JP2014237576A - Modified metal oxide nanoparticle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modified metal oxide nanoparticle which has excellent compatibility with a resin composition and can suppress the occurrence of poor appearance and the deterioration of mechanical strength even after long-term storage, and to provide a water and oil repellant and a flame retardant containing the modified metal oxide nanoparticles.SOLUTION: A modified metal oxide nanoparticle is modified by a functional group represented by the following formula (1): CF-X-R-Y-Si(CH)(-O-)(1) (where m is an integer of 1-12; Xis a single bond, -S-, -SO-, -SO-, -CHCHS-, -CHCHSO-, or -CHCHSO-; Ris an alkylene group having 1-10 carbon atoms, a phenylene group, or a phenyleneoxymethylene phenylene group; Yis a single bond, -OCONH(CH)-, NHCONH(CH)-, -OCO(CH)S(CH)-, -OCO(CH)SO(CH)- or the like; and n represents 0 or 1).

Description

The present invention includes a modified metal oxide nanoparticle that is excellent in flame retardancy or water repellency and can be produced at low cost, a water / oil repellent containing the modified metal oxide nanoparticle, and the modified metal oxide nanoparticle. It relates to flame retardants.

In recent years, as flame retardants for resins that impart flame retardancy to resin compositions such as organic synthetic fibers, for example, metal hydroxide (magnesium hydroxide, aluminum hydroxide) flame retardants, silicon (silicone, silica) ) Flame retardants, halogen (bromine) flame retardants, phosphorus (phosphoric acid esters, red phosphorus, etc.) flame retardants, and the like.

In addition, the metal hydroxide flame retardant has a problem that the amount of addition in the resin is increased, so that the mechanical properties of the resin are impaired, and the silicon flame retardant has a problem that the applicable resin composition is limited. is there.
In addition, halogen flame retardants tend to be used in a reduced amount because there is a risk that they may be detected from animals or breast milk or brominated dioxins may be generated during combustion.

Therefore, phosphorus-based flame retardants are currently attracting attention as an alternative to these flame retardants. However, this phosphorus-based flame retardant has problems such as generating gas when the resin composition is injection-molded and reducing the heat resistance of the resin composition.

For example, when a polycarbonate resin is used as the resin composition, a polystyrene sulfonate type flame retardant for resin, which is a metal salt type flame retardant, has been proposed (Patent Document 1, Patent Document 2 and Patent Document). 3).

However, in these proposals, the applicable resin composition is limited to polycarbonate resin, the flame-retardant effect is insufficient, the resin composition is not substantially uniformly dispersed, so-called poor compatibility, etc. In addition, there is a demand for a flame retardant for resin that is further excellent in flame retardant effect.

In particular, the flame retardant for resin proposed in Patent Document 3 has an amide group, a carboxyl group or the like that easily adsorbs water, and discolors when the stored resin composition is stored for a long period of time, thereby impairing the appearance. Or the resin itself becomes brittle, so-called mechanical strength may decrease.

The following compounds (A) to (D) are known as water and oil repellents, but the substrate is firmly bonded to glass and ceramics and has good durability, but the water and oil repellent performance is insufficient. Also, adhesion to metals and plastics is insufficient.
_{C 4 F 9 CH 2 CH 2} Si (OCH 3) 3 (A)
_{C 4 F 9 CH 2 CH 2} Si (OC 2 H 5) 3 (B)
C ₆ F ₁₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (C)
_{C 6 F 13 CH 2 CH 2} Si (OC 2 H 5) 3 (D)

JP 2001-181342 A JP 2001-181444 A JP 20012941 A

The present invention provides a modified metal oxide nanoparticle that is excellent in compatibility with a resin composition and that can suppress deterioration in appearance and mechanical strength even when the contained resin composition is stored for a long period of time. The present invention provides a water / oil repellent containing product nanoparticles and a flame retardant containing the modified metal oxide nanoparticles.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention is a modified metal oxide nanoparticle characterized by being modified with a functional group represented by the following formula (1).
_{^{C m F 2m + 1 -X 1}} -R 1 -Y 1 -Si (CH 3) n (-O-) 3-n (1)
{In the formula, m is an integer from 1 to 12, ^{X 1} is a single _{bond, -S -, - SO -,} - SO 2 -, - CH 2 CH 2 S -, - CH 2 CH 2 SO- or - CH ₂ CH ₂ SO ₂ —, R ¹ is an alkylene group having 1 to 10 carbon atoms, phenylene group or phenyleneoxymethylene phenylene group, Y ¹ is a single bond, —OCONH (CH ₂ ) ₃ —, —NHCONH. _{(CH 2) 3 -, -} OCO (CH 2) 2 S (CH 2) 3 -, - OCO (CH 2) 2 SO (CH 2) 3 -, - OCO (CH 2) 2 SO 2 (CH 2) _{3 -, - OCOCH (CH 3} ) CH 2 S (CH 2) 3 -, - OCOCH (CH 3) CH 2 SO (CH 2) 3 -, - OCOCH (CH 3) CH 2 SO 2 (CH 2) 3 _{-, - (CH 2) 2} S (CH 2) _{-, - (CH 2) 2} SO (CH 2) 3 - or _{- (CH 2) 2 SO 2} (CH 2) 3 - is and, n represents 0 or 1. }

