JP5085218B2 - Swelling oil-absorbing polymer particles - Google Patents

Description

  The present invention relates to swollen oil-absorbing polymer particles, and more particularly to swollen oil-absorbing polymer particles that exhibit selective and excellent absorbency with respect to highly polar oils such as fatty acids such as oleic acid and higher alcohols.

  Conventionally, inorganic porous powders such as silica and pearlite are known as oil-absorbing materials. However, although these inorganic porous powders have a high oil absorption rate, they have the disadvantage that they have a weak oil retention and absorb substances other than oil, such as water. In addition, when water is absorbed, it becomes difficult to absorb other components. Therefore, it is difficult to absorb the oil component in a system in which a large amount of water is present together with the oil component.

  In addition, swelling oil-absorbing polymer particles made of acrylic polymer particles obtained by copolymerizing a monomer mixture containing a (meth) acrylic acid alkyl ester and a crosslinkable monomer are known as an oil-absorbing material (Patent Document 1). To 3). However, these swelling oil-absorbing polymer particles exhibit oil-absorbing properties for all oil components (hydrocarbons, fats and oils, higher fatty acids, etc.) and are not suitable for applications that selectively absorb only specific oil components. Also, the oil absorption is not always satisfactory.

Japanese Patent No. 2813224 JP-A-5-209017 JP 2006-8757 A

  An object of the present invention is to provide swollen oil-absorbing polymer particles that have a low water-absorbing property and selectively exhibit a high oil-absorbing property with respect to highly polar oils such as fatty acids (such as oleic acid) and higher alcohols. is there.

  As a result of intensive studies to solve the above problems, the present inventors have polymerized a urethane prepolymer obtained by the reaction of a polyether polyol component having a specific structural unit and a polyisocyanate component with a specific chain extender. It was found that the polymer particles showed low absorbency for hydrocarbons such as water, silicone oil, and squalane, and selectively very high absorbency for highly polar oils such as oleic acid. Completed the invention.

That is, the present invention provides a urethane prepolymer having an isocyanate group at the molecular chain terminal obtained by a reaction between a polyol component containing 90% by mass or more of polytetramethylene glycol and a polyisocyanate component, and at least a trifunctional or more polyfunctional amine. A spherical swelling type oil-absorbing property comprising a polyurethane resin obtained by polymerizing with a chain extender containing, having an oleic acid absorption amount of at least twice its own weight , and an average particle diameter before swelling exceeding 4 μm and not exceeding 30 μm Polymer particles are provided.

  The swelling oil-absorbing polymer particles preferably have a water absorption amount, a squalane absorption amount, and a dimethicone absorption amount that are all less than 1 times their own weight.

The number average molecular weight of the polytetramethylene glycol is preferably 650 to 3000 . Before SL polyisocyanate component is preferably a non-aromatic polyisocyanate. The amount of residual isocyanate groups in the urethane prepolymer is preferably in the range of 2.0 to 10% by mass.

  The swelling oil-absorbing polymer particles can be composed of, for example, polyurethane resin particles obtained by polymerizing a dispersion obtained by dispersing a urethane prepolymer in an aqueous polyvinyl alcohol solution and adding a chain extender.

The present invention also relates to a method for producing the swellable oil-absorbing polymer particles, wherein the urethane prepolymer having an isocyanate group at the molecular chain terminal is obtained by a reaction between a polyol component containing 90% by mass or more of polytetramethylene glycol and a polyisocyanate component. A swelling type characterized in that a polymer is obtained and a polymer obtained by adding a chain extender containing at least a trifunctional or higher polyfunctional amine to a dispersion obtained by dispersing the obtained urethane prepolymer in an aqueous polyvinyl alcohol solution. A method for producing oil-absorbing polymer particles is provided .
In this specification, in addition to the above-described invention, a urethane prepolymer having an isocyanate group at the molecular chain terminal obtained by a reaction between a polyol component containing at least polytetramethylene glycol and a polyisocyanate component is a trifunctional or higher polyfunctional compound. A spherical swelling-type oil-absorbing polymer particle comprising a polyurethane resin obtained by polymerizing with a chain extender containing at least a functional amine and having an oleic acid absorption amount of at least twice its own weight is also described.

