ポリアクリル酸（東亞合成製 ジュリマーＡＣ−１０Ｐ）６７質量部を加え、よく混合した後、１．０ｋｇ／ｈの速度にて同方向回転２軸押出機（東洋精機製作所製 プラストミル二軸セグメント押出機２Ｄ２５Ｗ）の供給口に供給した。同押出機のシリンダー温度を１８０℃として溶融分散を行い、直径５ｍｍかつ長さ２０ｍｍの１本の孔を有するノズルから樹脂組成物を押出して冷却固化した。その後、得られた樹脂組成物に対して１０倍の質量の水を用いて当該ポリアクリル酸を水洗除去し、ポリ乳酸の真球状生分解性ポリマー粉体の縣濁液を得た。この縣濁液をろ過したうえで乾燥して、目的の球状生分解性ポリマー粉体を得た。（図５〜６参照。）
(Production Comparative Example: Production Example of True Spherical Biodegradable Polymer Powder having an Average Particle Diameter of 6.2 μm and an Average Aspect Ratio of 1.1)
As a water-insoluble biodegradable polymer, 67 parts by mass of polyacrylic acid (Durimer AC-10P, manufactured by Toagosei Co., Ltd.) is added to 33 parts by mass of polylactic acid (Terramac TP-4000CN manufactured by Unitika), and 1.0 kg after mixing well. The solution was supplied to the feed port of a co-rotating twin-screw extruder (Plastmill twin-screw segment extruder 2D25W, manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a speed of 1 / h. The melt and dispersion were performed with the cylinder temperature of the extruder set to 180 ° C., and the resin composition was extruded from a nozzle having one hole with a diameter of 5 mm and a length of 20 mm, and cooled and solidified. Thereafter, the polyacrylic acid was removed by water washing using 10 times the mass of water with respect to the obtained resin composition to obtain a suspension of true spherical biodegradable polymer powder of polylactic acid. The suspension was filtered and dried to obtain a target spherical biodegradable polymer powder. (See FIGS. 5-6.)
（実施例１：パウダーファンデーション）
下記の表１に示す処方に従ってパウダーファンデーションを得た。
(Example 1: Powder foundation)
A powder foundation was obtained according to the formulation shown in Table 1 below.
＜製造方法＞
成分Ａを粗混合した後、均一に溶解した成分Ｂを加えて良く攪拌した後に、容器に充填して製品を得た。
<Manufacturing method>
After roughly mixing component A, uniformly dissolved component B was added and stirred well, and then filled into a container to obtain a product.
（実施例２：パウダーファンデーション）
製造実施例１で作製した楕円状生分解性ポリマー粉体を、製造実施例２で作製した針状生分解性ポリマー粉体に代えた以外は、上記実施例１と同様にしてパウダーファンデーションを得た。
(Example 2: Powder foundation)
A powder foundation was obtained in the same manner as in Example 1 except that the elliptical biodegradable polymer powder produced in Production Example 1 was replaced with the needle-like biodegradable polymer powder produced in Production Example 2. It was.
（比較例１：パウダーファンデーション）
製造実施例１で作製した楕円状生分解性ポリマー粉体を、製造比較例で作製した球状生分解性ポリマー粉体に代えた以外は、上記実施例１と同様にしてパウダーファンデーションを得た。
（比較例２：パウダーファンデーション）
製造実施例１で作製した楕円状生分解性ポリマー粉体を、セリサイトＦＳＥに代えた以外は、上記実施例１と同様にしてパウダーファンデーションを得た。
(Comparative Example 1: Powder Foundation)
A powder foundation was obtained in the same manner as in Example 1 except that the elliptical biodegradable polymer powder produced in Production Example 1 was replaced with the spherical biodegradable polymer powder produced in Production Comparative Example.
(Comparative Example 2: Powder Foundation)
A powder foundation was obtained in the same manner as in Example 1 except that the elliptical biodegradable polymer powder produced in Production Example 1 was replaced with sericite FSE.
（平均粒子径）
製造実施例１および製造実施例２並びに製造比較例の生分解性ポリマー粉体については、図１、図３および図５に示されるように、レーザー回折・散乱式粒度分布計（日機装製 マイクロトラックＭＴ３３００ＥＸＩＩ）を用いて体積平均粒子径を測定した。
(Average particle size)
With respect to biodegradable polymer powders of Production Example 1 and Production Example 2 and Production Comparative Example, as shown in FIGS. 1, 3 and 5, a laser diffraction / scattering type particle size distribution analyzer (Nikkiso Microtrac) The volume average particle diameter was measured using MT3300EXII).
