JP5460429B2 - Textile treatment agent - Google Patents

Description

  The present invention relates to a fiber treatment agent.

  Development of fiber treatment agents containing functional substances such as fragrances and insect repellents is progressing in order to impart fragrance and insect repellent effects to clothing and the like. For example, Patent Document 1 discloses composite particles in which a perfume is absorbed in porous inorganic particles such as silica and zeolite Y, and a fiber softener composition including the composite particles and a fiber softener. However, zeolite Y has a pore size of 0.7 nm, and can only carry a perfume having a molecular size smaller than that. Silica gel and fumed silica have a structure in which primary particles of about 10 nm are aggregated and have pores of several nm to several tens of nm derived from voids between the primary particles. Therefore, it is difficult to control the release of the fragrance.

  On the other hand, mesoporous silica particles having pores (mesopores) having a uniform pore diameter of several nm are attracting attention as porous inorganic particles (Non-patent Document 1). For example, Patent Document 2 discloses a mesoporous medium having an average particle diameter of 0.01 to 5 μm in which a functional drug is supported in a fiber structure having one or more resin layers on one side. A functional fiber structure containing silica is disclosed. In particular, a mesoporous silica particle (hereinafter referred to as “hollow mesoporous silica particle”) having a mesoporous structure in the outer shell portion of the particle and having a cavity inside the outer shell portion (hereinafter also referred to as “hollow portion”). )) Can carry a large amount of the functional compound in the hollow part, and the release rate of the functional compound held in the hollow part to the outside of the particle can be controlled by controlling the structure of the particle. Therefore, hollow mesoporous silica particles are expected as a high-performance sustained release carrier. For example, Patent Document 3 discloses that composite silica particles having excellent perfume sustained release properties can be obtained by using hollow mesoporous silica particles as a sustained release carrier and supporting a perfume in the hollow part. Furthermore, Patent Document 4 discloses that perfume outflow into water can be suppressed by producing composite silica particles using hollow mesoporous silica particles that have been surface-treated with organosilane to reduce the mesopore diameter. Has been.

JP-A-5-209188 JP 2003-82580 A JP 2009-155400 A JP 2009-203116 A

C. T.A. Kresge, et. al. , Nature, 359, 710 (1992)

  However, when composite particles in which a functional substance is held in mesoporous silica particles are used as a component of a fiber treatment agent, there is a problem that the composite particles are difficult to adhere to fibers. In addition, there is a problem in that the functional substance held in the composite particles is likely to elute or flow out from the composite particles. Then, this invention provides the fiber processing agent containing the composite particle which the adhesiveness to the fiber of composite particle and the persistence to the composite particle of a functional substance improved.

  The present invention relates to a fiber treatment agent containing composite particles, wherein the composite particles include a mesoporous silica particle having a nonionic organic group having 2 or more carbon atoms on the particle surface and a functional substance. .

  ADVANTAGE OF THE INVENTION According to this invention, the fiber treatment agent containing the composite particle which can improve the adhesiveness of the composite particle to the fiber and the improvement of the persistence of the functional substance to the composite particle can be provided.

  In the composite particles in which a functional substance is held in mesoporous silica particles, the present invention improves the adsorptivity of the composite particles to fibers when the surface of the mesoporous silica particles is modified with a nonionic organic group. And based on the knowledge that elution and outflow to the water from this mesoporous silica particle of this functional substance are suppressed, and the function outstanding as a fiber processing agent component can be exhibited.

  That is, the present invention is a fiber treatment agent containing composite particles, wherein the composite particles include mesoporous silica particles having a nonionic organic group having 2 or more carbon atoms on the particle surface and a functional substance. The present invention relates to an agent (hereinafter also referred to as “fiber treatment agent of the present invention”). According to the fiber treatment agent of the present invention, it is possible to improve both the adhesion of the composite particles to the fibers and the improvement of the persistence of the functional substance to the composite particles. Maintenance of the function of the fiber can be improved.

  Although the detailed mechanism that makes it possible to improve both the adhesion of the composite particles to the fiber and the persistence of the functional substance to the composite particles is unknown, it is estimated as follows. First, by making the surface of the mesoporous silica particles hydrophobic, the affinity between the silica particles and the functional substance to be retained is increased, and the functional substance is less likely to elute or flow out. Since the fiber surface is usually hydrophobic, the composite particles having a hydrophobic surface are likely to adhere to the fiber. However, the present invention is not limited to this mechanism.

[Composite particles]
The fiber treatment agent of the present invention contains composite particles containing mesoporous silica particles having a nonionic organic group having 2 or more carbon atoms on the particle surface and a functional substance (hereinafter also referred to as “composite particles in the present invention”). Composition. In one embodiment, the fiber treatment agent of the present invention may be a liquid composition in which the composite particles of the present invention are dispersed or suspended in a solvent (for example, a base solution). Moreover, the fiber treatment agent of this invention may be the composite particle itself in this invention before disperse | distributing or suspending in a solvent (for example, base liquid) in another aspect.

[Nonionic mesoporous silica particles]
The mesoporous silica particles that are one of the constituent elements of the composite particles in the present invention are mesoporous silica particles having nonionic organic groups having 2 or more carbon atoms on the particle surface (hereinafter referred to as “nonionic mesoporous silica particles in the present invention”). It is also called).

[Mesoporous silica particles]
The mesoporous silica particles (one having no nonionic organic group; also referred to as “mesoporous silica particle raw material”), which is one of the components of the nonionic mesoporous silica particles in the present invention, are hexagonal array mesoporous (mesoporous). And particles having a (pore) structure. Specifically, the mesoporous silica particles have one or more peaks at a diffraction angle (2θ) corresponding to a crystal lattice spacing (d) in the range of 1 to 10 nm in powder X-ray diffraction measurement. Examples thereof include particles that do not show a peak at the diffraction angle (2θ) corresponding to the lattice spacing (d) of less than 1 nm. In powder X-ray diffraction (XRD) measurement, one or more peaks are shown at a diffraction angle (2θ) corresponding to a crystal lattice spacing (d) in the range of 1 to 10 nm. It means that the substance is a sex substance. Moreover, the fact that the crystal lattice spacing (d) does not show a peak at the diffraction angle (2θ) corresponding to a range of less than 1 nm means that it is different from a crystalline compound such as zeolite. As described later, the mesoporous silica constituting the nonionic mesoporous silica particles in the present invention includes hollow mesoporous silica and solid mesoporous silica, and the adhesion of the composite particles to the fibers and the composite particles of the functional substance are included. Hollow mesoporous silica is preferable from the standpoint of improving the persistence of the resin.

  The mesoporous silica particle raw material is composed mainly of silica, preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, and even more preferably 95 mol% or more is silicon dioxide. Converted to exist. Mesoporous silica particles have a form in which other elements such as Al, Ti, V, Cr, Co, Ni, Cu, Zn, Zr, B, Mn, Fe are supported, or a part of silica is substituted with other elements. It may be. When these elements are introduced, a metal raw material such as an alkoxy salt or a halogenated salt containing these metals may be added during or after production.