  The oil absorption performance exhibited by the swelling oil-absorbing polymer particles of the present invention is considered to be due to the polytetramethylene glycol skeleton in the polymer molecule. That is, fatty acids such as oleic acid and higher alcohols having a polarity relatively close to that of the polytetramethylene glycol skeleton are incorporated into the polytetramethylene glycol skeleton and have high absorbency, whereas the polytetramethylene glycol skeleton Compared with the polarity shown in FIG. 2, water such as water having a considerably high polarity and hydrocarbons such as squalane having a very low polarity are considered not to be incorporated into the polytetramethylene glycol skeleton so much and have low absorptivity. Moreover, since the swelling oil-absorbing polymer particles of the present invention have a three-dimensional network structure by crosslinking with a trifunctional or higher polyfunctional amine, the polymer particles do not reach dissolution but have an advantage that they remain swollen. In addition, since conventional inorganic porous powders such as silica and pearlite are absorbed by the porous material, in the presence of water and fatty acids such as oleic acid and oils such as higher alcohols, water and oleic acid are used. Both of fatty acids such as higher alcohols and oils such as higher alcohols are absorbed, and the absorption amount of fatty acids such as oleic acid and oils such as higher alcohols is substantially reduced. On the other hand, the swellable oil-absorbing polymer particles of the present invention are excellent in that they selectively absorb fatty acids such as oleic acid and higher alcohols even in the presence of water and exhibit high oil absorption. Therefore, for example, the swelling oil-absorbing polymer particles of the present invention are cosmetics for external use on the skin and hair, such as makeup cosmetics, skin care cosmetics, antiperspirant cosmetics, UV protective cosmetics, and hair cosmetics. It is useful as a raw material.

（式中、ｎは正の整数を示す）
で表されるポリテトラメチレングリコール（ＰＴＭＧ）を少なくとも含むポリオール成分（Ａ）［以下、ポリオール成分（Ａ）と称する場合がある］とポリイソシアネート成分（Ｂ）との反応により得られる分子鎖末端にイソシアネート基を有するウレタンプレポリマー（Ｃ）［以下、ウレタンプレポリマー（Ｃ）と称する場合がある］を、３官能以上の多官能アミンを少なくとも含む鎖延長剤（Ｄ）により高分子化して得られるポリウレタン樹脂からなる粒子である。 The swelling oil-absorbing polymer particles of the present invention have the following formula (1)

(In the formula, n represents a positive integer)
At the end of the molecular chain obtained by the reaction of the polyol component (A) containing at least polytetramethylene glycol (PTMG) represented by the formula (hereinafter sometimes referred to as polyol component (A)) and the polyisocyanate component (B). Obtained by polymerizing a urethane prepolymer (C) having an isocyanate group [hereinafter sometimes referred to as a urethane prepolymer (C)] with a chain extender (D) containing at least a trifunctional or higher polyfunctional amine. Particles made of polyurethane resin.

  The polyol component (A) only needs to contain at least polytetramethylene glycol (PTMG). Examples of the polyol component (A) include polyhydric alcohol, polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, polyacryl polyol, and castor oil. In the polyol component (A), examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, and 2-methyl. -1,3-trimethylenediol, 1,5-pentamethylenediol, neopentyl glycol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5 -Pentamethylenediol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), sugar alcohols (such as xylitol and sorbitol) ), And the like. Examples of the polyether polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and a plurality of alkylene oxides as monomer components such as an ethylene oxide-propylene oxide copolymer (alkylene oxide- And other alkylene oxide) copolymers.

  Examples of the polyester polyol include a condensation polymer of a polyhydric alcohol and a polyvalent carboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a reaction by three kinds of components: a polyhydric alcohol, a polyvalent carboxylic acid, and a cyclic ester. Things can be used. In the polycondensation product of a polyhydric alcohol and a polycarboxylic acid, the polyhydric alcohols exemplified above can be used as the polyhydric alcohol. On the other hand, examples of polycarboxylic acids include aliphatic dicarboxylic acids such as malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; 1,4-cyclohexane And alicyclic dicarboxylic acids such as dicarboxylic acids; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid, trimellitic acid, and the like. In the ring-opening polymer of cyclic ester, examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone. In the reaction product of the three types of components, those exemplified above can be used as the polyhydric alcohol, polycarboxylic acid, and cyclic ester. Examples of the polycarbonate polyol include a reaction product of a polyhydric alcohol and phosgene; a ring-opening polymer of a cyclic carbonate (such as alkylene carbonate). Specifically, in the reaction product of polyhydric alcohol and phosgene, the polyhydric alcohol exemplified above can be used as the polyhydric alcohol. In the ring-opening polymer of cyclic carbonate, examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like. In addition, the polycarbonate polyol should just be a compound which has a carbonate bond in a molecule | numerator, and the terminal is a hydroxyl group, and may have an ester bond with a carbonate bond.

The polyolefin polyol is a polyol having an olefin as a component (monomer component) of the skeleton (or main chain) of the polymer or copolymer and having at least two hydroxyl groups in the molecule (particularly at the terminal). The olefin may be an olefin having a carbon-carbon double bond at the terminal (for example, an α-olefin such as ethylene or propylene), or an olefin having a carbon-carbon double bond at a position other than the terminal. (For example, isobutene and the like) and diene (for example, butadiene, isoprene and the like) may be used. The polyacryl polyol is a polyol having (meth) acrylate as a component (monomer component) of a skeleton (or main chain) of a polymer or copolymer and having at least two hydroxyl groups in the molecule. (Meth) acrylate includes (meth) acrylic acid alkyl ester [for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid C _1-20 alkyl (meth) acrylates such as hexyl, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate Ester etc.] are preferably used. In addition, in polyolefin polyol and polyacryl polyol, in order to introduce a hydroxyl group in the molecule, α, β- having a hydroxyl group is used as a copolymer component of olefin or (meth) acrylate (a monomer component having copolymerizability). An unsaturated compound [for example, hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, etc.] can be used.

