JP7245755B2 - Hydrophobic inorganic particles and particle-containing resin composition - Google Patents

Description

The present invention relates to hydrophobic inorganic particles and particle-containing resin compositions.

Conventionally, a coating composition capable of forming a coating film having a deodorizing function by blending an inorganic deodorant, which is a composite of zinc oxide and silica hydrate, with a resin is known (for example, the following See Patent Document 1.).

JP 2019-35075 A

However, the coating film is required to exhibit higher functions such as a higher deodorizing function. However, the coating film formed from the coating composition described in Patent Document 1 has a problem that it cannot sufficiently satisfy the above requirements.

The present invention provides hydrophobic inorganic particles and a particle-containing resin composition capable of exhibiting high functionality.

The present invention (1) includes inorganic particles and a coating layer that coats the inorganic particles, the inorganic particles having an oil absorption of 50 mL/100 g or more and having a substantially spherical shape, the coating layer comprising: —SiR ₂ O— (the two Rs may be the same or different and each represents at least one monovalent hydrocarbon group selected from the group consisting of a monovalent saturated hydrocarbon group and a monovalent aromatic hydrocarbon group; A silicone containing a first oligomer containing a siloxane unit represented by a hydrocarbon group) and an RO group-containing siloxane unit containing an RO group (R represents a monovalent saturated hydrocarbon group) It contains hydrophobic inorganic particles that are a cured product of the composition.

The present invention (2) includes the hydrophobic inorganic particles according to (1), wherein the inorganic particles are deodorant particles.

The present invention (3) includes the hydrophobic inorganic particles according to (1) or (2), wherein the inorganic particles carry a functional component.

In the present invention (4), the silicone composition comprises —SiR ₂ O— (the two Rs may be the same or different, and are respectively a monovalent saturated hydrocarbon group and a monovalent aromatic hydrocarbon Represents at least one monovalent hydrocarbon group selected from the group consisting of groups) does not contain a siloxane unit represented by and contains an RO group (R represents a monovalent saturated hydrocarbon group) The hydrophobic inorganic particles according to any one of (1) to (3), further comprising a second oligomer containing an RO group-containing siloxane unit.

The present invention (5) is the hydrophobic inorganic particles according to (4), wherein the silicone composition further contains a silicone oil.

The present invention (6) includes a particle-containing resin composition containing the hydrophobic inorganic particles according to any one of (1) to (5) and a resin.

The present invention (7) includes the particle-containing resin composition according to (6), wherein the resin is an aqueous resin.

In the hydrophobic inorganic particles of the present invention, since the inorganic particles have an oil absorption of 50 mL/100 g or more, the volume of pores (described later) is sufficient. Therefore, the hydrophobic inorganic particles can sufficiently exhibit the functions of the inorganic particles.

Further, since the coating layer is a cured product of a silicone composition containing a first oligomer containing a siloxane unit, the hydrophobic inorganic particles are blended with the resin and the hydrophobic inorganic particles are added when molding the molded product. It can be unevenly distributed on the surface of the molded article.

Furthermore, since the inorganic particles have a substantially spherical shape, the above-described hydrophobic inorganic particles can be unevenly distributed quickly.

Therefore, a molded article molded from the particle-containing resin composition of the present invention containing hydrophobic inorganic particles can exhibit high functionality because the hydrophobic inorganic particles are unevenly distributed on the surface.

The hydrophobic inorganic particles and particle-containing resin composition of the present invention will be described in order.

The hydrophobic inorganic particles include inorganic particles and a coating layer that coats the inorganic particles.

Inorganic particles are functional particles that can exhibit functions. Functions include, for example, deodorization (including deodorization, deodorization, deodorization, etc.), gas adsorption, and support of functional components, for example. Functional components are described in detail below.

Examples of the inorganic particles include deodorant inorganic particles (including deodorant inorganic particles, deodorant inorganic particles, deodorizing inorganic particles, etc.), gas-adsorbing inorganic particles, and supporting inorganic particles (carrier particles). be done. Incidentally, the supporting inorganic particles are disclosed, for example, in Japanese Patent Application Laid-Open No. 2017-160450.

Examples of inorganic particle materials include oxides such as silica (silicon oxide), alumina (aluminum oxide), zinc oxide and magnesium oxide; nitrides such as boron nitride; carbonates such as calcium carbonate; , their composites (e.g., composite oxides (specifically, composite oxides of silica, alumina and zinc oxide, composite oxides of silica and alumina (silica-alumina)), e.g., sericite, aluminosilicates ( zeolite), talc, etc. Preferably, an oxide is used in order to ensure high reactivity with the OH group derived from the RO group in the first oligomer.

Further, when the inorganic particles are deodorizing inorganic particles, in order to ensure a high deodorizing function, more preferably a composite, more preferably a composite oxide, specifically silica, alumina and Composite oxides of zinc oxide can be mentioned.

Further, when the inorganic particles are supporting inorganic particles, oxides are more preferred, and silica is even more preferred, in order to ensure a high supporting function.

The shape of the inorganic particles is approximately spherical. The substantially spherical shape includes a true spherical shape and a shape with a sphericity close to 1 (specifically, a sphericity of 0.9 or more as described in Japanese Patent Application Laid-Open No. 2009-263155). Also, the inorganic particles are, for example, porous.

On the other hand, if the shape of the inorganic particles is plate-like, the floating property (uneven distribution) of the hydrophobic inorganic particles is low. Therefore, plate-like inorganic particles are not suitable for the present invention.

The average maximum length of the inorganic particles (the average particle diameter calculated as the median diameter if spherical) is, for example, 0.1 μm or more, preferably 1 μm or more, and, for example, 1,000 μm or less. , preferably 100 μm or less, more preferably 20 μm or less.

The inorganic particles have an oil absorption of 50 mL/100 g or more, preferably 100 mL/100 g or more, and for example, 1,000 mL/100 g or less, preferably 500 mL/100 g or less. If the oil absorption of the inorganic particles is less than 50 mL/100 g, the inorganic particles do not have a sufficient volume of pores (described later), and thus cannot sufficiently exhibit their own functions. If the oil absorption of the inorganic particles is 1,000 mL/100 g or less as described above, the workability when blending with the resin is excellent. The oil absorption of inorganic particles is measured according to JIS K5101-13-2 (2004).

Since the inorganic particles have an oil absorption of 50 mL/100 g or more, they have sufficiently wide pores inside. Inorganic particles can exhibit various functions based on pores. For example, if the inorganic particles are deodorant inorganic particles, odor components can be adsorbed in the pores. Further, for example, if the inorganic particles are supporting inorganic particles, the functional component can be reliably supported in the pores, so that the function of the functional component can be fully exhibited.

Commercially available inorganic particles can be used. For example, as deodorizing inorganic particles, the Seventol series (composite oxide of silica, alumina and zinc oxide, manufactured by Osaka Gas Chemicals Co., Ltd.), for example, as a carrier for support, the Silysia series (silica, manufactured by Fuji Silysia Ltd.), etc. is used.

The coating layer covers the inorganic particles. The coating layer is a cured silicone composition containing the first oligomer.

The first oligomer is the curing component in the silicone composition. Specifically, the first oligomer is —SiR ₂ O— (the two Rs may be the same or different, and each consists of a monovalent saturated hydrocarbon group and a monovalent aromatic hydrocarbon group Represents at least one monovalent hydrocarbon group selected from the group) and an RO group-containing siloxane unit containing an RO group (R represents a monovalent saturated hydrocarbon group.) contains

Examples of monovalent saturated hydrocarbon groups include alkyl groups. Examples of alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, n-hexyl and iso-hexyl. Examples include alkyl groups having 1 to 6 carbon atoms such as Methyl is preferred.