Furthermore, the present invention is a modified metal oxide nanoparticle that is further modified with a functional group represented by the following formula (2).
^{_{X 2 - (R 2) m}} -Si (CH 3) n (-O-) 3-n (2)
{In the formula, X ² is selected from the group consisting of vinyl group, thiol group, amino group, chlorine atom, acrylic group, methacryl group, styryl group, phenyl group, glycidoxy group, 3,4-epoxycyclohexyl group and blocked isocyanate group. It is a functional group selected, R ² is an alkylene group having 1 to 5 carbon atoms, m is 0 or 1, and n represents 0 or 1. }

Furthermore, the present invention is a modified metal oxide nanoparticle that is further modified with a functional group represented by the following formula (3).
^{_{MOS (= O) 2 -R 3}} -Si (CH 3) n (-O-) 3-n (3)
{Wherein M is a hydrogen ion, an alkyl group having 1 to 4 carbon atoms, a metal ion or an ammonium (NR ³ ₄ ) group, R ³ is an alkylene group having 1 to 10 carbon atoms (in the alkylene chain, a urethane bond or a urea) binding may _{contain), - C 6 H 4 (} CH 2) 2 S (CH 2) 3 -, - C 6 H 4 (CH 2) 2 SO (CH 2) 3 - and _C 6 _{H 4} (CH ₂ ) ₂ SO ₂ (CH ₂ ) ₃ —, R ³ is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, which may be the same or different, and n represents 0 or 1. }

Further, the present invention is a water / oil repellent containing the modified metal oxide nanoparticles.

Further, the present invention is a structure containing or coated with the water / oil repellent.

Moreover, this invention is a flame retardant containing the said modified metal oxide nanoparticle.

Moreover, this invention is a flame retardant resin composition which consists of the said flame retardant and resin.

Moreover, this invention is a molded object formed by shape | molding the said flame-retardant resin composition.

Further, the present invention is a structure containing or coated with the flame retardant.

The modified metal oxide nanoparticles of the present invention have a large flame retardant effect, can be produced at low cost, and can be added.
In addition, the modified metal oxide nanoparticles of the present invention have a great water and oil repellency effect, excellent adhesion to metals and plastics, and the effect that they can be added or coated.

In the present invention, the modified metal oxide nanoparticles are modified with a functional group represented by the following formula (1).
_{^{C m F 2m + 1 -X 1}} -R 1 -Y 1 -Si (CH 3) n (-O-) 3-n (1)
{In the formula, m is an integer from 1 to 12, ^{X 1} is a single _{bond, -S -, - SO -,} - SO 2 -, - CH 2 CH 2 S -, - CH 2 CH 2 SO- or - CH ₂ CH ₂ SO ₂ —, R ¹ is an alkylene group having 1 to 10 carbon atoms, a phenylene group or a phenyleneoxymethylene phenylene group; Y ¹ is a single bond, —OCONH (CH ₂ ) ₃ —, NHCONH ( _{CH 2) 3 -, - OCO} (CH 2) 2 S (CH 2) 3 -, - OCO (CH 2) 2 SO (CH 2) 3 -, - OCO (CH 2) 2 SO 2 (CH 2) 3 _{-, - OCOCH (CH 3)} CH 2 S (CH 2) 3 -, - OCOCH (CH 3) CH 2 SO (CH 2) 3 -, - OCOCH (CH 3) CH 2 SO 2 (CH 2) 3 - _{, - (CH 2) 2 S} (CH 2) 3 _{-, - (CH 2) 2} SO (CH 2) 3 - or _{- (CH 2) 2 SO 2} (CH 2) 3 - is and, n represents 0 or 1. }

In the above formula (1), examples of the alkylene group having 1 to 10 carbon atoms of R ¹ include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group. Of these, methylene group and ethylene group are preferred in consideration of cost and raw material availability.