  As the polyol component (A), polyether polyol, polyester polyol, and polycarbonate polyol can be suitably used.

  The ratio of polytetramethylene glycol in the polyol component (A) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more. Most preferably, it is composed only of tetramethylene glycol.

  The number average molecular weight of polytetramethylene glycol is preferably about 650 to 3000, and more preferably about 1000 to 2000. When the number average molecular weight is less than 650, the content of hard segments (parts corresponding to the polyisocyanate component) in the final polyurethane resin increases, and the oil absorption characteristics tend to be lowered. Moreover, since the viscosity of a urethane prepolymer will increase when a number average molecular weight exceeds 3000, when manufacturing a polymer particle, it becomes the tendency for a handleability and workability | operativity to worsen.

  The polyisocyanate component (B) is not particularly limited as long as it is a compound having two or more isocyanate groups in the molecule, and conventionally known polyisocyanate compounds (diisocyanate compounds and other polyisocyanate compounds) can be used. The polyisocyanate component (B) can be used alone or in combination of two or more.

  Examples of the polyisocyanate component (B) include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanate compounds, and araliphatic polyisocyanate compounds.

  Examples of the aliphatic polyisocyanate compound include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl-1,5-pentamethylene Diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methylcaproate, lysine Such as isocyanate, and the like.

  Examples of the alicyclic polyisocyanate compound include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, methylene bis ( 4-cyclohexyl isocyanate) (= 4,4′-dicyclohexylmethane diisocyanate; hydrogenated MDI), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, Examples include 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, norbornane diisocyanate. ,

  Examples of the aromatic polyisocyanate compound include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthylene-1,4-diisocyanate, and naphthylene-1,5- Diisocyanate, 4,4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'- Such as methoxy-4,4'-diisocyanate.

  Examples of the araliphatic polyisocyanate compound include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,4-bis (1-isocyanate- 1-methylethyl) benzene, 1,3-bis (1-isocyanate-1-methylethyl) benzene, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene and the like.

  In addition, when yellowing of resin becomes a problem, non-aromatic polyisocyanate (aliphatic polyisocyanate compound, alicyclic polyisocyanate compound or araliphatic polyisocyanate compound) is used as the polyisocyanate component (B). Is preferred. As the polyisocyanate component (B), isophorone diisocyanate, 1,6-hexamethylene diisocyanate, hydrogenated MDI and the like are particularly preferable.

  There is no restriction | limiting in particular in the synthesis | combining method of a urethane prepolymer (C), It can manufacture by a well-known method. For example, a polyol component (A) is charged into a reactor equipped with a stirrer, a condenser, and a nitrogen gas stream device, and dehydrated under reduced pressure as necessary, and a polyisocyanate component (B) is added. A urethane-based composition containing a urethane prepolymer can be obtained by reacting at about 3 to 8 hours.

  The reaction can be carried out in the absence of a solvent, but a solvent can also be used to adjust the viscosity of the product. The solvent is not particularly limited as long as it is inert to the reaction, and for example, methyl ethyl ketone can be preferably used.

  In the reaction, a polymerization catalyst can be used. As the polymerization catalyst, a polymerization catalyst (curing catalyst) usually used when reacting polyisocyanate and polyol can be used. More specifically, examples of the polymerization catalyst include organic tin compounds, metal complexes, basic compounds such as amine compounds, and organic phosphoric acid compounds.

  Moreover, it is preferable that the quantity of NCO in a urethane prepolymer (C) is the range of 2.0-10 mass% of the whole urethane prepolymer (C), especially the range of 3.0-7.5 mass%. When there is too much quantity (mass%) of NCO, content of the hard segment (part corresponding to a polyisocyanate component) in a final polyurethane resin will increase, and it will become a tendency for oil absorption characteristics to fall. In addition, when the amount (% by mass) of NCO is too small, the viscosity of the urethane prepolymer (C) increases, so that the handleability and workability tend to be deteriorated in producing polymer particles.

  In the present invention, when the urethane prepolymer (C) is polymerized and granulated, a chain extender containing at least a trifunctional or higher polyfunctional amine is used. The trifunctional or higher polyfunctional amine is not particularly limited as long as it is an amine compound (polyamine) having a total of 3 or more primary amino groups and secondary amino groups, and typical examples thereof include diethylenetriamine, Examples include triethylenetetramine, tetraethylenepentamine, and dipropylenetriamine. When a polyfunctional amine having three or more functional groups is used as a chain extender, a three-dimensional network structure is formed, and polymer particles excellent in swelling properties that swell to the absorbed component but do not reach dissolution are obtained. .

  As the chain extender, other chain extenders can be used together with the trifunctional or higher polyfunctional amine. Examples of other chain extenders include bifunctional amines, amine chain extenders such as hydrazine and derivatives thereof, and polyhydric alcohols.