Examples of monovalent aromatic hydrocarbon groups include aryl groups. Examples of aryl groups include aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl. Phenyl is preferred.

The monovalent hydrocarbon group is preferably methyl and/or phenyl, more preferably methyl.

The siloxane unit represented by -SiR ₂ O- is a straight-chain siloxy unit for introducing straight-chain siloxane bonds into the cured product during the reaction. The siloxane unit represented by —SiR ₂ O— preferably includes a dialkylsiloxane unit and an alkylarylsiloxane unit.

The dialkylsiloxane unit preferably includes a dimethylsiloxane unit.

The alkylarylsiloxane unit preferably includes a methylphenylsiloxane unit.

RO groups include, for example, alkoxy groups and aryloxy groups, preferably alkoxy groups, and more preferably methoxy.

（式中、Ｒ^１～Ｒ^６は、互いに同一または相異なってもよく、１価の飽和炭化水素基および１価の芳香族炭化水素基からなる群から選ばれる少なくとも１つの１価の炭化水素基を示す。式中、Ｒ^７～Ｒ^９は、互いに同一または相異なってもよく、１価の飽和炭化水素基を示す。Ｘは、シロキサンユニットである。） Specifically, the first oligomer is a siloxane oligomer containing units IV represented by the following formula (1) as structural units.

(Wherein, R ¹ to R ⁶ may be the same or different, and at least one monovalent hydrocarbon selected from the group consisting of monovalent saturated hydrocarbon groups and monovalent aromatic hydrocarbon groups group, wherein R ⁷ to R ⁹ may be the same or different and represent a monovalent saturated hydrocarbon group, and X is a siloxane unit.)

As at least one monovalent hydrocarbon group represented by R ¹ to R ⁶ and selected from the group consisting of monovalent saturated hydrocarbon groups and monovalent aromatic hydrocarbon groups, the same monovalent and a hydrocarbon group of The monovalent hydrocarbon groups represented by R ⁷ to R ⁹ include the monovalent saturated hydrocarbon groups exemplified for RO above.

In the first oligomer, unit I is an RO group-containing siloxane unit. a means the number of R ⁷ O groups bonded to the silicon atoms in unit I, for example 1 or 2, preferably 2; In that case, in unit I, the number (3-a) of monovalent hydrocarbon groups represented by R ¹ bonded to silicon atoms is preferably 1 (=3-2).

In unit I, the oxygen atom in Si—O— is bonded to one of the silicon atoms in units II to IV described below. Thereby, the Si—O— of this unit I forms a siloxane bond in the first oligomer. Unit I is a molecular terminal unit in the first oligomer.

Unit II is an RO group-containing siloxane unit. Unit II is a branched siloxy unit that serves as a starting point for three-dimensionalization during the reaction. The number of units II is not particularly limited, and is, for example, 2 or more, preferably 3 or more, and is, for example, an integer of 20 or less, preferably 13 or less.

Unit III is a siloxane unit having two oxygen atoms bonded to the silicon atom. Unit III is a branched siloxy unit. Unit III may also contain an RO group.

Examples of the siloxane unit represented by X include unit VI alone represented by the following formula (2), a combination of unit II and unit I (in the case of having unit I at the end via unit II), unit II and unit V (when having unit V at the terminal via unit II), and combinations of unit II and unit VI (when having unit VI at the terminal via unit II).

（式中、ｃは、２以上の整数である。Ｚ^１は、上記したＲで示される１価の炭化水素基またはＲＯ基である。） Unit VI includes a cyclic siloxane unit represented by the following formula (2).

(In the formula, c is an integer of 2 or more. Z ¹ is a monovalent hydrocarbon group or RO group represented by R above.)

The monovalent hydrocarbon group and RO group represented by Z ¹ are the same as above.

The number of units III is not particularly limited, and is, for example, 2 or more, and is, for example, an integer of 10 or less, preferably 6 or less.

Unit IV is a siloxane unit represented by —SiR ₂ O— above. Unit IV is a linear siloxy unit. The number of units IV is, for example, 1 or more, preferably 2 or more, and an integer of 20 or less, preferably 6 or less.

Unit V is an RO group-containing siloxane unit. The silicon atom in unit V bonds to any oxygen atom in units II to IV. The silicon atom in unit V thereby constitutes a siloxane bond in the first oligomer. Unit V is a molecular terminal unit in the first oligomer.

b means the number of OR ⁹ groups attached to the silicon atoms in unit V, for example 1 or 2, preferably 2; In that case, the number (3-e) of l-valent hydrocarbon groups represented by R ⁶ bonded to silicon atoms in unit V is preferably 1 (=3-2).

Each unit and its number described above are specified by ¹ H-NMR and ²⁹ Si-NMR.

The first oligomer can also be represented by the following average compositional formula (A).

Average compositional formula (A):
R ^p _α Si(OR ^q ) _β O _(4-α-β) (A)
(In the formula, R ^p and R ^q may be the same or different. R ^p is at least one selected from the group consisting of monovalent saturated hydrocarbon groups and monovalent aromatic hydrocarbon groups. represents a monovalent hydrocarbon group, R ^q represents a saturated monovalent hydrocarbon group, α represents a value whose average value is in the range of 0.40 to 1.70, β represents an average Indicates the value at which the ratio of OR ^q bonded to silicon atoms in the composition formula (A) is 5% by mass or more and less than 40% by mass.)

In the average composition formula (A), R ^p includes the same monovalent hydrocarbon groups as those of R ^l to R ⁶ in the general formula (1) described above, and R ^q includes the general formula ( The same monovalent saturated hydrocarbon groups as R ⁷ to R ⁹ in 1) can be mentioned.

In addition, β in the average composition formula (A) is such that the ratio of OR ^q bonded to silicon atoms in the average composition formula (A) is, for example, 10% by mass or more, preferably 20% by mass or more, or, for example, , 35% by mass or less, preferably 30% by mass or less.

As the first oligomer, for example, a dialkylsiloxane unit-containing oligomer containing a dialkylsiloxane unit in which R ¹ to R ⁹ in formula (1) are alkyl, for example, R ¹ to R ⁶ in formula (1) are alkyl and aryl, wherein R ⁷ -R ⁹ are alkyl, alkylarylsiloxane unit-containing oligomers. A dialkylsiloxane unit-containing oligomer does not contain an alkylarylsiloxane unit. On the other hand, the alkylarylsiloxane unit-containing oligomer may further contain a dialkylsiloxane unit.

More specifically, the dialkylsiloxane unit-containing oligomer preferably includes a dimethylsiloxane unit-containing oligomer in which R ¹ to R ⁹ in formula (1) are methyl and contains a dimethylsiloxane unit. Dimethylsiloxane unit-containing oligomers are produced, for example, from methyltrimethoxysilane and dimethyldimethoxysilane.

The alkylarylsiloxane unit-containing oligomer is preferably methylphenylsiloxane in which R ¹ to R ⁶ are methyl and phenyl, R ⁷ to R ⁹ are methyl, and a methylphenylsiloxane unit is contained in formula (1). Unit-containing oligomers are included. The methylphenylsiloxane unit-containing oligomer may further contain a dimethylsiloxane unit. Methylphenylsiloxane unit-containing oligomers are produced, for example, from methylphenyldimethoxysilane and methyltrimethoxysilane.