[Nonionic organic group]
In the nonionic mesoporous silica particles of the present invention, the nonionic organic group having 2 or more carbon atoms can improve the adhesion of the composite particles to the fiber and improve the persistence of the functional substance to the composite particles. Therefore, it may be present at least on the surface of the particle and further in the mesopores. The nonionic organic group having 2 or more carbon atoms is, for example, a group capable of imparting nonionicity to the mesoporous silica particles, and improving the adhesion of the composite particles to the fibers and the composite particles of a functional substance. From the standpoint of improving the persistence of the above, a hydrophobic organic group having 2 or more carbon atoms is preferred. The hydrophobic organic group has 2 carbon atoms that may be substituted with a halogen or thiol group from the viewpoint of improving the adhesion of the composite particles to the fiber and improving the persistence of the functional substance to the composite particles. Is preferably a hydrocarbon group having ˜30, more preferably an alkyl group, alkenyl group or aryl group having 2 to 30 carbon atoms which may be substituted with a halogen or thiol group, and an alkyl group which may be substituted with a halogen or thiol group. More preferably, an alkyl group having 2 to 30 carbon atoms is even more preferable. In the nonionic mesoporous silica particles of the present invention, the nonionic organic groups can be used alone or in combination of two or more.

  The number of carbon atoms of the nonionic organic group is 2 or more, preferably 4 or more, from the viewpoint of improving the adhesion of the composite particles to the fiber and improving the persistence of the functional substance to the composite particles. 6 or more is more preferable, and 10 or more is more preferable. From the same viewpoint, the carbon number is preferably 30 or less, more preferably 20 or less.

Specific examples of the nonionic organic group having 2 or more carbon atoms include CH ₃ CH ₂ —, ClCH ₂ CH ₂ —, CH ₂ ═CH—, CF ₃ CH ₂ CH ₂ —, CH ₃ CH ₂ CH ₂ —, _{CH 2 = CHCH 2 -, (} CH 3) 2 CH-, BrCH 2 CH 2 CH 2 -, ClCH 2 CH 2 CH 2 -, CF 3 CH 2 CH 2 CH 2 -, SHCH 2 CH 2 CH 2 -, ( _{CH 2 = CH) 2 -,} CH 3 CH 2 CH 2 CH 2 -, (CH 3) 2 CHCH 2 -, (C 2 H 5) 2 -, CH 3 CH 2 CH 2 CH 2 CH 2 -, CF 3 _{(CF 2) 3 CH 2 CH} 2 -, Ph -, (CH 2 = CHCH 2) 2 -, C 5 H 21 -, C 6 H 11 -, C 6 H 13 -, C 8 H 17 -, C 10 _{H 21 -, C 12 H 25} -, C 14 H 29 -, C 16 H 33 -, C 18 H 37 -, (C 2 H 5) 3 -, CH 3 Ph -, (C 3 H 7) 3 - , OCNC _{2 CH 2 CH 2 -, (} C 3 H 7) 2 -, CH 2 = CHPh -, (Ph) 2 -, (C 6 H 13) 2 -, (C 4 H 9) 2 -, (C 4 H _{9) 3 -, (Ph)} 3 -, BrC 11 H 23 -, CH 3 OCO (CH 2) 10 -, CH 3 OCOCH 2 CH 2 -, ClCH 2 CH (CH 3) CH 2 -, C 8 H 15 _{-, C 5 H 9 -,} (C 2 H 5) 2 -, (C 8 H 17) 2 -, C 22 H 45 -, ICH 2 CH 2 CH 2 -, OCNCH 2 CH 2 CH 2 -, CH 3 _{C (CH 3) 2 CH 2} CH (CH 3) CH 2 -, HS (CH 2) 11 -, CH 3 OCH 2 CH 2 CH 2 -, CH 3 O (CH 2 CH 2 O) 3 (CH 2) _3- and the like. From the viewpoint of improving the adhesion of the composite particles to the fiber and improving the persistence of the functional substance to the composite particles, CH ₃ CH ₂ —, CH ₃ CH ₂ CH ₂ —, CH ₃ CH ₂ CH ₂ CH _{2 -, C 5 H 21 -} , C 6 H 13 -, C 8 H 17 -, C 10 H 21 -, C 12 H 25 -, C 14 H 29 -, C 16 H 33 -, C 18 H 37 - CF ₃ CH ₂ CH ₂ CH ₂ — and SHCH ₂ CH ₂ CH ₂ — are preferred, and C ₁₀ H ₂₁ —, C ₁₂ H ₂₅ —, C ₁₄ H ₂₉ —, C ₁₆ H ₃₃ —, C ₁₈ H ₃₇ — Is more preferable.

In the nonionic mesoporous silica particles in the present invention, the amount of the nonionic organic group is selected from the viewpoint of improving the adhesion of the composite particles to the fiber and improving the persistence of the functional substance to the composite particles. / Si atomic ratio is preferably 0.15 to 1.20, more preferably 0.2 to 1.10, and still more preferably 0.25 to 1.00. In addition, the amount of nonionic organic groups in the nonionic mesoporous silica particles in the present invention is from the viewpoint of both improving the adhesion of composite particles to fibers and improving the persistence of functional substances to composite particles. 1-50 mass% is preferable, 5-30 mass% is more preferable, 10-20 mass% is further more preferable. The nonionic mesoporous silica particles of the present invention preferably contain 50 to 90% by mass, more preferably 70 to 90% by mass of silica in terms of SiO ₂ mass. These physical properties are identified and quantified by measuring silicon atoms ( ²⁹ Si-NMR) and carbon atoms ( ¹³ C-NMR) using nuclear magnetic resonance measurement, infrared spectroscopic analysis, elemental analysis, thermogravimetric analysis, etc. Specifically, it can be measured by the method shown in the following examples.

[Average pore diameter]
In the present specification, the average pore diameter of the mesoporous structure of the nonionic mesoporous silica particles in the present invention is compatible with the improvement of the adhesion of the composite particles to the fiber and the improvement of the persistence of the functional substance to the composite particles. From this viewpoint, 1 to 10 nm is preferable, 1 to 5 nm is more preferable, 1 to 2 nm is more preferable, and 1 to 1.5 nm is even more preferable. The average pore diameter of mesopores can be determined by nitrogen adsorption measurement and determined from the nitrogen adsorption isotherm by the BJH method, and specifically by the method described in the examples. Further, the mesoporous silica particles preferably have uniform mesopore diameters from the viewpoint of improving the adhesion of the composite particles to the fibers and improving the persistence of the functional substance to the composite particles. Preferably, 70% or more, more preferably 75% or more, and still more preferably 80% or more falls within the average pore diameter of ± 30%. In addition, the structure of the outer shell part which has a mesopore structure can be observed using a transmission electron microscope (TEM), and can be specifically measured by the method as described in an Example. Further, by TEM observation, the pore diameter, pore regularity, and in the case of hollow mesoporous silica particles, it is possible to confirm how the pores are connected from the outer shell to the inside.