  Examples of the bifunctional amine include ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,3-pentamethylenediamine, 1,5-pentamethylenediamine, and 1,6-hexamethylenediamine. 1,2-propylenediamine, 1,2-butylenediamine, 2,3-butylenediamine, 1,3-butylenediamine, 2-methyl-1,5-pentamethylenediamine, 3-methyl-1,5-penta Aliphatic diamines such as methylenediamine, 2,4,4-trimethyl-1,6-hexamethylenediamine, 2,2,4-trimethyl-1,6-hexamethylenediamine; 1,3-cyclopentanediamine, 1, 4-cyclohexanediamine, 1,3-cyclohexanediamine, 1-amino-3-aminomethyl-3,5 5-trimethylcyclohexane, 1-amino-1-methyl-4-aminomethylcyclohexane, 1-amino-1-methyl-3-aminomethylcyclohexane, 4,4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (3-methyl-cyclohexylamine), methyl-2,3-cyclohexanediamine, methyl-2,4-cyclohexanediamine, methyl-2,6-cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4 -Alicyclic diamines such as bis (aminomethyl) cyclohexane, isophoronediamine, norbornanediamine; m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, naphthylene-1, 4-diamine, naphthylene-1,5 Diamine, 4,4′-diphenyldiamine, 4,4′-diphenylmethanediamine, 2,4′-diphenylmethanediamine, 4,4′-diphenyletherdiamine, 2-nitrodiphenyl-4,4′-diamine, 2, 2'-diphenylpropane-4,4'-diamine, 3,3'-dimethyldiphenylmethane-4,4'-diamine, 4,4'-diphenylpropanediamine, 3,3'-dimethoxydiphenyl-4,4'- Aromatic diamines such as diamines; 1,3-xylylenediamine, 1,4-xylylenediamine, α, α, α ′, α′-tetramethyl-1,3-xylylenediamine, α, α, α ′ , Α′-tetramethyl-1,4-xylylenediamine, ω, ω′-diamino-1,4-diethylbenzene, 1,3-bis (1-amino-1-methylethyl) benze , 1,4-bis (1-amino-1-methyl ethyl) benzene, 1,3-bis (alpha, alpha-dimethylaminomethyl) such as aromatic-aliphatic diamines such as benzene.

  Examples of hydrazine and derivatives thereof include hydrazine and dihydrazide compounds. Examples of the dihydrazide compounds include aliphatic dicarboxylic acid dihydrazides such as carbodihydrazide (carbohydrazide), oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide; isophthalic acid dihydrazide, diphthalide Aromatic dicarboxylic acid dihydrazides such as 1,4-cyclohexanedicarboxylic acid dihydrazide, and the like.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 1,5-pentamethylene diol, and neopentyl. Examples include glycol, 1,6-hexamethylenediol, glycerin, trimethylolpropane, trimethylolethane, 1,4-cyclohexanediol, bisphenols (such as bisphenol A), and sorbitol.

  The proportion of the trifunctional or higher polyfunctional amine in the chain extender (D) is preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 70% by mass or more.

  The amount of the chain extender (D) used is preferably equivalent to the isocyanate group at the end of the urethane prepolymer (C). For example, 0.8 to 1.2 equivalents of 1 equivalent of the isocyanate group. You may select from a range.

  For example, the swelling oil-absorbing polymer particles of the present invention are obtained by dispersing a urethane prepolymer (C) in an aqueous mixture (such as an aqueous solution) containing a dispersant, and then adding a chain extender (D). Can be obtained. Alternatively, the urethane prepolymer (C) can be obtained by dispersing simultaneously with the polymerization in an aqueous mixture (aqueous solution or the like) containing a dispersant and a chain extender (D).

  Examples of the dispersant include surfactants such as anionic surfactants, cationic surfactants, and nonionic surfactants; polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, starch, polyvinyl alkyl Examples thereof include polymer dispersants such as ether. Among these, a polymer dispersant, particularly polyvinyl alcohol is preferable. The polyvinyl alcohol is not particularly limited, and polyvinyl alcohol generally used as a dispersant, an emulsifier and the like can be used, and may be modified polyvinyl alcohol such as acetoacetylated polyvinyl alcohol. The polyvinyl alcohol may be either a partially saponified product or a completely saponified product, and two or more kinds of polyvinyl alcohols having different molecular weights or saponification degrees may be used in combination.

  Although the density | concentration of the dispersing agent in the water mixed liquid containing a dispersing agent can be suitably selected in the range which does not impair the dispersibility of a urethane prepolymer (C), it is 3-20 mass% normally, Preferably it is about 5-15 mass%. is there.

  The amount of urethane prepolymer (C) used (in terms of solid content) is preferably about 3 to 20 parts by mass, and more preferably about 5 to 15 parts by mass with respect to 100 parts by mass of the water mixture containing the dispersant. The urethane prepolymer (C) may be supplied to a water mixture containing a dispersant in a form dissolved in a solvent.