The molecular weight of the first oligomer is, for example, 500 or more, preferably 1,000 or more, and for example, 3,000 or less, preferably 2,000 or less.

A commercially available product is used as the first oligomer. For example, X-40-9250 (in formula (1), the number of units II is 8, the number of units III is 4, the number of units IV is 4, and R ¹ to R ⁹ are methyl) containing a dimethylsiloxane unit oligomer, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

The ratio of the first oligomer in the silicone composition is, for example, 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and particularly preferably 6% by mass. % or more, and, for example, less than 50% by mass, preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, particularly preferably 20% by mass or less, most preferably Preferably, it is 15% by mass or less.

The silicone composition preferably further contains a second oligomer.

The second oligomer forms a strong siloxane matrix with the first oligomer in the coating layer. The second oligomer is the curing component in the silicone composition. The second oligomer is —SiR ₂ O— (the two Rs may be the same or different, and are each at least selected from the group consisting of a monovalent saturated hydrocarbon group and a monovalent aromatic hydrocarbon group. Represents one monovalent hydrocarbon group) does not contain a siloxane unit represented by, and contains an RO group-containing siloxane unit containing an RO group (R represents a monovalent saturated hydrocarbon group) .

The monovalent hydrocarbon group and RO group include the same monovalent hydrocarbon group and RO group as in the above-described first oligomer.

The siloxane unit not contained in the second oligomer and represented by -SiR ₂ O- is a linear siloxy unit contained in the first oligomer.

（式中、Ｒ^ｌｌ～Ｒ^１４は、互いに同一または相異なってもよく、１価の飽和炭化水素基および１価の芳香族炭化水素基からなる群から選ばれる少なくとも１つの１価の炭化水素基を示す。Ｒ^１５～Ｒ^１７は、１価の飽和炭化水素基を示す。Ｙは、シロキサンユニットである。） Specifically, the second oligomer is a siloxane oligomer containing units XI to XIV represented by the following formula (3) as constitutional units.

(Wherein, R ¹¹ to R ¹⁴ may be the same or different, and at least one monovalent hydrocarbon selected from the group consisting of monovalent saturated hydrocarbon groups and monovalent aromatic hydrocarbon groups group, R ¹⁵ to R ¹⁷ each represent a monovalent saturated hydrocarbon group, and Y is a siloxane unit.)

The monovalent hydrocarbon groups represented by R ¹¹ to R ¹⁴ include the same monovalent hydrocarbon groups as R above. The monovalent saturated hydrocarbon groups represented by R ¹⁵ to R ¹⁷ include the same monovalent saturated hydrocarbon groups as R above.

In the second oligomer, unit XI is an RO group-containing siloxane unit. d means the number of R ¹⁵ O groups bonded to the silicon atom in unit XI, preferably two. In that case, the number (3-d) of monovalent hydrocarbon groups represented by R ¹¹ bonded to silicon atoms in unit XI is preferably 1 (=3-2).

The oxygen atom in unit XI is bonded to the silicon atom in unit XII or unit XIII described below. Thereby, the Si—O— of this unit XI forms a siloxane bond in the second oligomer. Unit XI is a molecular terminal unit in the second oligomer.

Unit XII is an RO group-containing siloxane unit. Unit XII is a branched siloxy unit. The number of units XII is not particularly limited, and is, for example, 2 or more, preferably 3 or more, and is an integer of, for example, 20 or less, preferably 17 or less.

Unit XIII is a siloxane unit having two oxygen atoms bonded to a silicon atom. Unit XIII is a branched siloxy unit. Unit XIII may also contain an RO group.

The siloxane unit represented by Y includes, for example, unit XV represented by the following formula (3) alone, unit XII and unit XI in combination (when unit XI is at the terminal via unit XII), unit XII and unit XIV (when having unit XIV at the terminal via unit XII), and combinations of unit XII and unit XV (when having unit XV at the terminal via unit XII).

（式中、ｆは、２以上の整数である。Ｚ^２は、上記した１価の炭化水素基またはＲＯ基である。） Unit XV includes a cyclic siloxane unit represented by the following formula (4).

(Wherein, f is an integer of 2 or more. Z ² is the monovalent hydrocarbon group or RO group described above.)

The monovalent hydrocarbon group and RO group represented by ^Z2 are the same as above.

The number of units XIII is not particularly limited, and is, for example, 2 or more, preferably 3 or more, and is an integer of, for example, 18 or less, preferably 15 or less.

The silicon atom in unit XIV is bonded to the oxygen atom in unit XII or unit XIII. The silicon atom in unit XIV thereby forms a siloxane bond in the second oligomer. Unit XIV is a molecular terminal unit in the second oligomer.

In unit XIV, the number of OR ¹⁷ groups attached to silicon atoms is for example 1 or 2, preferably 2. In that case, in unit XIV, the number (3-e) of monovalent hydrocarbon groups represented by R ¹⁴ bonded to silicon atoms is preferably 1 (=3-2).

Each unit described above and its number are specified by ¹ H-NMR and ²⁹ Si-NMR.

The second oligomer can also be represented by the following average compositional formula (B).

Average compositional formula (B):
R ^t _γ Si(OR ^s ) _δ O _(4-γ-δ) (B)
(In the formula, R ^t and R ^s may be the same or different. R ^t is at least one selected from the group consisting of monovalent saturated hydrocarbon groups and monovalent aromatic hydrocarbon groups. represents a monovalent hydrocarbon group, R ^s represents a monovalent saturated hydrocarbon group, γ represents a value whose average value is in the range of 0.40 to 1.70, δ represents an average Indicates the value at which the ratio of OR ^s bonded to silicon atoms in the composition formula (B) is 5% by mass or more and less than 40% by mass.)

In the average composition formula (B), R ^t includes the same monovalent hydrocarbon groups as those of R ¹¹ to R ¹⁴ in the general formula (3) described above, and R ^s includes the groups represented by the general formula (3 ), the same monovalent saturated hydrocarbon groups as R ¹⁵ to R ¹⁷ in ).

In addition, δ in the average composition formula (B) is such that the ratio of ^ORS bonded to silicon atoms in the average composition formula (B) is, for example, 10% by mass or more, preferably 20% by mass or more. This value is 35% by mass or less.

Specifically, the second oligomer does not contain, for example, a linear siloxy unit represented by -SiR ₂ O- and does not contain a linear siloxy unit in which R ¹¹ to R ¹⁷ in formula (3) are alkyl. -alkyl-based oligomers, for example, containing no linear siloxy units represented by -SiR ₂ O-, R ¹¹ to R ¹⁴ are alkyl and aryl, and R ¹⁵ to R ¹⁷ in formula (3) are alkyl straight-chain siloxy unit-free alkylaryl oligomers; Linear siloxy unit-free-alkyl-based oligomers do not contain alkylaryl siloxane units.

More specifically, linear siloxy unit-free alkyl-based oligomers preferably include linear siloxy unit-free methyl-based oligomers in which R ¹¹ to R ¹⁷ in formula (3) are methyl. . Linear siloxy unit-free-methyl-based oligomers are produced, for example, from methyltrimethoxysilane.

The straight-chain siloxy unit-free alkylaryl-based oligomer is a straight-chain siloxy unit-free-methyl oligomer in which R ¹¹ to R ¹⁴ in formula (3) are methyl and phenyl, and R ¹⁵ to R ¹⁷ are methyl. Examples include phenyl oligomers. Linear siloxy unit-free-methylphenyl-based oligomers are produced, for example, from phenyltrimethoxysilane and methyltrimethoxysilane.