  Adjustment of the pore diameter of the nonionic mesoporous silica particles may be performed using, for example, a mesoporous silica particle raw material having a pore diameter close to a desired pore diameter and before imparting a nonionic group. There is a possibility that a slight decrease in the pore size may occur in the step of applying the nonionic group. In consideration of this point, it is possible to prepare a target pore size. In addition, when synthesizing the raw material of the mesoporous silica particles before adding the nonionic group, the alkyl chain length of the surfactant that acts as a template for the pore diameter, the ratio between the hydrophilicity and lipophilicity of the water-soluble polymer compound, etc. are appropriately adjusted. By doing so, the pore diameter of the mesoporous silica particles can be adjusted. In particular, in order to prepare a mesoporous silica particle raw material having an average pore diameter of about 5 nm or more, it is preferable to use a nonionic polymer compound comprising block polymerization of polyethylene oxide and polypropylene oxide, and mesoporous having an average pore diameter of 8 nm or less. In order to obtain a silica particle raw material, it is preferable to use a quaternary ammonium salt.

[BET specific surface area]
The BET specific surface area of the nonionic mesoporous silica particles in the present invention is from 100 to 1500 m ² / g from the viewpoint of improving the adhesion of the composite particles to the fiber and improving the persistence of the functional substance to the composite particles. Is preferable, more preferably 200 to 1500 m ² / g, still more preferably 500 to 1000 m ² / g. Specifically, the BET specific surface area can be measured by the method described in Examples.

[Average primary particle size]
The average primary particle size of the nonionic mesoporous silica particles in the present invention is preferably 0.02 from the viewpoint of improving the adhesion of the composite particles to the fiber and improving the persistence of the functional substance to the composite particles. It is 10-10 micrometers, More preferably, it is 0.05-5 micrometers, More preferably, it is 0.1-1 micrometer. In the present specification, the average primary particle diameter of the nonionic mesoporous silica particles in the present invention is a number average particle diameter obtained using TEM, and can be specifically measured by the method described in Examples. The nonionic mesoporous silica particles in the present invention are composed of a group of particles having uniform particle diameters from the viewpoint of improving the adhesion of composite particles to fibers and improving the persistence of functional substances to composite particles. It is preferable. Specifically, the nonionic mesoporous silica particles in the present invention are preferably 80% or more, more preferably 85% or more, still more preferably 90% or more, particularly preferably 95% of the entire primary particles from the same viewpoint. The above preferably has a primary particle size within an average primary particle size of ± 30%.

[Hollow silica particles (A-1) and (A-2)]
The shape of the nonionic mesoporous silica particles in the present invention is not particularly limited, and may be indefinite or spherical, and may be a mixture thereof, but spherical is preferred from the viewpoint of sustained release of the functional substance. In particular, a hollow mesoporous silica particle (A-1) having a nonionic organic group (hereinafter referred to as “hollow silica particle (A-1)”) which is a spherical particle having an outer shell portion having a mesoporous structure and a hollow inside. Solid mesoporous silica particles having nonionic organic groups (A-2) (hereinafter referred to as spherical particles in which mesopores are not hollow and are radially arranged from the center thereof) , Also referred to as “solid silica particles (A-2)”), and hollow silica particles (A-1) are more preferable from the viewpoint of increasing the amount of the functional substance retained in the composite particles in the present invention.

[Average thickness of outer shell part and average diameter of hollow part]
The average thickness of the outer shell portion (mesoporous silica portion) of the hollow silica particles (A-1) is preferably as thin as the composite particles can maintain the strength as a carrier. Moreover, the one where the average diameter of the said hollow silica particle (A-1) is larger is preferable from a viewpoint of hold | maintaining many inclusions. From these viewpoints, the average thickness of the outer shell is preferably 10 to 500 nm, more preferably 20 to 400 nm, and still more preferably 100 to 300 nm. From the same viewpoint, the average diameter of the hollow portion is preferably 10 to 5000 nm, more preferably 100 to 1000 nm, and still more preferably 200 to 800 nm. In addition, the ratio of the average thickness of the outer shell part to the average particle diameter (outer shell part thickness / average particle diameter) improves the adhesion of the composite particles to the fibers and improves the persistence of the functional substance to the composite particles. From the viewpoint of compatibility, it is preferably 0.001 to 0.4, more preferably 0.01 to 0.3, and still more preferably 0.1 to 0.3. Furthermore, the ratio of the average diameter of the hollow part to the average thickness of the outer shell part (average hollow part diameter / outer shell part thickness) is preferably 0.1 to 100, more preferably 1 to 10 from the same viewpoint. It is. The average thickness of the outer shell part and the average diameter of the hollow part can be measured by TEM observation, and specifically can be measured as described in Examples described later.

[Compound (B) having nonionic organic group]
The nonionic mesoporous silica particles in the present invention can be obtained by treating a mesoporous silica particle raw material with a compound (B) having a nonionic organic group. Although there is no restriction | limiting in particular as a compound (B) which has a nonionic organic group in this invention, From a viewpoint of making a mesoporous silica particle contain a nonionic organic group (preferably hydrophobic organic group) efficiently, it is the above-mentioned. The hydrolyzable organosilane compound having a nonionic organic group is preferable, and the above-mentioned alkoxysilane having a nonionic organic group is more preferable. More specifically, an alkoxysilane having a nonionic organic group represented by the following general formula (1) and derivatives thereof may be mentioned. The derivative is a compound derivable from the general formula (1), and specific examples thereof include a hydrolyzate or hydrolysis condensate of the alkoxysilane.

R ¹ R ² _n-1 Si (OR ³ ) _4-n (1)
(In the general formula (1), R ¹ is the above-described nonionic organic group, and R ² is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. OR ³ Is an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, particularly preferably a methoxy group or an ethoxy group, n is a number of 1 to 3, R ² may be the same or different.)

  Specific examples of the alkoxysilane having a nonionic organic group include ethyltrimethoxysilane, ethyltriethoxysilane, diethoxydiethylsilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, Pentatriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, diethoxymethyloctadecylsilane, octadecyltriethoxysilane 3-bromopropyltrimethoxysilane, 11-bromoundecyltrimethoxysilane, 10- (carbomethoxy) decyldimethylmethoxysilane, 2 (Carbomethoxy) ethyltrimethoxysilane, 2-chloroethylmethyldimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloroisobutyldimethylmethoxysilane, 3-chloropropyldimethylmethoxysilane, 3-chloropropyldimethylethoxysilane, 3 -Chloropropylmethyldimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltrimethoxysilane, dibutyldimethoxysilane, diethyldiethoxysilane, dioctyldimethoxysilane, docosyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyl Triethoxysilane, hexadecyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, 3-iodopropyltrimethoxysilane 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, isooctyltriethoxysilane, isooctyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 11-mercaptoundecyltrimethoxysilane, 3- Methoxypropyltrimethoxysilane, methoxytriethyleneoxypropyltrimethoxysilane, octadecyldiethoxychlorosilane, octadecyldimethylmethoxysilane, octadecylmethoxydichlorosilane, octadecylmethyldiethoxysilane, octadecyltrimethoxysilane, octadecylmethyldimethoxysilane, octyldimethylmethoxysilane , Octylmethyldiethoxysilane, octylmethyldimethoxysilane, octyltrimethoxy Examples include silane, (3,3,3-trifluoropropyl) trimethoxysilane, (3,3,3-trifluoropropyl) methyldimethoxysilane, and the like. Among these, decyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, from the viewpoint of improving the adhesion of composite particles to fibers and improving the persistence of functional substances to composite particles, Hexadecyltrimethoxysilane and octadecyltrimethoxysilane are more preferable. The compound (B) which has a nonionic organic group can be used individually or in mixture of 2 or more types.