  The dispersion of the urethane prepolymer (C) can be prepared by mixing using a general stirring and mixing means used for emulsification, dispersion, and stirring. As the stirring and mixing means, for example, known stirring and mixing means such as a homomixer, a homogenizer, a high-pressure homogenizer, and an ultrasonic disperser can be used.

  The temperature at which the urethane prepolymer (C) is dispersed in the dispersant-containing water mixed solution is generally 0 to 50 ° C, preferably about 10 to 30 ° C. When the urethane prepolymer (C) is dispersed in a dispersant-containing water mixture such as an aqueous polyvinyl alcohol solution, an oil-in-water (O / W type) emulsion is usually obtained. The mixing time depends on the type of mixing apparatus, but is, for example, about 0.1 to 30 minutes, preferably about 1 to 10 minutes.

  Next, the chain extender (D) is added to the dispersion of the urethane prepolymer (C) thus prepared, and polymerized by chain extension to produce solid spherical polyurethane resin particles. The chain extender (D) can be used as it is or in the form of a solution dissolved in a solvent such as water.

  The temperature at the time of chain extension is, for example, about 20 to 100 ° C, preferably about 30 to 90 ° C. The time for chain extension is generally about 5 to 200 hours, preferably about 10 to 120 hours.

  After chain extension, the reaction mixture (suspension) is filtered, centrifuged, etc., separated into solid and liquid, and the resulting solid is washed with water and dried to give a spherical shape (preferably a true spherical shape) The polyurethane resin particles are obtained. The polyurethane resin particles thus obtained have the property of absorbing oil components and swelling. In particular, the polyurethane resin fine particles have low absorbency with respect to water and low polar components such as hydrocarbons and silicone oils, and specific oil agents such as higher fatty acids, higher alcohols, fats and oils, sebum, fatty acid esters, ketones, ethers. Highly oil-absorbing property selectively with respect to substances having medium polarity. Therefore, the oil component can be efficiently absorbed even in the presence of water. Moreover, compared with conventional oil-absorbing materials such as inorganic porous powder, it is excellent in oil retention and sustained release. Accordingly, the swelling oil-absorbing polymer particles of the present invention are a sustained release base material for oil components such as cosmetics for absorbing sebum, spilled oil and waste oil absorbents (recovery agents), fragrances, insecticides, and bactericides. It is useful as such.

  Since the swelling oil-absorbing polymer particles of the present invention have a polytetramethylene glycol skeleton in the polymer molecule, fatty acids such as oleic acid and higher alcohols having a polarity relatively close to that of the polytetramethylene glycol skeleton. Is incorporated into the polytetramethylene glycol skeleton and has a high absorbency, compared to the polarity exhibited by the polytetramethylene glycol skeleton, water such as water with a considerably higher polarity and hydrocarbons such as squalane with a much lower polarity, It is not so much absorbed in the polytetramethylene glycol skeleton and has low absorbency. Moreover, since the swelling oil-absorbing polymer particles of the present invention have a three-dimensional network structure by crosslinking with a trifunctional or higher polyfunctional amine, the polymer particles do not reach dissolution but remain in swelling. For example, the swellable oil-absorbing polymer particles of the present invention have a characteristic that the amount of oleic acid absorbed is at least twice that of its own weight (for example, about 2 to 10 times). The amount of oleic acid absorbed is preferably 3 times or more (for example, about 3 to 10 times), more preferably 4 times or more (for example, about 4 to 10 times). Further, the water absorption amount and the squalane absorption amount of the swelling oil-absorbing polymer particles of the present invention are each usually less than 1 times the own weight (for example, 0.001 to less than 1 time), preferably 0.8 times or less (for example, 0.001 to 0.8 times), more preferably 0.6 times or less (for example, 0.001 to 0.6 times). Furthermore, the dimethicone absorption amount of the swelling oil-absorbing polymer particles of the present invention is usually less than 1 time (for example, 0.01 or more and less than 1 time), preferably 0.6 or less (for example, 0.01 to 0.00). 6 times), more preferably 0.4 times or less (for example, 0.01 to 0.4 times). Therefore, the swelling oil-absorbing polymer particles of the present invention, unlike conventional absorption by porous materials such as inorganic porous powders such as silica and pearlite, selectively fatty acids such as oleic acid, even in the presence of water, Absorbs oils such as higher alcohols and exhibits high oil absorption. Therefore, for example, the swelling oil-absorbing polymer particles of the present invention are cosmetics for external use on the skin and hair, such as makeup cosmetics, skin care cosmetics, antiperspirant cosmetics, UV protective cosmetics, and hair cosmetics. Can be used as raw material.

  In addition, the absorption amount of oil or water means a saturated absorption amount, and can be measured by the following method. That is, 0.2 g of swelling oil-absorbing polymer particles are immersed in 10 ml of each oil (or water) and left for 3 days to sufficiently absorb the oil (or water) and then sucked for 10 minutes using a membrane filter. The excess oil (or water) is removed by filtration, and the amount of absorption (g / 100 g) is calculated from the weight increase of the swollen sample.