The molecular weight of the second oligomer is, for example, 500 or more, preferably 1,000 or more, and for example, 4,000 or less, preferably 3,000 or less.

A commercial product is used as the second oligomer. For example, KC-89 (manufactured by Shin-Etsu Chemical Co., Ltd.), KR-515 (manufactured by Shin-Etsu Chemical Co., Ltd.), KR-500 (in formula (3), the number of units XII is 10 and the number of units XIII is 4). Chain siloxy unit-free-methyl-based oligomer, manufactured by Shin-Etsu Chemical Co., Ltd.), X-40-9225 (in formula (3), linear siloxy unit-free-methyl having 12 units XII and 10 units XIII) system oligomer, manufactured by Shin-Etsu Chemical Co., Ltd.), US-SG2403 (manufactured by Dow Corning Toray Co., Ltd.), KR-401N (in formula (3), R ¹¹ to R ¹⁴ are methyl and phenyl, R ¹⁵ to R ¹⁷ are methyl, Some linear siloxy unit-free-methylphenyl-based oligomers) can be exemplified.

The ratio of the second oligomer in the silicone composition is, for example, 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and particularly preferably 30% by mass. % or more, and for example, less than 50% by mass, preferably 45% by mass or less.

The ratio of the first oligomer to the second oligomer (first oligomer/second oligomer: mass ratio) is, for example, 0.15 or more, preferably 0.16 or more, more preferably 0.18 or more, and still more preferably , 0.20 or more, more preferably 0.22 or more. Further, the ratio of the first oligomer to the second oligomer (first oligomer/second oligomer: mass ratio) is, for example, 10 or less, preferably 9 or less, more preferably 7 or less, still more preferably 5 or less, Particularly preferably, it is 2 or less, further 1.0 or less, furthermore 0.5 or less.

The ratio of the total amount of the first oligomer and the second oligomer (curing component) in the silicone composition is, for example, 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, and still more preferably 35% by mass. % by mass or more, particularly preferably 40% by mass or more, most preferably 45% by mass or more. The ratio of the total amount of the first oligomer and the second oligomer (curing component) in the silicone composition is, for example, 60% by mass or less, preferably 55% by mass or less. If the ratio of the first oligomer and/or the second oligomer is within the above range, the hydrophobic inorganic particles can sufficiently exhibit their functions.

The silicone composition more preferably further contains silicone oil.

The silicone oil improves the liftability (uneven distribution) of the hydrophobic inorganic particles when molding a molded article from the particle-containing resin composition containing the hydrophobic inorganic particles. Silicone oil has a linear main chain, for example, a repeating polysiloxane structure (-(SiO) _n -). Examples of silicone oils include straight silicone oils (unmodified silicone oils) such as polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. In addition to straight silicone oils, silicone oils include those whose main chain ends and/or side chains are modified with hydrogen atoms, alkyl groups, alkenyl groups (including vinyl groups), alkynyl groups, phenyl groups, ionic groups, etc. and modified silicone oils. The ionic group includes, for example, an anionic group such as a mercapto group, and a cationic group such as an amino group. These silicone oils can be used alone or in combination of two or more. The silicone oil preferably includes straight silicone oil, more preferably polydimethylsiloxane.

The kinematic viscosity of the silicone oil at 25° C. is, for example, 100 mm ² /s or higher, preferably 200 mm ² /s or higher, more preferably 500 mm ² /s or higher, still more preferably 1000 mm ² /s or higher. In addition, the kinematic viscosity of the silicone oil at 25° C. is, for example, 1,000,000 mm ² /s or less, preferably 500,000 mm ² /s or less, more preferably 100,000 mm ² /s or less, still more preferably 1 10,000 mm ² /s or less. If the kinematic viscosity of the silicone oil is equal to or less than the upper limit described above, the silicone oil can be easily handled and the silicone composition can be easily prepared.

As the silicone oil, commercially available products are used, for example, KF-96 series (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-965 series (manufactured by Shin-Etsu Chemical Co., Ltd.), SH200 series (manufactured by Dow Corning Toray Co., Ltd.), TSF451 series. (manufactured by Momentive Performance Materials Japan), YF-33 series (manufactured by Momentive Performance Materials Japan), and the like are used.

The ratio of silicone oil to the silicone composition is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and still more preferably 1.5% by mass. % by mass or more, and for example, 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less. The number of parts by mass of the silicone oil with respect to 100 parts by mass of the total amount of the first oligomer and the second oligomer is, for example, 1 part by mass or more, preferably 3 parts by mass or more, more preferably 5 parts by mass or more. 20 parts by mass or less, preferably 10 parts by mass or less, more preferably 7 parts by mass or less. If the number of parts by mass of the silicone oil is within the above range, the floating property (uneven distribution) of the hydrophobic inorganic particles can be improved.

The ratio of the total amount of the first oligomer, the second oligomer, and the silicone oil to the silicone composition is, for example, 21% by mass or more, preferably 26% by mass or more, more preferably 31% by mass or more, and still more preferably 36% by mass. % by mass or more. The ratio of the total amount of the first oligomer, the second oligomer and the silicone oil to the silicone composition is, for example, 70% by mass or less, preferably 60% by mass or less, more preferably 55% by mass or less. If the proportion of the above total amount is equal to or higher than the above lower limit, it is possible to prevent the proportion of the curing component from becoming excessively small, and to reliably form the coating layer on the surfaces of the hydrophobic inorganic particles. When the ratio of the above total amount is equal to or less than the above upper limit, excessive decrease in yield can be suppressed.

The silicone composition can further contain catalysts and organic solvents.

The catalyst is a curing catalyst that reacts with moisture in the air to hydrolyze and cause condensation of the first oligomer (and the second oligomer) when the silicone composition cures.

Examples of catalysts include metal alkoxides, metal chelate compounds (e.g., tris(2,4-pentanedionato)aluminum, etc.), metal carboxylates (e.g., bis(2-ethylhexanoic acid), acids (phosphoric acid, etc. ), etc. The catalyst can be used alone or in combination, preferably metal alkoxides, metal chelate compounds, and metal carboxylates, and more preferably metal alkoxides.

Examples of metal alkoxides include titanium alkoxide, aluminum alkoxide (eg, aluminum tetra-n-butoxide, aluminum tetra-n-propoxide), zirconium alkoxide (eg, zirconium tetra-n-butoxide, zirconium tetra-n-propoxide), germanium alkoxide. (e.g. germanium tetraethoxide), tin alkoxides (e.g. tin tetra n-butoxide, tin tetra tert-butoxide), hafnium alkoxides (e.g. hafnium tetra-2-propoxide, hafnium tetra tert-butoxide), niobium alkoxides (e.g. niobium pentaethoxide), tantalum alkoxides (eg, tantalum penta-n-butoxide, tantalum pentaethoxide), and the like. Titanium alkoxide is preferred.

Examples of titanium alkoxide include titanium trialkoxide, titanium tetraalkoxide and the like, preferably titanium tetraalkoxide. Titanium tetraalkoxides include, for example, titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide (e.g., titanium tetraisopropoxide, titanium tetra-n-propoxide, etc.), titanium tetrabutoxide (e.g., titanium tetraisobutoxide , titanium tetra n-butoxide, etc.), titanium tetrapentoxide, titanium tetrahexoxide, titanium tetra(2-ethylhexoxide) and the like.