[Treatment with Compound (B) Having Nonionic Organic Group]
The processing method by the compound (B) which has a nonionic organic group is not specifically limited, It can carry out in accordance with conventional methods, such as a gaseous-phase method and a liquid phase method. Although depending on the type of the compound (B) having a nonionic organic group, the liquid phase method is preferred from the viewpoint of ease of production. Examples of the liquid phase method include a method in which a mesoporous silica particle raw material is dispersed in a toluene solution of the compound (B) having a nonionic organic group, stirred at 120 ° C. for 1 day, washed, and dried. As a specific example, the compound (B) having a nonionic organic group can be added by adding 1 to 500 parts by mass with respect to 100 parts by mass of the mesoporous silica particle raw material and treating at 20 to 150 ° C. for 1 to 120 hours. .

  When the liquid phase treatment is performed using the above-mentioned alkoxysilane having a nonionic organic group as the compound (B) having a nonionic organic group, the addition of the alkoxysilane is performed from the viewpoint of performance expression, manufacturability, and cost. The amount is preferably 1 to 500 parts by weight, more preferably 10 to 200 parts by weight, still more preferably 20 to 100 parts by weight, and particularly preferably 25 to 60 parts by weight with respect to 100 parts by weight of the mesoporous silica particle raw material. Moreover, although a process solvent is dependent also on the kind etc. of this alkoxysilane, a non-aqueous solvent is preferable, methanol, ethanol, n-hexane, and toluene are more preferable, and toluene is further more preferable. A processing solvent can be used individually or in combination of 2 or more types. The treatment temperature is preferably 20 to 150 ° C, more preferably 50 to 140 ° C, further preferably 80 to 130 ° C, and the treatment time is preferably 1 to 120 hours, more preferably 2 to 80 hours, and 3 to 30 hours. Is more preferable. After the treatment step of the compound (B) having a nonionic organic group, in order to remove unreacted compounds and by-products, heat treatment is performed at a temperature equal to or higher than the boiling point of the unreacted compounds and by-products, or unreacted compounds It can also be washed with a solvent in which the by-product compound is soluble.

  In order to obtain the hollow silica particles (A-1), the hollow mesoporous silica particle raw material (C-1) (hereinafter also referred to as “hollow silica particle raw material (C-1)”) is replaced with solid silica particles ( In order to obtain A-2), the solid mesoporous silica particle raw material (C-2) (hereinafter also referred to as “solid silica particle raw material (C-2)”) each contains a nonionic organic group. It is preferable to make it react with the compound (B).

  Although there is no restriction | limiting in particular in the manufacturing method of a hollow silica particle raw material (C-1), It prepares easily by the method of Unexamined-Japanese-Patent No. 2008-110905, Unexamined-Japanese-Patent No. 2008-150229, and Unexamined-Japanese-Patent No. 2008-174435. be able to.

  There is no restriction | limiting in particular in the manufacturing method of a solid silica particle raw material (C-2). For example, silica sources such as tetramethylsilane and tetraethoxysilane that produce silanol compounds by hydrolysis can be used in the presence of a cationic surfactant or ethylene oxide-propylene oxide block polymer that acts as a template for mesopores. It can be produced by reacting in an aqueous solution.

[Functional substances]
As the functional substance contained in the composite silica particles in the present invention, one kind selected from a fragrance, an agrochemical substrate, an insect repellent substrate, an antifungal substrate, a pharmaceutical substrate, a skin care substrate, a moisturizing material and the like. The above is preferable, and among them, a fragrance is preferable. In the composite particles in the present invention, these functional substances can be used alone or in combination of two or more. In general, these functional substances are likely to flow out and are difficult to maintain their effects. However, by holding them in mesoporous silica particles having nonionic organic groups, water or a solvent (for example, (Base solution) can be blended stably. Further, by hydrophobizing the surface of the mesoporous silica particles with a nonionic organic group, the affinity between the silica particles and the functional substance is improved to prevent elution in water or a solvent (for example, a base solution). Therefore, the functional substance is preferably a hydrophobic substance.

  In the composite silica particles in the present invention, the nonionic mesoporous silica particles in the present invention retain a functional substance. In one embodiment, the composite silica particles in the present invention can be obtained by retaining a functional substance in the nonionic mesoporous silica particles in the present invention obtained by the above-described method. In another embodiment, the composite silica particles of the present invention can be obtained by introducing a nonionic organic group into mesoporous silica particles holding a functional substance or template-containing silica particles holding a functional substance. Can be obtained. From the viewpoint of improving the adhesion of the composite particles to the fiber and improving the persistence of the functional substance to the composite particles, the method of retaining the functional substance in the nonionic mesoporous silica particles in the present invention is preferable.

[Fragrance]
As a fragrance | flavor used in this specification, both a natural fragrance | flavor and a synthetic | combination fragrance | flavor can be used, and it can be used by solid or liquid under normal temperature normal pressure. The fragrance is selected from hydrocarbon fragrance, alcohol fragrance, aldehyde fragrance, ketone fragrance, ester fragrance, phenol fragrance, ether fragrance, amine fragrance, lactone fragrance, acetal fragrance, and nitrile fragrance. Can be appropriately selected and used alone or in combination of two or more. Although main examples are shown below, it is not limited to these fragrance components. In addition, the name of the fragrance | flavor raw material used by this invention followed the description of Motoichi Into, "Synthetic fragrance | flavor chemistry and merchandise knowledge" (Chemical Industry Daily, published on March 6, 1996).

  Examples of the hydrocarbon-based fragrances include α-pinene, β-pinene, camphene, limonene, diterpene, terpinolene, myrcene, and the like, and alcohol-based fragrances include geraniol, dihydromyrsenol, linalool, sandalmysole core, 2- Methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol, tetrahydrolinalol, phenylethyl alcohol, citronellol, 1- (2-t-butylcyclohexyloxy) -2-butanol, terpineol, 3-methyl-5-phenylpentanol, ethyl linalool, tetrahydromegol, cis-3-hexenol, nerol, l-menthol, 3-phenylpropyl alcohol, 2,2,6-trimethylcyclohexyl -3-hexa Nord, acetylisoeugenol, estragole, trimethylhexanol and the like.

  Aldehyde perfumes include aldehyde C-111, citral, citronellal, hexylcinnamic aldehyde, lyial, amylcinamic aldehyde, 4 (3)-(4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxyl Aldehyde (Lilal), Heliotropin, Vanillin, Ethylvanillin, Anisaldehyde, Mylacaldehyde, Dimethyltetrahydrobenzaldehyde (Triplal), 2,4-Dimethyl-3-cyclohexenylcarboxaldehyde, n-hexanal, n-octanal, n- Nonanal, cis-4-decenal, helional, benzaldehyde, 10-undecenal, and the like. Examples of the ketone flavor include methylionone G, iso-e super, acetyl Drain, raspberry ketone, α-ionone, β-yonone, methyl-β-naphthyl ketone, heptylcyclopentanone, benzylacetone, methylenetetramethylheptanone, heliotopylacetone, cis-jasmon, ethylmaltol, cyclohexadecenone, muscone , Α-damascon, β-damascon, δ-damascon, damacenone, isodamascon, and the like.