  The average particle diameter of the swellable oil-absorbing polymer particles (before swelling) of the present invention is, for example, 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably about 1 to 30 μm, as a median diameter. When the average particle size is less than 0.1 μm, the production tends to be difficult, and when the average particle size is too large, for example, when used as a raw material for cosmetics, the feeling of use tends to be impaired. In addition, the measurement of an average particle diameter disperse | distributes the obtained particle | grains with deionized water, and uses a laser scattering type particle size distribution measuring apparatus (for example, brand name "LA-920", the Horiba Seisakusho make), and is in volume reference mode. Can be done.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples. Unless otherwise specified, “part” represents “part by mass” and “%” represents “mass%”. The average particle diameter (median diameter) and the amount of absorption were measured by the methods described above.

Preparation Example 1
In a four-necked separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a condenser, 300 parts of polytetramethylene glycol (PTMG) (number average molecular weight 3000, hydroxyl value: 37.4 mg-KOH / g), methyl ethyl ketone Charge 20 parts, add isophorone diisocyanate [isocyanate content (NCO content): 37.8%, IPDI] 45.0 parts, dibutyltin dilaurate 0.04 part, under nitrogen flow at a temperature of 75-80 ° C. The reaction was performed for 5 hours to obtain an isocyanate group-terminated urethane prepolymer (prepolymer 1) having a residual isocyanate group of 2.5% in the prepolymer.

Preparation Example 2
In a four-necked separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a condenser, 300 parts of polytetramethylene glycol (number average molecular weight 650, hydroxyl value: 172.6 mg-KOH / g) and 20 parts of methyl ethyl ketone were added. Preparation, isophorone diisocyanate [isocyanate content (NCO content): 37.8%, IPDI] 205.5 parts, 0.04 part of dibutyltin dilaurate were added, and the reaction was carried out at 75-80 ° C. under a nitrogen stream for 5 hours. To obtain an isocyanate group-terminated urethane prepolymer (prepolymer 2) having a residual isocyanate group content of 7.7% in the prepolymer.

Preparation Example 3
In a four-necked separable flask equipped with a stirrer, nitrogen inlet tube, thermometer and condenser, polytetramethylene glycol (number average molecular weight 1000, hydroxyl value: 111.5 mg-KOH / g) 300 parts, methyl ethyl ketone 20 parts. Charge, isophorone diisocyanate [isocyanate content (NCO content): 37.8%, IPDI] 104.8 parts, 0.04 part of dibutyltin dilaurate were added, and the reaction was carried out at 75-80 ° C. under nitrogen stream for 5 hours. To obtain an isocyanate group-terminated urethane prepolymer (prepolymer 3) having a residual isocyanate group in the prepolymer of 3.6%.

Preparation Example 4
The product name “PCDL T-6002” (manufactured by Asahi Kasei Chemicals, polycarbonate diol, number average molecular weight 2000, hydroxyl value: 56.1 mg) was added to a four-necked separable flask equipped with a stirrer, nitrogen inlet tube, thermometer and condenser. -KOH / g) 300 parts, methyl ethyl ketone 20 parts, isophorone diisocyanate [isocyanate content (NCO content): 37.8%, IPDI] 67.4 parts, dibutyltin dilaurate 0.04 parts, 75 Reaction was performed at a temperature of -80 ° C. under a nitrogen stream for 5 hours to obtain an isocyanate group-terminated urethane prepolymer (prepolymer 4) having a residual isocyanate group of 3.5% in the prepolymer.

Preparation Example 5
In a four-necked separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a condenser, 300 parts of polytetramethylene glycol (number average molecular weight 650, hydroxyl value: 172.6 mg-KOH / g) and 20 parts of methyl ethyl ketone were added. Preparation, isophorone diisocyanate [isocyanate content (NCO content): 37.8%, IPDI] 247.6 parts, dibutyltin dilaurate 0.04 part was added, and the reaction was carried out at a temperature of 75 to 80 ° C. under a nitrogen stream for 5 hours. And an isocyanate group-terminated urethane prepolymer (prepolymer 5) having a residual isocyanate group of 10% in the prepolymer was obtained.

Example 1
A four-neck separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a condenser was charged with 100 parts of the trade name “PVA-205” (manufactured by Kuraray Co., Ltd., partially saponified polyvinyl alcohol) and 900 parts of deionized water. After heating to 90 ° C. to dissolve the polyvinyl alcohol, the solution was cooled to room temperature to obtain a dispersant solution. After adding 100 parts of prepolymer 1 to the obtained dispersant solution, it was mixed for 5 minutes at 8000 rpm using a homomixer to obtain a dispersion of urethane prepolymer. After charging 19 parts of a 10% aqueous solution of diethylenetriamine in the resulting dispersion, the temperature was raised to 80 ° C., and the reaction was carried out for 20 hours while maintaining the same temperature. Next, the dispersant was washed and dried to obtain spherical polyurethane resin fine particles 1. The median diameter of the obtained particles was 15 μm. Moreover, the absorption with respect to each oil and water was 695 g / 100 g of oleic acid, 594 g / 100 g of decanol, 15 g / 100 g of squalane, 11 g / 100 g of dimethicone, and 11 g / 100 g of water.