（平均アスペクト比）
製造実施例１および製造実施例２並びに製造比較例の生分解性ポリマー粉体については、図２、図４および図６に示されるように、走査型電子顕微鏡を用いて形状観察を行った。形状観察の際に撮影した写真からランダムに１００個の粒子を選び長径と短径を測定し、長径を短径で除した値であるアスペクト比を算出し、その平均値を平均アスペクト比とした。
(Average aspect ratio)
The shape of the biodegradable polymer powders of Production Example 1 and Production Example 2 and Production Comparative Example was observed using a scanning electron microscope as shown in FIG. 2, FIG. 4 and FIG. 100 particles were randomly selected from a photograph taken during shape observation, the major axis and minor axis were measured, the aspect ratio, which was a value obtained by dividing the major axis by the minor axis, was calculated, and the average value was taken as the average aspect ratio. .
以下、非球状生分解性ポリマー粉体及び化粧料の評価を示す。
（１）付着性
黒色の人口皮革にパフを用いて、それぞれの粉体を７ｃｍ×１０ｃｍの範囲に１０回重ねて塗布した。
Hereinafter, evaluation of non-spherical biodegradable polymer powder and cosmetics will be shown.
(1) Adhesion Each powder was applied 10 times in a range of 7 cm × 10 cm using a puff on black artificial leather.
図７の結果から、製造実施例２で作成した針状の生分解性ポリマー粉体はやや引っかかりが確認されるものの製造実施例１および製造実施例２で作成した非球状の生分解性ポリマー粉体は塗布後脱落せず均一に付着していることが判った。しかし、製造比較例で作製した球状生分解性ポリマー粉体（図７（ｃ）参照）は塗布による筋が確認される様に、重ね塗りの際にすでに塗布されていた粉体が脱落する現象が確認された。 From the results of FIG. 7, the needle-like biodegradable polymer powder prepared in Production Example 2 shows slight sticking. The non-spherical biodegradable polymer powder produced in Production Example 1 and Production Example 2 It was found that the body did not fall off after application and adhered uniformly. However, in the spherical biodegradable polymer powder (see FIG. 7 (c)) prepared in the manufacture comparative example, the phenomenon in which the powder that has already been applied during the recoating is dropped so that streaks due to application are confirmed. Was confirmed.
（２）パウダーファンデーションの評価
女性パネラー１０名に、パウダーファンデーションを使用してもらい、のびの良さ、毛穴の見えにくさ、カバー力、透明感および肌へのつきの良さをアンケート形式で回答してもらった。評価が悪い場合を０点、評価が良い場合を５点とし、パネラーの平均点数で評価結果とした。したがって点数が高いほど評価が優れていることを示している。その結果が表２に示されている。
(2) Evaluation of powder foundation A female panelist was asked to use powder foundation, and the questionnaire was used to answer goodness in spreading, difficulty in visualizing pores, covering power, transparency and goodness to skin. It was. When the evaluation was poor, 0 points were given, and when the evaluation was good, 5 points, and the average score of the panelists was used as the evaluation result. Therefore, the higher the score, the better the evaluation. The results are shown in Table 2.
表２の結果から、製造実施例１および製造実施例２で作製した非球状生分解性ポリマー粉体をパウダーファンデーションに配合した実施例１および実施例２は、製造比較例で作製した球状生分解性ポリマー粉体を配合した比較例と比較して、のびの良さを維持したまま、毛穴の見えにくさ、カバー力、透明感および肌へのつきの良さに優れることが判った。 From the results of Table 2, Example 1 and Example 2 in which the non-spherical biodegradable polymer powders prepared in Production Example 1 and Production Example 2 were blended in the powder foundation were spherical biodegradation produced in the production comparative example. As compared with the comparative example which mix | blended the property polymer powder, it turned out that it is excellent in the difficulty of seeing a pore, covering power, a transparency, and the good touch to skin, maintaining the goodness of spreading.
本発明の非球状生分解性ポリマー粉体の製造方法によって得られた非球状生分解性ポリマー粉体は、毛穴ぼかし効果、素肌感・透明感、塗布時の感触やすべり性に加え、肌への付着性およびカバー力に優れた化粧料を得ることができるので、産業上の利用効果が大である。
The non-spherical biodegradable polymer powder obtained by the method for producing the non-spherical biodegradable polymer powder of the present invention has a pore blurring effect, a feeling of skin / transparency, a touch and slipperiness during application, and is applied to the skin. Industrial use effect is large, because it is possible to obtain a cosmetic with excellent adhesion and covering power.
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