Examples of ester flavors include phenylethyl acetate, allyl amyl glycolate, styraryl acetate, ot-butylcyclohexyl acetate, citronellyl acetate, geranyl acetate, linalyl acetate, acetyl eugenol, cinnamyl acetate, dimethylbenzyl carvinyl acetate, cyclohexyl salicylate, Tricyclodecenyl acetate, ethyl-2-tert-butylcyclohexyl carbonate, benzyl acetate, ethyl tricyclo [5.2.1.0 ^2.6 ] decane-2-carboxylate, benzyl salicylate, terpinyl acetate, trisipropionate Octdecenyl, ethyl 2-cyclohexylpropionate, amyl salicylate, allyl heptanoate, cis-3-hexenyl salicylate, cedolyl acetate (cedenyl), styrylyl propionate, propylpropionate Cyclohexane, neryl acetate, manzanate, allyl hexanoate (allyl caproate), ethyl 2-methylbutyrate, isoamyl acetate, isobornyl acetate, cis-3-hexenyl acetate, 2,2-dimethylpropionic acid-3-methyl-3- Examples include butenyl and ethyl 2-ethylcaproate.

  Examples of phenolic fragrances include eugenol, isoeugenol, mussins, thymol, and banitrope. Ether-based fragrances include ambroxan, anethole, methylisoeugenol, neroline jarara, galaxolide, β-naphthol ethyl ether, ethoxymethylcyclododecyl. Examples include ether, diphenyl oxide, rose oxide, and anthoxane.

  Examples of amine-based fragrances include methyl N-methylanthranilate, methyl anthranilate, and isobutylquinoline. Examples of lactone-based fragrances include oxacyclohexadecen-2-one, cyclopentadecanolide, γ-undecalactone, Coumarin, ethylene brushate, γ-decalactone, δ-decalactone, δ-dodecalactone, γ-nonalactone and the like. Examples of acetal fragrances include caranal, 2-butyl-4,4,6-trimethyl-1,3. -Dioxane etc. are mentioned, As a nitrile fragrance | flavor, a peonyl, a citronellyl nitrile, etc. are mentioned.

In the present specification, from the viewpoints of improving the adhesion of composite particles to the fiber and improving the persistence of functional substances to the composite particles, the mesoporous silica particle raw material and / or the nonionic mesoporous in the present invention is used. It is preferable to use a fragrance smaller than the pore diameter of the silica particles. Depending on the raw material of mesoporous silica particles used and / or the pore size of the nonionic mesoporous silica particles in the present invention, among the fragrances, limonene as a hydrocarbon-based fragrance and geraniol as an alcohol-based fragrance Linalool, phenylethyl alcohol, citronellol, cis-3-hexenol, l-menthol, trimethylhexanol, aldehyde fragrances such as citral, rigliall, vanillin, ethyl vanillin, helional, and ketone fragrances as iso-e-super , Δ-damascone, ester-based fragrances such as tert-butylcyclohexyl acetate, linalyl acetate, ethyltricyclo [5.2.1.0 ^2.6 ] decane-2-carboxylate, and amine-based fragrances such as methyl anthranilate. Etc. are suitable Limonene, ethyl vanillin, helional, δ-damascone, ethyltricyclo [5.2.1.0 ^2.6 ] decane-2-carboxylate, and methyl anthranilate are more preferable.

[Fragrance impregnation]
The perfume can be retained, for example, by impregnating the perfume into the mesoporous silica particle raw material and / or the nonionic mesoporous silica particles in the present invention. Hereinafter, the case where a hollow silica particle (A-1) is impregnated with a fragrance will be described as an example.

  The impregnation treatment of the fragrance is not particularly limited as long as the fragrance can impregnate the mesoporous silica particles, and a known vacuum impregnation method or the like can be adopted. For example, the fragrance and the hollow silica particles (A-1) are mixed in a container, and the vapor pressure of nitrogen in the mesopores of the hollow silica particles (A-1) used is higher than the vapor pressure of the fragrance in the container. It is preferable to impregnate under a condition smaller than the pressure. In this case, the vapor pressure of nitrogen in the mesopores is obtained from the nitrogen adsorption isotherm. Under these conditions, the pores of the hollow silica particles (A-1) are degassed and impregnated with a fragrance. For example, after standing for 1 minute to 10 hours, preferably 1 minute to 1 hour, the pressure in the container is temporarily increased. A method of introducing the fragrance into the hollow interior through the mesopores of the mesoporous silica particles by returning to atmospheric pressure and allowing to stand for 1 minute to 10 hours, preferably 1 hour to 10 hours, is further mentioned. The degree of impregnation is preferably carried out until the fragrance is included in all of the mesoporous silica particles (hollow portions, mesopores). In the case of a fragrance that is solid at normal temperature and pressure, a method in which it is impregnated in a liquid state by heating and melting at a temperature equal to or higher than the melting point of the fragrance is preferred. Moreover, you may impregnate the solution which melt | dissolved the solid fragrance | flavor in the solvent.

  The content of the functional substance in the composite particle in the present invention is not particularly limited, but from the viewpoint of maintaining the function of the functional substance, the composition in the composite particle in the present invention is preferably 10 to 90% by mass, more Preferably it is 10-80 mass%, More preferably, it is 20-50 mass%. In addition, the content of the functional substance in the composite particles in the present invention can be determined by conventional methods such as thermogravimetric analysis, gas chromatography, liquid chromatography and the like. In the composite particle in the present invention, first, the volatilization of the functional substance held near the outer surface of the composite particle starts, and then the functional substance held in the hollow part and the mesopore is stable for a long time. Volatilization control is easy because it volatilizes at a reduced speed. Among these functional substances, even if the inorganic powders having catalytic activity such as acids, alkalis, zeolites, etc., are unstable esters and acetals, they are stable if they are kept inside the mesoporous silica particles. It is possible to obtain composite particles that are retained and have excellent sustained release properties and residual fragrance characteristics (in the case of a fragrance). For example, if a plurality of fragrances are used in combination, and each is held in different mesoporous silica particles, a wide and effective fragrance can be performed.

[Surfactant]
The fiber treatment agent of the present invention may contain a surfactant as long as the effects of the present invention are not inhibited from the viewpoint of dispersion stability and the like. As the surfactant, anionic, nonionic, cationic or amphoteric surfactants can be used. More specifically, linear alkylbenzene sulfonate (alkali metal salt, etc., the same shall apply hereinafter), α-olefin sulfonate, sulfo fatty acid methyl ester salt, long-chain alkyl sulfate ester salt, oxyalkylene addition type nonionic surfactant And amine hydrochloride.

[Other ingredients]
Furthermore, additives that are usually blended in fiber treatment agents, such as water-soluble inorganic salts, antioxidants, chelating agents, ultraviolet absorbers, solvents, and pigments, are blended at normal doses as long as the effects of the present invention are not impaired. Can be used. Examples of water-soluble inorganic salts include sodium chloride, calcium chloride, magnesium chloride, and potassium chloride. Examples of antioxidants include sodium sulfite and dibutylhydroxytoluene. Examples of chelating agents include ethylenediaminetetraacetate, Citric acid and the like can be mentioned.