The three or four RO groups in the metal alkoxide differ in reactivity depending on the number of carbon atoms and the presence or absence of branching. On the other hand, if the hydrolysis proceeds too quickly, the handleability (stability) may deteriorate. Therefore, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetraisobutoxide, and titanium tetra-n-butoxide are preferred among titanium alkoxides in consideration of reactivity and stability.

As the catalyst, a commercially available product such as D-25 (titanium tetra-n-butoxide, manufactured by Shin-Etsu Chemical Co., Ltd.) is used.

The ratio of the catalyst in the silicone composition is, for example, 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and is, for example, 25% by mass or less, preferably 15% by mass. % by mass or less, more preferably 10% by mass or less. The number of parts by mass of the catalyst with respect to 100 parts by mass of the first oligomer is, for example, 1 part by mass or more, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and for example, 250 parts by mass or less, preferably , 100 parts by mass or less, more preferably 50 parts by mass or less.

The organic solvent is added to the particle-containing resin composition in order to suppress uneven thickness of the coating layer caused by excessively rapid drying after mixing with the inorganic particles.

Examples of organic solvents include alcohol solvents such as methyl alcohol, ethyl alcohol and isopropyl alcohol (2-propanol); ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate; glycol ether solvents; It is selected from solvents, naphthenic solvents, aromatic solvents and the like. A single organic solvent is selected, or two or more organic solvents are selected and used. As the organic solvent, an alcoholic solvent is preferably selected.

The ratio of the organic solvent to the silicone composition is, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more. % by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. The ratio of the organic solvent to the total amount of 100 parts by mass of the first oligomer, the second oligomer and the silicone oil is, for example, 40 parts by mass or more, preferably 80 parts by mass or more, and for example, 300 parts by mass or less, preferably is 200 parts by mass or less, more preferably 160 parts by mass or less, and still more preferably 100 parts by mass or less.

When the proportion of the organic solvent is at least the above lower limit, the silicone composition is excellent in handleability and suppresses thickness unevenness of the coating layer caused by excessively rapid drying after mixing with the inorganic particles. can be done. On the other hand, when the proportion of the organic solvent is equal to or less than the above upper limit, it is possible to suppress an excessive decrease in yield.

The ratio of the mass of the cured product in the silicone composition to the silicone composition before curing is, for example, 15% by mass or more, preferably 20% by mass or more, and more preferably 30% by mass or more. The ratio of each component described above is set so as to be 60% by mass or less, preferably 50% by mass or less. The mass of the cured product (and components incorporated into the cured product (specifically, silicone oil, catalyst, etc.)) is the total mass of each component minus the organic solvent and hydrolysis product. The mass of the cured product can also be calculated from the mass loss of the silicone composition before and after curing.

In addition, the proportion of units derived from the first oligomer in the cured product of the silicone composition is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass. % by mass or more, and for example, 100% by mass or less, preferably 75% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

Next, a method for producing hydrophobic inorganic particles will be described.

This method for producing hydrophobic inorganic particles comprises a first step of mixing inorganic particles and a silicone composition, and a second step of curing the silicone composition and coating the surface of the inorganic particles with a cured product of the silicone composition. 2 steps.

In the first step, inorganic particles and a silicone composition are blended and stirred and mixed. A mixture is thus prepared. To prepare the silicone composition, the above ingredients are blended. While the inorganic particles are stirred with a stirrer such as a disper, the silicone composition is added dropwise thereto.

The ratio of the cured product (solid content after curing) of the silicone composition to 100 parts by mass of the inorganic particles is, for example, 1 part by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and , for example, 250 parts by mass or less, preferably 100 parts by mass or less, more preferably 50 parts by mass or less. The proportion of the cured silicone composition (solid content after curing) in the hydrophobic inorganic particles is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, or , for example, 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 15% by mass or less.

If the proportion of the cured product is at least the lower limit described above, when molding a molded article from the particle-containing resin composition, more specifically, the particle-containing resin composition becomes a liquid composition due to gelation, drying and solidification. While becomes a solid molded body, the hydrophobic inorganic particles can be reliably floated from the inside of the molded body toward the surface and unevenly distributed on the surface of the molded body.

On the other hand, when the proportion of the cured product is equal to or less than the upper limit described above, excessive clogging of the pores of the inorganic particles can be suppressed, and inhibition of the functional expression of the inorganic particles can be suppressed.

Subsequently, in the second step, the mixture is heated, for example.

The leaving time is, for example, 10 minutes or more, preferably 30 minutes or more, and is, for example, 10 hours or less, preferably 2 hours or less.

As a result, in the first oligomer (and the second oligomer), the curing reaction proceeds due to the condensation reaction of the RO groups.

At the same time, if the material of the inorganic particles is an oxide (especially silica), it undergoes a condensation reaction with hydroxyl group-containing groups (specifically, silanol groups [Si—OH]) present on the surface of the inorganic particles to form inorganic The particles and the first oligomer (and the second oligomer) form chemical bonds.

Alcohol, which is a by-product of the curing reaction of the RO groups of the first oligomer (and second oligomer), is removed (distilled off) together with the organic solvent.

Thereby, the silicone composition is cured to prepare a cured product of the silicone composition. The surface of the inorganic particles is coated with this cured product. That is, a coating layer is formed on the surfaces of the inorganic particles. If necessary, the cured product connecting adjacent inorganic particles is pulverized by a jet mill or the like to produce individual hydrophobic inorganic particles.

Thereby, hydrophobic inorganic particles containing inorganic particles and a coating layer are produced.

The coating layer covers the surface of the inorganic particles, further includes a mode of coating the inner surface (inner surface of the pores), a mode of partially coating the surface of the inorganic particles, and the like. In other words, the coating layer may cover at least part of the surfaces of the inorganic particles.

Next, a mode in which the inorganic particles support the functional component will be described.

The function of the functional component may be a function originally possessed by the inorganic particles, or may be a different function. Specifically, functional components include, for example, antibiotic compounds, flame retardants, curing agents, pigments, fragrances, enzymes, and bird and animal repellents. Moreover, the functional ingredient may be either water-soluble or water-insoluble. Water-insoluble functional ingredients are preferred when used in applications requiring water resistance.

Antibiotically active compounds are bactericidal, antibacterial, antiseptic, algicidal, antifungal, selected from herbicides, insecticides, attractants and repellents, and the like;

Bactericidal, antiseptic, antialgal, antifungal agents (including antiseptic, antifungal agents) include, for example, organic iodine compounds, triazole compounds, carbamoyl imidazole compounds, dithiol compounds, isothiazoline compounds, nitroalcohol compounds, and paraoxybenzoic acid. Esters, benzimidazole-based compounds, triazine-based compounds, pyrithione-based compounds, and the like.

Examples of organic iodine compounds include 3-iodo-2-propynylbutylcarbamate (IPBC), 1-[[(3-iodo-2-propynyl)oxy]methoxy]-4-methoxybenzene, 3-bromo-2 , 3-diiodo-2-propenylethyl carbonate and the like.

Examples of triazole compounds include 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole (propico nazol), bis(4-fluorophenyl)methyl(1H-1,2,4-triazol-1-ylmethylsilane (also known as flusilazole, 1-[[bis(4-fluorophenyl)methylsilyl]methyl]-1H- 1,2,4-triazole) and the like.

Carbamoyl imidazole compounds include, for example, N-propyl-N-[2-(2,4,6-trichloro-phenoxy)ethyl]imidazole-1-carboxamide (prochloraz).

Dithiol compounds include, for example, 4,5-dichloro-1,2-dithiol-3-one.