Example 2
A four-neck separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a condenser was charged with 100 parts of the trade name “PVA-205” (manufactured by Kuraray Co., Ltd., partially saponified polyvinyl alcohol) and 900 parts of deionized water. After heating to 90 ° C. to dissolve the polyvinyl alcohol, the solution was cooled to room temperature to obtain a dispersant solution. 100 parts of Prepolymer 2 was added to the obtained dispersant solution, and then mixed at 8000 rpm for 5 minutes using a homomixer to obtain a urethane prepolymer dispersion. After adding 75 parts of a 10% aqueous solution of isophoronediamine to the resulting dispersion, 30 parts of a 10% aqueous solution of diethylenetriamine was added, the temperature was raised to 80 ° C., and the reaction was carried out for 20 hours while maintaining the same temperature. Next, the dispersant was washed and dried to obtain spherical polyurethane resin fine particles 2. The median diameter of the obtained particles was 7 μm. Moreover, the absorption with respect to each oil and water was oleic acid 650g / 100g, decanol 562g / 100g, squalane 21g / 100g, dimethicone 8g / 100g, water 7g / 100g.

Example 3
A four-neck separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a condenser was charged with 100 parts of the trade name “PVA-205” (manufactured by Kuraray Co., Ltd., partially saponified polyvinyl alcohol) and 900 parts of deionized water. After heating to 90 ° C. to dissolve the polyvinyl alcohol, the solution was cooled to room temperature to obtain a dispersant solution. After adding 100 parts of prepolymer 3 to the obtained dispersant solution, it was mixed at 8000 rpm for 5 minutes using a homomixer to obtain a urethane prepolymer dispersion. To the obtained dispersion, 28 parts of a 10% aqueous solution of diethylenetriamine was added, the temperature was raised to 80 ° C., and the reaction was carried out for 20 hours while maintaining the same temperature. Next, the dispersant was washed and dried to obtain spherical polyurethane resin fine particles 3. The median diameter of the obtained particles was 12 μm. Moreover, the absorption with respect to each oil and water was oleic acid 536g / 100g, decanol 396g / 100g, squalane 56g / 100g, dimethicone 25g / 100g, water 40g / 100g.

Example 4 (referred to as a reference example)
A four-necked separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a condenser was charged with 100 parts of the trade name “PVA-205” (manufactured by Kuraray Co., Ltd., partially saponified polyvinyl alcohol) and 900 parts of deionized water. After heating to 90 ° C. to dissolve the polyvinyl alcohol, the solution was cooled to room temperature to obtain a dispersant solution. 80 parts of Prepolymer 3 and 20 parts of Prepolymer 4 were added to the resulting dispersant solution, and then mixed at 8000 rpm for 5 minutes using a homomixer to obtain a urethane prepolymer dispersion. After charging 28 parts of a 10% aqueous solution of diethylenetriamine in the obtained dispersion, the temperature was raised to 80 ° C., and the reaction was carried out for 20 hours while maintaining the same temperature. Next, the dispersant was washed and dried to obtain spherical polyurethane resin fine particles 4. The median diameter of the obtained particles was 16 μm. Moreover, the absorbability with respect to each oil and water was 442 g / 100 g of oleic acid, 314 g / 100 g of decanol, 48 g / 100 g of squalane, 22 g / 100 g of dimethicone, and 28 g / 100 g of water.

Example 5 (referred to as a reference example)
A four-neck separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a condenser was charged with 100 parts of the trade name “PVA-205” (manufactured by Kuraray Co., Ltd., partially saponified polyvinyl alcohol) and 900 parts of deionized water. After heating to 90 ° C. to dissolve the polyvinyl alcohol, the solution was cooled to room temperature to obtain a dispersant solution. 50 parts of Prepolymer 3 and Prepolymer 4 were added to the resulting dispersant solution, and then mixed at 8000 rpm for 5 minutes using a homomixer to obtain a urethane prepolymer dispersion. After charging 28 parts of a 10% aqueous solution of diethylenetriamine in the obtained dispersion, the temperature was raised to 80 ° C., and the reaction was carried out for 20 hours while maintaining the same temperature. Next, the dispersant was washed and dried to obtain spherical polyurethane resin fine particles 5. The median diameter of the obtained particles was 28 μm. Moreover, the absorption with respect to each oil and water was oleic acid 296g / 100g, decanol 211g / 100g, squalane 44g / 100g, dimethicone 20g / 100g, water 23g / 100g.