[Fiber treatment agent]
The dosage form of the fiber treatment agent of the present invention is not particularly limited, and can be used in various forms such as liquid and powder. From the viewpoint of ease of use, an oil-in-water (O / W type) emulsion and It is preferable to do. When using the fiber treatment agent of the present invention, they are dispersed in an aqueous liquid, and the fiber product to be treated is immersed and / or stirred in the liquid, or washing water or rinsing water containing the fiber product to be treated is used. By adding an appropriate amount of the fiber treatment agent of the present invention, the composite particles in the fiber treatment agent can be efficiently attached and adsorbed on the surface or inside of the fiber product, and functions such as residual fragrance can be imparted. Moreover, although it can also be mix | blended and used for a softener, a detergent, a glue, etc., it is preferable to use as a softener. The softening agent is not particularly limited as long as it keeps the suppleness of the clothes after washing. Examples thereof include a cationic surfactant having a long chain hydrocarbon group. The fiber product to be treated is not particularly limited, and can be suitably used for any treatment of natural fiber products, synthetic fiber products, and semi-synthetic fiber products.

  Using the hollow mesoporous silica particles produced in the following Production Examples 1 to 5, fiber treatment agents of Examples 1 to 3 and Comparative Examples 1 to 2 were produced, and the perfume residual rate, the silica adhesion rate, and the residual fragrance property were evaluated. Various measurements and evaluations were performed by the following methods.

(1) Measurement of powder X-ray diffraction (XRD) pattern of mesoporous silica particles X-ray source: Cu-kα, tube voltage: 40 mA using a powder X-ray diffractometer (manufactured by Rigaku Corporation, trade name: RINT2500VPC) , Tube current: 40 kV, sampling width: 0.02 °, divergence slit: 1/2 °, divergence slit length: 1.2 mm, scattering slit: 1/2 °, and light receiving slit: 0.15 mm Line diffraction measurement was performed. A continuous scanning method with a scanning range of diffraction angle (2θ) of 1 to 20 ° and a scanning speed of 4.0 ° / min was used. The measurement was performed by packing the pulverized sample in an aluminum plate.

(2) Observation of particle shape of mesoporous silica particles The particle shape was observed using an electrolytic emission type high resolution scanning electron microscope (manufactured by Hitachi, Ltd., trade name: FE-SEM S-4000).

(3) Measurement of average primary particle diameter, average hollow part diameter, and average outer shell part thickness of mesoporous silica particles Acceleration voltage using a transmission electron microscope (TEM) (trade name: JEM-2100, manufactured by JEOL Ltd.) The particles were observed at 160 kV. The diameter, hollow diameter, and outer shell thickness of all particles in five fields of view containing 20-30 particles were measured on a photograph, and the average primary particle diameter, average hollow diameter, and average outer shell thickness were measured. Asked. In addition, observation was performed using what attached to Cu mesh (200-A mesh by Oken Shoji Co., Ltd.) with the carbon support film for high resolution, and removed the excess sample by the blow.

(4) Measurement of BET specific surface area and average pore diameter of mesoporous silica particles Using a specific surface area / pore distribution measuring device (manufactured by Shimadzu Corporation, trade name: ASAP2020), BET is a multipoint method using liquid nitrogen. The specific surface area was measured, and the value was derived within the range where parameter C was positive. The BJH method was adopted for deriving the BET specific surface area, and the peak top was defined as the average pore diameter. The sample was pretreated at 250 ° C. for 5 hours.

(5) Measurement of average aggregate particle diameter of mesoporous silica particles Using a laser scattering particle size distribution meter (manufactured by Horiba, Ltd., trade name: LA-920), a relative refractive index of 1.06, an ultrasonic intensity of 7, and ultrasonic irradiation Measurement was performed at room temperature under conditions of 1 minute at time, circulation rate 4 and ethanol as a dispersion medium, and the median diameter in terms of volume was defined as the average aggregated particle diameter.

(6) Quantitative analysis of nonionic organic groups of mesoporous silica particles having nonionic organic groups Using a differential type differential thermal balance (TG-DTA) Thermo plus TG8120 manufactured by Rigaku Denki Kogyo Co., Ltd., air flow (300 mL) / Min) from room temperature to 700 ° C. at a rate of 10 ° C./min. The mass remaining at 700 ° C. was derived from silica (SiO ₂ ), and the weight loss from 150 to 700 ° C. was derived from nonionic organic groups. The ratio of carbon atoms to silicon atoms (C / Si atomic ratio) was determined from mass% derived from nonionic organic groups and mass% derived from silica.

(7) Measurement of total perfume amount of perfume composite particles From Rigaku Denki Kogyo Co., Ltd., differential type differential thermal balance (TG-DTA) Thermo plus TG8120, from room temperature to 100 ° C. under air flow (300 mL / min) The temperature was raised at a rate of 10 ° C./min, then held at 100 ° C. for 5 hours, and further heated to 700 ° C. at a rate of 10 ° C./min. The weight loss up to 700 ° C. was defined as the total amount of the fragrance and the nonionic organic group, and the mass remaining at 700 ° C. was defined as the mass of silica. Further, the mass of the nonionic organic group of the composite particle is calculated using the ratio of the nonionic organic group to the silica weight of the mesoporous silica particle before carrying the fragrance obtained from the measurement method of (6), and the nonionic property is obtained. All fragrances other than organic groups and silica were used. From these results, a fragrance composite particle composition composed of SiO ₂ , an organic group and a total fragrance was determined.

(8) Evaluation of Perfume Residual Ratio of Perfume Composite Particles Regarding ethyltricyclo [5.2.1.0 ^2.6 ] decane-2-carboxylate perfume composite particles, the perfume composite particles before and after dispersion in the fiber treatment step From the difference in the amount of fragrance carried, the fragrance residual ratio of the fragrance composite particles after the fiber treatment step was determined. The amount of fragrance carried by the fragrance composite particles before and after dispersion in the fiber treatment step was determined as follows. The fragrance | flavor composite particle 0.03g was disperse | distributed to 5 mL hexane, and it stirred for 1 hour, and extracted the fragrance | flavor in particle | grains. After the stirring, 0.01 g of decane was added as an internal standard, and the mixture was filtered with a membrane filter (manufactured by ADVANTEC, material: cellulose acetate, pore size: 0.2 μm). The amount of ethyl tricyclo [5.2.1.0 ^2.6 ] decane-2-carboxylate fragrance in the filtrate was calculated using Agilent Technologies, gas chromatography, HP6890, and the amount of fragrance carried by the fragrance composite particles. It was.

The residual rate of the fragrance composite particles was determined as follows. First, 0.67 g of a fiber treatment agent containing ethyltricyclo [5.2.1.0 ^2.6 ] decane-2-carboxylate fragrance composite particles was added to 2000 g of water in a 2 L beaker having an inner diameter of 13 cm, and the mixture was stirred for 6 minutes at room temperature. Dispersion treatment was performed by magnetic stirring. The stirrer piece used was a cross of 3.5 cm in length, and the stirring speed was set so that the top of the swirl came to 1/3 from the bottom of the water level during stirring. Immediately after the stirring, the mixture was filtered for about 10 minutes with a membrane filter (manufactured by ADVANTEC, material: cellulose acetate, pore size: 0.2 μm).