Examples of isothiazoline compounds include 2-n-octyl-4-isothiazolin-3-one (OIT), 4,5-dichloro-2-n-octylisothiazolyl-3-one (DCOIT), 5-chloro -2-methyl-4-isothiazolin-3-one (Cl-MIT) and 2-methyl-4-isothiazolin-3-one (H-MIT).

Examples of nitroalcohol compounds include 2,2-dibromo-2-nitro-1-ethanol (DBNE) and 2-bromo-2-nitropropane-1,3-diol (bronopol).

Examples of paraoxybenzoic acid esters include butyl parahydroxybenzoate and propyl parahydroxybenzoate.

Examples of benzimidazole compounds include methyl 1H-benzimidazol-2-ylcarbamate hydrochloride (carbendazim hydrochloride).

Examples of triazine compounds include hexahydro-1,3,5-tris(2-hydroxyethyl)-1,3,5-triazine.

Examples of pyrithione compounds include sodium 2-pyridinethiol-1-oxide (NaPt).

Examples of termiticides (anticides) include pyrethroid compounds, neonicotinoid compounds, organochlorine compounds, organophosphorus compounds, carbamate compounds, and oxadiazine compounds.

Examples of pyrethroid compounds include pyrethroid insecticides such as pyrethrins, synerins, and jasmolins obtained from Pleurotus sycamore, and allethrins derived from these, bifenthrin, acrinathrin, alphacypermethrin, tralomethrin, cyfluthrin, cyphenothrin, and prallethrin. , etofenprox (2-(4-ethoxyphenyl)-2-methylpropyl-3-phenoxybenzyl ether), silafluofen, fenvalerate and other pyrethroid insecticides.

Examples of neonicotinoid compounds include (E)-N1-[(6-chloro-3-pyridyl)methyl]-N2-cyano-N1-methylacetamidine (acetamiprid).

Examples of organic chlorine compounds include kersene.

Examples of organic phosphorus compounds include phoxime, pyridafenthion, fenitrothion, tetrachlorbinphos, diclofenthion, propetamphos, and the like.

Examples of carbamate compounds include fenocarb and propoxur.

Oxadiazine-based compounds include, for example, indoxacarb.

Furthermore, herbicides include, for example, pyraclonil, pendimethalin, indanophan, and the like.

Examples of insecticides include pyriproxyfen and the like.

Examples of repellents include DEET, capsaicins (pungent components), and the like. Capsaicins are preferred.

Examples of capsaicins include capsaicin (N-[(4-hydroxy-3-methoxyphenyl)methyl]-8-methyl-6-nonenamide) and capsaicin derivatives. Capsaicin derivatives include, for example, N-vanillylnonanamide (nonylic acid vanillylamide), decylic acid vanillylamide, nordihydrocapsaicin, dihydrocapsaicin, homodihydrocapsaicin, homocapsaicin and the like.

The antibiotic compound preferably includes an antiseptic and antifungal agent, more preferably an organic iodine compound, and still more preferably IPBC.

When the functional component is supported on the inorganic particles, the functional component and the inorganic particles are blended if the functional component is liquid at 25°C.

On the other hand, if the functional ingredient is in a semi-solid or solid state at 25° C., the functional ingredient is dissolved in an organic solvent to prepare a solution of the functional ingredient, the solution and inorganic particles are blended, and then the organic solvent is mixed. to remove Examples of organic solvents include organic solvents optionally contained in the silicone composition, preferably ketone solvents. The organic solvent and the functional component are added so that the blending ratio of the functional component is, for example, 30% by mass or more, preferably 50% by mass or more, and, for example, 80% by mass or less, relative to the total amount of the organic solvent and the functional component. Adjust the mixing ratio of the ingredients.

The number of parts by mass of the functional component with respect to 100 parts by mass of the inorganic particles is, for example, 10 parts by mass or more, preferably 40 parts by mass or more, more preferably 75 parts by mass or more, and for example, 500 parts by mass or less, preferably , 250 parts by mass or less, more preferably 125 parts by mass or less.

Also, the volume of the solution of the functional component is smaller than, for example, the oil absorption capacity of the inorganic particles (the value obtained by multiplying the oil absorption amount of the inorganic particles by the blended mass of the inorganic particles). Specifically, the number of volume parts of the functional ingredient solution to 100 volume parts of the oil absorption volume of the inorganic particles is, for example, less than 100 volume parts, preferably 75 volume parts or less, more preferably 50 volume parts or less, and even more preferably , 30 parts by volume or less and, for example, 10 parts by volume or more.

This causes the inorganic particles to support the functional component.

The inorganic particles are then coated with a coating layer. The method for coating the inorganic particles with the coating layer is the same as described above.

As a result, functional component-supporting hydrophobic inorganic particles are obtained.

The number of parts by mass of the coating layer relative to 100 parts by mass of the functional component is, for example, 10 parts by mass or more, preferably 40 parts by mass or more, more preferably 75 parts by mass or more, and for example, 500 parts by mass or less, preferably , 250 parts by mass or less, more preferably 125 parts by mass or less.

The number of parts by mass of the coating layer with respect to 100 parts by mass of the total amount of the inorganic particles and the functional component is, for example, 0.5 parts by mass or more, preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and still more preferably 10 parts by mass. parts by mass or more and, for example, 500 parts by mass or less, preferably 250 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 50 parts by mass or less.

Hydrophobic inorganic particles (including functional component-supporting hydrophobic inorganic particles) are, for example, blended (added) to various resins and used as additives for preparing particle-containing resin compositions.

However, the hydrophobic inorganic particles are not used as cosmetic additives added to cosmetics, that is, they are not cosmetic additives.

Next, a particle-containing resin composition containing hydrophobic inorganic particles will be described.

The particle-containing resin composition contains the hydrophobic inorganic particles described above and a resin.

The resin is not particularly limited as long as it is a resin capable of unevenly distributing hydrophobic inorganic particles on the surface thereof when it becomes a coating film or a molded article, for example. Examples of resins include aqueous resins. Examples of water-based resins include resins dispersed or dissolved in water. Such resins include, for example, acrylic resins, acrylic-styrene resins, styrene resins, vinyl acetate resins, ethylene vinyl acetate, and vinyl chloride. Resins, polyester resins, silicone resins, urethane resins, fluorine resins and the like can be used. Further, examples of resins include soft resins (elastomers) having a glass transition temperature of room temperature (25° C.) or lower.

In addition to water-based resins, resins obtained by dispersing or dissolving the above resins in a solvent can also be used. Examples of such resins include liquid thermosetting resins such as unsaturated polyester resins, vinyl ester resins, urethane acrylate resins, and alkyd resins. Furthermore, injection molding, extrusion molding, molds, extruder dies, cylinders, and screws are made hydrophobic with silicone oil, etc., so that thermoplastic resins containing the above resins are melted and molded. , the hydrophobic inorganic particles of the present invention can be unevenly distributed on the surface.

The resin preferably includes an aqueous resin. If it is a water-based resin, the hydrophobic inorganic particles are more likely to be unevenly distributed on the surface of the molded article.

The form of the aqueous resin is not particularly limited, and examples thereof include latex.

The ratio of the hydrophobic inorganic particles to the total amount of the resin (solid content) and the hydrophobic inorganic particles is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, and more preferably 1% by mass or more. Also, for example, it is 25% by mass or less, preferably 5% by mass or less. The number of parts by mass of the hydrophobic inorganic particles with respect to 100 parts by mass of the resin (solid content) is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and For example, it is 25 parts by mass or less, preferably 5 parts by mass or less.