Example 6
A four-neck separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a condenser was charged with 100 parts of the trade name “PVA-205” (manufactured by Kuraray Co., Ltd., partially saponified polyvinyl alcohol) and 900 parts of deionized water. After heating to 90 ° C. to dissolve the polyvinyl alcohol, the solution was cooled to room temperature to obtain a dispersant solution. After adding 100 parts of prepolymer 5 to the obtained dispersant solution, it was mixed for 5 minutes at 8000 rpm using a homomixer to obtain a dispersion of urethane prepolymer. After charging 79 parts of a 10% aqueous solution of diethylenetriamine into the obtained dispersion, the temperature was raised to 80 ° C., and the reaction was carried out for 20 hours while maintaining the same temperature. Next, the dispersant was washed and dried to obtain spherical polyurethane resin fine particles 6. The median diameter of the obtained particles was 5 μm. Moreover, the absorption with respect to each oil and water was oleic acid 320g / 100g, decanol 260g / 100g, squalane 41g / 100g, dimethicone 14g / 100g, and water 1g / 100g.

Comparative Example 1
A four-necked separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a condenser was charged with 100 parts of the trade name “PVA-205” (manufactured by Kuraray Co., Ltd., partially saponified polyvinyl alcohol) and 900 parts of deionized water. After heating to 90 ° C. to dissolve the polyvinyl alcohol, the solution was cooled to room temperature to obtain a dispersant solution. After adding 100 parts of prepolymer 4 to the obtained dispersant solution, it was mixed for 5 minutes at 8000 rpm using a homomixer to obtain a dispersion of urethane prepolymer. After charging 27 parts of a 10% aqueous solution of diethylenetriamine into the obtained dispersion, the temperature was raised to 80 ° C., and the reaction was carried out for 20 hours while maintaining the same temperature. Next, the dispersant was washed and dried to obtain spherical polyurethane resin fine particles 8. The median diameter of the obtained particles was 8 μm. Moreover, the absorption with respect to each oil and water was oleic acid 54g / 100g, decanol 36g / 100g, squalane 24g / 100g, dimethicone 8g / 100g, and water 10g / 100g.

Comparative Example 2
Commercially available porous silica (oil absorption 300 ml / 100 g, median diameter 15 μm) was used. The absorbability with respect to each oil and water was 121 g / 100 g of oleic acid, 125 g / 100 g of decanol, 127 g / 100 g of squalane, 123 g / 100 g of dimethicone, and 182 g / 100 g of water.

  The above results are shown in Tables 1 and 2.

  As shown in the table, the polyurethane resin fine particles of the examples have very high oleic acid absorption, but low absorption of squalane, dimethicone and water. On the other hand, the fine particles of Comparative Example 1 have a low oleic acid absorption amount, an absorption amount equivalent to various absorbed components and no selectivity. The fine particles (porous silica) of Comparative Example 2 do not have a very high amount of oleic acid absorption, have the same absorption amount with respect to the component to be absorbed, have no selectivity, and have a high water absorption amount.

Claims (8)

A urethane prepolymer having an isocyanate group at the molecular chain terminal obtained by a reaction between a polyol component containing 90% by mass or more of polytetramethylene glycol and a polyisocyanate component is increased by a chain extender containing at least a trifunctional or higher polyfunctional amine. Spherical, swollen oil-absorbing polymer particles comprising a polyurethane resin obtained by molecularization, having an oleic acid absorption of at least twice its own weight , and an average particle diameter before swelling of more than 4 μm and not more than 30 μm .   The swollen oil-absorbing polymer particles according to claim 1, wherein the water absorption amount, the squalane absorption amount, and the dimethicone absorption amount are all less than 1 times their own weight.   The swelling oil-absorbing polymer particles according to claim 1 or 2, wherein the polytetramethylene glycol has a number average molecular weight of 650 to 3,000. The swelling oil-absorbing polymer particles according to any one of claims 1 to 3, which are spherical dry swelling oil -absorbing polymer particles.   The swelling type oil-absorbing polymer particle according to any one of claims 1 to 4, wherein the polyisocyanate component is a non-aromatic polyisocyanate.   The swelling type oil-absorbing polymer particles according to any one of claims 1 to 5, wherein the amount of residual isocyanate groups in the urethane prepolymer is 2.0 to 10% by mass.   The swelling type according to any one of claims 1 to 6, comprising polyurethane resin particles obtained by polymerizing a dispersion obtained by dispersing a urethane prepolymer in an aqueous polyvinyl alcohol solution by adding a chain extender. Oil-absorbing polymer particles. It is a manufacturing method of the swelling type oil-absorbing polymer particle in any one of Claims 1-7, Comprising: At the molecular chain terminal by reaction with the polyol component and polyisocyanate component which contain 90 mass% or more of polytetramethylene glycols Obtaining a urethane prepolymer having an isocyanate group, and adding a chain extender containing at least a trifunctional or higher polyfunctional amine to a dispersion obtained by dispersing the obtained urethane prepolymer in an aqueous polyvinyl alcohol solution, thereby polymerizing the urethane prepolymer. A method for producing swelling oil-absorbing polymer particles characterized by