  Immediately after filtration, gas chromatographic measurement was performed to quantify the fragrance carried on the dispersed mesoporous silica particles. The ratio of the amount of the fragrance carried after dispersion to the dispersion before dispersion was defined as the residual rate.

(9) Evaluation of silica adhesion rate on towel In an electric bucket (Panasonic Corporation, N-BK2), 1.9 g of a fiber treatment agent containing fragrance composite particles was added to 5.7 L of water, and immediately a commercially available towel 3 A sheet (about 285 g) was added, washed for 6 minutes, and dehydrated for 3 minutes in a washing machine. The towel was dried by flat drying in the room for 24 hours to prepare a treated towel. The Si concentration in the aqueous solution in which the treated towel was ashed and dissolved was quantified by ICP.

  In the case of a fiber treatment agent containing no fragrance composite particles (only fragrance), a treated towel was prepared in the same manner, and the Si concentration was quantified. The difference between the Si amount in the towel treated with the fiber treatment agent containing the fragrance composite particles and the Si amount in the towel treated with the fiber treatment agent not containing the fragrance composite particles is the amount of Si derived from silica adhered to the towel. did. The ratio of the amount of Si attached to the towel to the amount of Si blended in the fiber treatment agent was defined as the silica adhesion rate.

(10) Evaluation of residual fragrance on treated towel As a pretreatment, 20 towels were washed with a commercially available liquid attack (manufactured by Kao Corporation) in an electric washer-dryer (manufactured by Panasonic, NA-FV8000) (25 g of detergent, tap water) 38 L of water, water temperature 20 ° C., washing 9 minutes, rinsing 2 times, dehydration 7 minutes). Next, three pretreated towels (about 285 g) were placed in 5.7 L of water in an electric bucket (Panasonic Corporation, N-BK2), and 1.9 g of the fiber treatment agent containing fragrance composite particles was immediately added. After washing for 6 minutes, it was dehydrated for 3 minutes with an electric washing dryer. Towels were dried by flat-drying indoors for 24 hours.

The sensory evaluation was performed by 11 expert panelists on the scent of the dried towel and the scent after the towel was rubbed, and evaluated according to the following criteria.
〔Evaluation criteria〕
◎: More than 9 out of 11 panelists who felt a strong scent compared to the case containing no fragrance composite particles (only fragrance only) ○: Stronger than the case containing no fragrance composite particles (only fragrance only) Panelists who felt the scent 6 or more but less than 9 out of 11 ×: Panelists who felt the scent strongly less than 6 out of 11 compared to the case where no fragrance composite particles were contained (only the fragrance)

[Production of hollow mesoporous silica particles]
Production Example 1 (Production of hollow mesoporous silica particles)
(1) In a 1 L-separafull flask, 600 g of ion-exchanged water, 99.5 g of methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 0.5 g of methacryloyloxyethyltrimethylammonium chloride (manufactured by Mitsubishi Rayon Co., Ltd.) are placed. The internal temperature was raised to 70 ° C.

  Next, 0.5 g of 2,2′-azobis (2-amidinopropane) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-50) is dissolved in 5 g of ion-exchanged water as a water-soluble polymerization initiator. The solution was added and stirred with heating for 3 hours. Thereafter, the mixture is further cooled by heating and stirring at 75 ° C. for 3 hours, and then the aggregate is filtered through a 200-mesh filter (mesh size: about 75 μm) to obtain a suspension of cationic polymer particles (solid content (effective Min) content 14% by mass, average primary particle diameter 250 nm).

  (2) Next, 192 kg of ion-exchanged water, 64 kg of methanol, 1.44 kg of 1M sodium hydroxide aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) 1.44 kg, 0.96 kg of dodecyltrimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) Then, 1.04 kg of the suspension of the cationic polymer particles obtained above was added and stirred, and 1.09 kg of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the aqueous solution in 30 seconds, and the mixture was brought to room temperature. And stirred at 70 rpm for 5 hours. The stirring speed was reduced to 25 rpm and stirring was continued for 18 hours. Next, the obtained white precipitate was filtered through a membrane filter having a pore size of 0.2 μm, washed with 10 L of water, and dried at a temperature of 100 ° C. for 5 hours.

  The obtained dry powder was heated to 600 ° C. at a rate of 1 ° C./min with an air flow (3 L / min) using a baking furnace (product name: Superburn), and at 600 ° C. The organic component was removed by baking for 2 hours.

  The obtained powder was subjected to dry crushing (20000 rpm) and dry classification (passing through a 0.2 mm pore size screen) using a rotor speed mill (manufactured by FRITSCH, trade name: pulverisetel 4), thereby forming hollow mesoporous silica particles. A powder was obtained.

  (3) The hollow silica particles had one or more peaks at a diffraction angle corresponding to a range of d = 2 to 12 nm in a powder X-ray diffraction (XRD) pattern. Moreover, it was confirmed by SEM observation that the particle shape of the hollow mesoporous silica particle raw material was spherical.

  Furthermore, from TEM observation, this hollow mesoporous silica particle raw material has a hollow structure, the average primary particle diameter is 410 nm, the average hollow part diameter is 250 nm, the average outer shell part thickness is 80 nm, and the outer shell part has a hexagonal arrangement. It was confirmed that the uniform mesopores shown in the figure were formed, and the mesopores penetrated radially from the center of the particle toward the outside of the outer shell. All primary particles had a primary particle size within an average primary particle size of ± 30%.

The hollow mesoporous silica particle raw material powder had a BET specific surface area of 1188 m ² / g, an average pore diameter of 1.6 nm, and an average aggregated particle diameter of 0.7 μm. The results are shown in Table 1.

Production Example 2 [Production of hollow mesoporous silica particles (C18) having nonionic organic groups]
(1) Under stirring at room temperature, 0.6 g of octadecyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) is dissolved in 50 g of toluene, and then 2 g of the hollow mesoporous silica particle powder obtained in Production Example 1 is dispersed at 24 ° C. at 24 ° C. Time processed. The treatment liquid was filtered with a filter having a pore size of 0.2 μm, washed with ethanol, and dried at 100 ° C. for 24 hours to obtain hollow mesoporous silica particles (C18) powder treated with octadecyltrimethoxysilane.

  (2) This alkylsilane-treated hollow mesoporous silica particle (C18) powder has one or more peaks at a diffraction angle corresponding to a range of d = 2 to 12 nm in a powder X-ray diffraction (XRD) pattern. It was. Moreover, it was confirmed by SEM observation that the particle shape of the hollow mesoporous silica particle raw material was spherical.

  Further, from TEM observation, the hollow mesoporous silica particles (C18) have a hollow structure, the average primary particle diameter is 410 nm, the average hollow part diameter is 250 nm, the average outer shell part thickness is 80 nm, and the outer shell part is hexagonal. It was confirmed that they had uniform mesopores indicating the arrangement, and the mesopores penetrated radially from the particle center toward the outside of the outer shell. All primary particles had a primary particle size within an average primary particle size of ± 30%.

The hollow mesoporous silica particles (C18) powder had a BET specific surface area of 521 m2 / g and an average pore diameter of 1.3 nm. Furthermore, as a result of TG-DTA measurement of the hollow mesoporous silica particles (C18) powder, SiO ₂ was 87% by mass, nonionic organic group was 14% by mass, and the nonionic organic group amount C / Si atomic ratio was 0. .75. The results are shown in Table 1.