To prepare the particle-containing resin composition, the above-described hydrophobic inorganic particles and a resin are blended. Then stir them.

In addition, when the resin is prepared in a form containing water, the particle-containing resin composition may contain such water. The solid content ratio in the particle-containing resin composition is, for example, 5% by mass or more, preferably 25% by mass or more, and is, for example, 75% by mass or less, preferably 60% by mass or less.

In addition, known additives can be added to the particle-containing resin composition in an appropriate ratio.

Thereafter, a molded body is molded from the particle-containing resin composition. Examples of molding methods include cast molding (including thermal gelation method), spray-up molding, hand lay-up molding, slush molding, extrusion molding, impregnation molding, and dipping method (including salt solidification method).

Thereby, a molded article made of the particle-containing resin composition is obtained.

Examples of molded articles include wallpaper, floor materials, ceiling materials, building materials such as sealing materials, and the like.

When the hydrophobic inorganic particles of the present invention are used as an additive for paint and a coating film is formed from the particle-containing resin composition, the hydrophobic inorganic particles are unevenly distributed on the surface of the coating film, and the effect of the hydrophobic inorganic particles is exhibited. can be used effectively.

When the hydrophobic inorganic particles of the present invention are blended with a thermoplastic resin (including compositions in which the hydrophobic inorganic particles are dispersed in a small amount of resin to prepare a masterbatch and this is blended with the remaining resin), The hydrophobic inorganic particles are unevenly distributed on the surface of the molded product, and the effect of the hydrophobic inorganic particles can be effectively exhibited.

(Effect)
Since the hydrophobic inorganic particles have an oil absorption of 50 mL/100 g or more, the inorganic particles have a sufficient pore volume. Therefore, the porous function of the inorganic particles can be fully exhibited.

Further, since the coating layer is a cured product of the silicone composition containing the first oligomer containing the siloxane unit represented by —SiR ₂ O—, the hydrophobic inorganic particles can be unevenly distributed on the surface of the molded body. .

Furthermore, since the inorganic particles have a substantially spherical shape, the above-described hydrophobic inorganic particles can be unevenly distributed quickly.

Therefore, a molded article molded from a particle-containing resin composition containing hydrophobic inorganic particles can exhibit high performance since the hydrophobic inorganic particles are unevenly distributed on the surface of the molded article.

Further, when the inorganic particles are deodorant particles, a particle-containing resin composition containing hydrophobic inorganic particles and a resin can be prepared as a composition for a deodorant molded article, and then the deodorant molded article is prepared. can be molded. In this deodorant molded article, since the hydrophobic inorganic particles are unevenly distributed on the surface of the deodorant molded article, high deodorizing properties can be exhibited.

In the case where the inorganic particles carry a functional component, a particle-containing resin composition containing the functional component-carrying hydrophobic inorganic particles and a resin can be prepared as a composition for a molded body exhibiting function. , a function-exhibiting molded product can be molded. In this function-expressing molded article, since the hydrophobic inorganic particles carrying the functional component are unevenly distributed on the surface of the function-expressing molded body, it is possible to exhibit higher functions based on the functional component.

Specifically, when the functional component carries an antiseptic/antifungal agent, a particle-containing resin composition containing hydrophobic inorganic particles and a resin can be prepared as an antiseptic/antifungal molded article composition. Then, an antiseptic and antifungal molding can be molded. In this antiseptic-antifungal molded article, since the hydrophobic inorganic particles carrying the antiseptic-antifungal agent are unevenly distributed on the surface of the antiseptic-antifungal molded article, a high antiseptic-antifungal effect can be exhibited.

Moreover, when the silicone composition contains the second oligomer in addition to the first oligomer, a strong siloxane matrix can be formed in the coating layer together with the first oligomer.

Furthermore, when the silicone composition contains silicone oil in addition to the first oligomer (and the second oligomer), it is possible to improve the liftability (uneven distribution) of the hydrophobic inorganic particles. Therefore, the hydrophobic inorganic particles can be reliably floated from the interior of the molded body toward the surface and unevenly distributed on the surface of the molded body.

MODIFIED EXAMPLES In the following modified examples, the same reference numerals are given to members and steps similar to those described above, and detailed description thereof will be omitted. In addition, the modification can have the same effects as those described above, unless otherwise specified.

In a variant, the inorganic particles can have multiple functions, for example, they can be both deodorant inorganic particles and supporting inorganic particles. This inorganic particle carries another functional component.

Specific numerical values such as the mixing ratio (content ratio), physical property values, and parameters used in the following description are described in the above "Mode for Carrying Out the Invention", the corresponding mixing ratio (content ratio ), physical properties, parameters, etc. can.

First, details such as raw materials are described.
・X-40-9250: a dimethylsiloxane unit-containing oligomer having 8 units II, 4 units III, and 4 units IV in formula (1), and wherein R ¹ to R ⁹ are methyl (First Oligomer) KR-500 manufactured by Shin-Etsu Chemical Co., Ltd.: Linear siloxy in which the number of units XII is 10, the number of units XIII is 4, and R ¹¹ to R ¹⁷ are methyl in formula (3) Unit-free-methyl-based oligomer (second oligomer), Shin-Etsu Chemical Co., Ltd. KR-401N: Linear chain in which R ¹¹ to R ¹⁴ are methyl and phenyl, and R ¹⁵ to R ¹⁷ are methyl in formula (3) Siloxy unit-free-methylphenyl oligomer (second oligomer), manufactured by Shin-Etsu Chemical Co., Ltd. KF-96-1000cs: Polydimethylsiloxane, kinematic viscosity (25° C.): 1,000 mm ² /s, manufactured by Shin-Etsu Chemical Co., Ltd.・ D-25: Titanium (IV) tetra n-butoxide, manufactured by Shin-Etsu Chemical Co., Ltd. ・ IPA: Isopropyl alcohol ・ IPBC: Trade name “Fungitrol 400”, 3-iodo-2-propynyl butyl carbamate, water-insoluble antiseptic Mildew Agent, International Specialty Products Seventol OM-1: Contains a composite of silica, alumina and zinc oxide. Average particle diameter of 5 μm, oil absorption of 120 mL/100 g, deodorizing particles, Silicia 310P manufactured by Osaka Gas Chemicals Co., Ltd.: Silica. Average particle size 2.7 μm, oil absorption 330 mL / 100 g, carrier for support, manufactured by Fuji Silysia Ltd.

Preparation Examples 1 to 3
(Preparation of silicone composition)
Each component described in Table 1 was blended to prepare the silicone composition (1) of Preparation Example 1, the silicone composition (2) of Preparation Example 2, and the silicone composition (3) of Preparation Example 3, respectively. was prepared.

Comparative example 1
Seventol OM-1 was prepared as inorganic particles of Comparative Example 1 as it was.

Examples 1 to 7
(Preparation of hydrophobic inorganic particles)
According to the description in Table 2, while stirring the inorganic particles of Comparative Example 1 with a disper, the silicone composition (Preparation Example 1, Preparation Example 2, or Preparation Example 3) was added dropwise. After standing for 24 hours, it was heated at 100° C. for 1 hour to cure the silicone composition and form a coating layer. After that, they were pulverized by a jet mill to prepare hydrophobic inorganic particles of Examples 1 to 7 containing inorganic particles and a coating layer.

Examples 8 to 14
(Preparation of deodorant molding)
As a water-based resin, each of the hydrophobic inorganic particles of Examples 1 to 7 was added to acrylic-styrene resin latex "Ultrasol C-63" (manufactured by Aica Kogyo Co., Ltd.) and stirred. The ratio of the hydrophobic inorganic particles to the total amount of the aqueous resin (solid content) and the hydrophobic inorganic particles was 3% by mass.

Next, the composition for a deodorant molded article was poured into a glass plate partitioned on four sides so that the thickness when dry was 3 mm, and air-dried in a horizontal state to obtain the deodorant molded articles of Examples 8 to 14. The plate was molded (cast). In all of the deodorant molded plates of Examples 8 to 14, the hydrophobic inorganic particles protruded from the inside of the deodorant molded plate and were unevenly distributed on the surface of the deodorant molded plate.

Comparative example 2
Except for using the inorganic particles of Comparative Example 1 instead of the hydrophobic inorganic particles of Example 1, the same process as in Example 7 was carried out to mold (cast) a deodorant molded plate. In the deodorant molded plate of Comparative Example 2, the inorganic particles settled with respect to the aqueous resin.

Comparative example 3
A molded plate was molded (cast) in the same manner as in Example 7, except that the hydrophobic inorganic particles of Example 1 were not blended.

<Evaluation>
The following deodorizing test was performed to evaluate the deodorizing property [Ammonia deodorizing test]

Each of the molded deodorant plates of Examples 8 to 14 and Comparative Example 2 was cut into squares to prepare samples. Samples were weighed into aluminum petri dishes and sealed in 1 L Tedlar bags. At this time, the mass of the inorganic particles (OM-1) was adjusted to 10 mg. After that, 1 L of ammonia-containing gas with a concentration of 100 ppm was injected into the 1 L Tedlar bag. 2 hours after the gas injection and 24 hours after the gas injection, the ammonia gas concentration was measured with an ammonia detector tube. The molded plate of Comparative Example 3 was also measured in the same manner as described above. The results are listed in Table 3.

[Hydrogen sulfide deodorant test]
Each of the molded deodorant plates of Examples 8 to 14 and Comparative Example 2 was cut into squares to prepare samples. Samples were weighed into aluminum petri dishes and sealed in 1 L Tedlar bags. At this time, the mass of the inorganic particles (OM-1) was adjusted to 10 mg. After that, 1 L of hydrogen sulfide-containing gas with a concentration of 40 ppm was injected into the 1 L Tedlar bag. After 2 hours and 24 hours from the gas injection, the gas concentration of hydrogen sulfide was measured with a hydrogen sulfide detector tube. The molded plate of Comparative Example 3 was also measured in the same manner as described above. The results are listed in Table 4.

Comparative example 4
(Preparation of IPBC-supported inorganic particles)
A 60% solution of IPBC in acetone was added to the support inorganic particles (Sylysia 310P) with disper stirring. After that, by vacuum drying at 60° C. for 3 hours, IPBC-supporting inorganic particles supporting IPBC were prepared.

Examples 15 to 21
(Preparation of IPBC-supporting hydrophobic inorganic particles)
While the IPBC-supported inorganic particles of Comparative Example 4 were being disper-stirred, the silicone composition was added dropwise. After standing for 24 hours, it was heated at 100° C. for 1 hour to cure the silicone composition and form a coating layer. After that, they were pulverized by a jet mill to prepare IPBC-supporting hydrophobic inorganic particles.

Comparative example 5
(Preparation of aqueous dispersion of IPBC)
An aqueous dispersion of IPBC (flowable agent) was prepared. Specifically, 88.0 g of deionized water, 10.0 g of IPBC (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 2.0 g of Pelex SS-L (manufactured by Kao) were blended, and these were mixed in a beer mill (bead size : 1 mm) at 2,000 rpm for 10 minutes. Thus, a flowable formulation in which IPBC is dispersed in water was prepared. The median diameter of the flowable agent was 6.9 μm when measured with a laser diffraction scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.).

Examples 22 to 28
Each of the IPBC-supporting hydrophobic inorganic particles of Examples 15 to 21 was added to acrylic-styrene resin latex "Ultrasol C-63" (manufactured by Aica Kogyo Co., Ltd.), IPBC in the antiseptic antifungal molded article composition They were blended and stirred so that the concentration was 500 ppm. In this way, compositions for antiseptic and antifungal moldings of Examples 22 to 28 were prepared. Next, the antiseptic and antifungal molding composition was poured into a glass plate partitioned on four sides so that the thickness when dry was 3 mm, and air-dried in a horizontal state to obtain the antiseptic products of Examples 22 to 28. A molded (cast) antifungal plate was molded. In all of the antiseptic and antifungal molded plates of Examples 22 to 28, the IPBC-supporting hydrophobic inorganic particles protruded from the inside of the antiseptic and antifungal molded plate and were segregated on the surface.

Comparative example 6
Except for using the IPBC-supported inorganic particles of Comparative Example 4 instead of the IPBC-supported hydrophobic inorganic particles of Example 15, the same process as in Example 19 was performed to form an antiseptic-antifungal molded plate (cast molding). bottom. In the antiseptic and antifungal molded plate of Comparative Example 6, the IPBC-supporting inorganic particles sedimented against the aqueous resin.

Comparative example 7
An antiseptic and antifungal molded plate was molded (cast molding) in the same manner as in Example 19 except that the IPBC flowable agent in Comparative Example 5 was used instead of the IPBC-supported hydrophobic inorganic particles in Example 15. bottom.

[Antifungal test]
The mold resistance was evaluated according to Examples 22 to 28 and Comparative Examples 6 to 7 according to JIS Z 2911 (2010). Evaluation criteria are shown below.
0: Growth of fungi was not observed.
1: Fungal growth was observed, and the area of the grown portion was ⅓ or less of the total area of the fiber.
2: Fungal growth was observed, and the area of the grown portion exceeded 1/3 of the total area of the fiber.

Claims (7)

Including inorganic particles and a coating layer covering the inorganic particles,
The inorganic particles are oxides, have an oil absorption of 50 mL/100 g or more, and have a substantially spherical shape,
The coating layer is composed of —SiR ₂ O— (two Rs may be the same or different, and are each at least selected from the group consisting of a monovalent saturated hydrocarbon group and a monovalent aromatic hydrocarbon group). Represents one monovalent hydrocarbon group) and an RO group-containing siloxane unit containing an RO group (R represents a monovalent saturated hydrocarbon group) A hydrophobic inorganic particle, characterized by being a cured product of a silicone composition containing an oligomer. 2. The hydrophobic inorganic particles according to claim 1, wherein the inorganic particles are deodorizing particles. 3. The hydrophobic inorganic particles according to claim 1, wherein the inorganic particles carry a functional component. The silicone composition contains -SiR ₂ O- (the two Rs may be the same or different and are each selected from the group consisting of a monovalent saturated hydrocarbon group and a monovalent aromatic hydrocarbon group. Represents at least one monovalent hydrocarbon group) does not contain a siloxane unit represented by, and contains an RO group-containing siloxane unit containing an RO group (R represents a monovalent saturated hydrocarbon group) 4. The hydrophobic inorganic particles according to any one of claims 1 to 3, further comprising a second oligomer. 5. The hydrophobic inorganic particles according to claim 4, wherein said silicone composition further contains silicone oil. With the hydrophobic inorganic particles according to any one of claims 1 to 5,
A particle-containing resin composition characterized by containing a resin. 7. The particle-containing resin composition according to claim 6, wherein said resin is an aqueous resin.