Production Example 3 [Production of Hollow Mesoporous Silica Particles (C12) Having Nonionic Organic Groups]
In Production Example 2 (1), Production Example 2 and Except that 1.2 g of dodecyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd.) was used instead of 0.6 g of octadecyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd.) Similarly, hollow mesoporous silica particles (C12) powder treated with dodecyltrimethoxysilane was obtained.

As a result of powder X-ray diffraction (XRD) measurement and TEM observation of the hollow mesoporous silica particles (C12) powder, the same results as in Production Example 2 were obtained. The hollow mesoporous silica particles (C12) powder had a BET specific surface area of 808 m ² / g and an average pore diameter of 1.4 nm. Further, as a result of TG-DTA measurement of the hollow mesoporous silica particles (C12) powder, SiO ₂ was 87% by mass, nonionic organic group was 11% by mass, and the nonionic organic group amount C / Si atomic ratio was 0. .49. The results are shown in Table 1.

Production Example 4 [Production of hollow mesoporous silica particles (C10) having nonionic organic groups]
In Production Example 2 (1), the same as Production Example 2 except that 0.4 g of decyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 0.6 g of octadecyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.). Thus, hollow mesoporous silica particles (C10) powder treated with decyltrimethoxysilane was obtained.

As a result of powder X-ray diffraction (XRD) measurement and TEM observation of the hollow mesoporous silica particles (C10) powder, the same results as in Production Example 2 were obtained. The hollow mesoporous silica particles (C10) powder had a BET specific surface area of 679 m ² / g and an average pore diameter of 1.3 nm. As a result of TG-DTA measurement of the hollow mesoporous silica particle (C10) powder, SiO ₂ was 83% by mass, nonionic organic group was 10% by mass, and the nonionic organic group amount C / Si atomic ratio was 0. .60. The results are shown in Table 1.

Production Example 5 [Production of hollow mesoporous silica particles (C1) having nonionic organic groups]
1 g of hollow mesoporous silica particle powder obtained in Production Example 1 and 0.1 g of hexamethyldisilazane (manufactured by Wako Pure Chemical Industries, Ltd.) are placed in a 1 L tetrabag, sealed, and left in an electric dryer at 80 ° C. for 2 days. As a result, a disilazane-treated hollow mesoporous silica particle (C1) powder was obtained.

As a result of powder X-ray diffraction (XRD) measurement and TEM observation of the hollow mesoporous silica particles (C1) powder, the same results as in Production Example 2 were obtained. The hollow mesoporous silica particles (C1) powder had a BET specific surface area of 1026 m ² / g and an average pore diameter of 1.3 nm. As a result of TG-DTA measurement of the hollow mesoporous silica particles (C1) powder, the SiO ₂ content was 92 mass%, the nonionic organic group content was 3 mass%, and the nonionic organic group content C / Si atomic ratio was 0. .12. The results are shown in Table 1.

[Production of perfume composite particles]
The hollow mesoporous silica particle powders obtained in Production Examples 1 to 5, 0.5 g each were put into a 20 mL sample bottle, and ethyl tricyclo [5.2.1.0 ^2.6 ] decane-2-carboxylate fragrance was added thereon. 6.0 g was poured. The container was transferred into a glass desiccator and decompressed for 3 minutes using a rotary pump, and then filled with nitrogen gas to return the internal pressure to normal pressure. After repeating this operation three times, the sample was allowed to stand overnight. The next day, the mixture was filtered with a membrane filter (manufactured by ADVANTEC, material: polytetrafluoroethylene, pore size: 0.2 μm) to obtain fragrance composite particles.

Example 1 [Preparation and Evaluation of Fiber Treatment Agent Containing Fragrance Composite Particles (C18)]
(1) Preparation of fiber treatment agent base solution In a 300 mL beaker, 144 g of ion-exchanged water was added, and the temperature was raised to 60 ° C. in a water bath. While stirring with a stirring blade having a length of 2 cm and a width of 0.8 cm (200 r / min), a nonionic surfactant (average of 20 moles of ethylene oxide in a linear primary alcohol having 12 carbon atoms) Of the cationic surfactant (N- (3-alkanoylaminopropyl) -N- (2-alkanoylhydroxyethyl) -N-methylamine hydrochloride) 34 g of an ethanol solution (ethanol content 10%, where the alkanoyl group is a fatty acid residue derived from hard beef tallow) was added, then calcium chloride (final concentration 0.05% by mass) was added and stirred for 5 minutes, The pH was adjusted to 2.4 with 10% aqueous hydrochloric acid and 10% aqueous sodium hydroxide, and then 16 g of ion exchange water at 60 ° C. was added. Transfer the beaker Tabasu, with stirring (80 r / min), and cooled to room temperature (25 ° C.).
(2) Preparation of Fiber Treatment Agent Containing Fragrance Composite Particles Into the fiber treatment agent base solution obtained in (1) above, ethyl tricyclo [5.2.1.0 ^2.6 ] decane-2-carboxylate fragrance was added. The fiber treatment agent which contains a fragrance | flavor composite particle by mix | blending the fragrance | flavor composite particle (C18) so that a density | concentration might be 2 mass% was obtained. The results are shown in Table 2.
(3) Fiber treatment with fiber treatment agent containing fragrance composite particles The silica adhesion rate and residual fragrance property of the fiber treatment agent obtained in the above (2) were evaluated. The results are shown in Table 2.

Examples 2-3 and Comparative Examples 1-2 [Preparation and Evaluation of Fiber Treatment Agent Containing Fragrance Composite Particles]
Table 2 was prepared so that the concentration of ethyltricyclo [5.2.1.0 ^2.6 ] decane-2-carboxylate perfume was 2% by mass in the fiber treatment agent base solution obtained in Example 1 (1). The fiber processing agent which mix | blended the fragrance | flavor composite particle shown in FIG. The fiber treatment agents were evaluated in the same manner as in Example 1. The results are shown in Table 2.

  As shown in Table 2 above, it was confirmed that the fiber treatment agents of Examples 1 to 3 were superior in silica adhesion and residual fragrance compared to the fiber treatment agents of Comparative Examples 1 and 2.

  The present invention is useful, for example, in the field of fiber treatment agents.

Claims (7)

A fiber treatment agent containing composite particles,
The composite particle is a fiber treatment agent comprising mesoporous silica particles having a nonionic organic group having 2 or more carbon atoms on the particle surface and a functional substance. The fiber treatment agent according to claim 1, wherein the mesoporous silica particles are hollow mesoporous silica particles. The fiber treatment agent according to claim 1 or 2, wherein the nonionic organic group is an alkyl group. The mesoporous silica particles having a nonionic organic group having 2 or more carbon atoms on the particle surface are obtained by treating mesoporous silica particles with an alkoxysilane having an alkyl group having 2 or more carbon atoms. 4. The fiber treatment agent according to any one of 3. The fiber treatment agent according to any one of claims 1 to 4, wherein the nonionic organic group is an alkyl group having 10 or more carbon atoms. The fiber treatment agent according to any one of claims 1 to 5, wherein the content of the functional substance with respect to the composite particles is 10 to 90% by weight. The fiber treatment agent according to any one of claims 1 to 6, wherein the functional substance is a fragrance.