Specific examples of the functional group represented by the formula (1) include the following.
  C₄F₉CH₂CH₂Si (-O-)₃
  C₆F₁₃CH₂CH₂Si (-O-)₃
  C₈F₁₇CH₂CH₂Si (-O-)₃
CF₃CH₂OCONHCH₂CH₂CH₂Si (-O-)₃  
C₄F₉CH₂CH₂OCONHCH₂CH₂CH₂Si (-O-)₃
C₆F₁₃CH₂CH₂OCONHCH₂CH₂CH₂Si (-O-)₃
C₈F₁₇CH₂CH₂OCONHCH₂CH₂CH₂Si (-O-)₃
C₄F₉SCH₂CH₂OCONHCH₂CH₂CH₂Si (-O-)₃
  C₆F₁₃SCH₂CH₂OCONHCH₂CH₂CH₂Si (-O-)₃
C₈F₁₇SCH₂CH₂OCONHCH₂CH₂CH₂Si (-O-)₃
  C₄F₉SOCH₂CH₂OCONHCH₂CH₂CH₂Si (-O-)₃
C₆F₁₃SOCH₂CH₂OCONHCH₂CH₂CH₂Si (-O-)₃
C₈F₁₇SOCH₂CH₂OCONHCH₂CH₂CH₂Si (-O-)₃
C₄F₉SO₂CH₂CH₂OCONHCH₂CH₂CH₂Si (-O-)₃
C₆F₁₃SO₂CH₂CH₂OCONHCH₂CH₂CH₂Si (-O-)₃
  C₈F₁₇SO₂CH₂CH₂OCONHCH₂CH₂CH₂Si (-O-)₃
C₄F₉SCH₂CH₂HNCONHCH₂CH₂CH₂Si (-O-)₃
  C₆F₁₃SCH₂CH₂HNCONHCH₂CH₂CH₂Si (-O-)₃
C₈F₁₇SCH₂CH₂HNCONHCH₂CH₂CH₂Si (-O-)₃
  C₄F₉SOCH₂CH₂HNCONHCH₂CH₂CH₂Si (-O-)₃
C₆F₁₃SOCH₂CH₂HNCONHCH₂CH₂CH₂Si (-O-)₃
C₈F₁₇SOCH₂CH₂HNCONHCH₂CH₂CH₂Si (-O-)₃
C₄F₉SO₂CH₂CH₂HNCONHCH₂CH₂CH₂Si (-O-)₃
C₆F₁₃SO₂CH₂CH₂HNCONHCH₂CH₂CH₂Si (-O-)₃
  C₈F₁₇SO₂CH₂CH₂HNCONHCH₂CH₂CH₂Si (-O-)₃
C₄F₉SC₆H₄HNCONHCH₂CH₂CH₂Si (-O-)₃
  C₆F₁₃SC₆H₄HNCONHCH₂CH₂CH₂Si (-O-)₃
C₈F₁₇SC₆H₄HNCONHCH₂CH₂CH₂Si (-O-)₃
  C₄F₉SOC₆H₄HNCONHCH₂CH₂CH₂Si (-O-)₃
C₆F₁₃SOC₆H₄HNCONHCH₂CH₂CH₂Si (-O-)₃
C₈F₁₇SOC₆H₄HNCONHCH₂CH₂CH₂Si (-O-)₃
C₄F₉SO₂C₆H₄HNCONHCH₂CH₂CH₂Si (-O-)₃
C₆F₁₃SO₂C₆H₄HNCONHCH₂CH₂CH₂Si (-O-)₃
  C₈F₁₇SO₂C₆H₄HNCONHCH₂CH₂CH₂Si (-O-)₃
C₄F₉CH₂CH₂OCOCH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₆F₁₃CH₂CH₂OCOCH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₈F₁₇CH₂CH₂OCOCH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₄F₉SC₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₆F₁₃SC₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₈F₁₇SC₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₄F₉SOC₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₆F₁₃SOC₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₈F₁₇SOC₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₄F₉SO₂C₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₆F₁₃SO₂C₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₈F₁₇SO₂C₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₄F₉CH₂CH₂SC₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₆F₁₃CH₂CH₂SC₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₈F₁₇CH₂CH₂SC₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₄F₉CH₂CH₂SOC₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₆F₁₃CH₂CH₂SOC₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₈F₁₇CH₂CH₂SOC₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₄F₉CH₂CH₂SO₂C₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₆F₁₃CH₂CH₂SO₂C₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃
C₈F₁₇CH₂CH₂SO₂C₆H₄OCH₂C₆H₄CH₂CH₂SCH₂CH₂CH₂Si (-O-)₃

Examples of the metal oxide nanoparticles include silica-based nanoparticles, alumina-based nanoparticles, titania-based nanoparticles, and zirconia-based nanoparticles. Those sols are preferred. That is, silica sol, alumina sol, titania sol, zirconia sol, and the like. A silica-based sol is more preferable, and an organosilica-based sol is particularly preferable.
The organosol is a colloidal solution in which surface-modified colloidal silica is stably dispersed in an organic solvent at a nano level, and can be dispersed in various organic solvents such as alcohol, ketone, ether, and toluene.
Specifically, organosilica sol (methanol silica sol, IPA-ST, IPA-ST, IPA-ST-UP, IPA-ST-ZL, EG-ST, NPC-ST-30, DMAC-ST, MEK manufactured by Nissan Chemical Co., Ltd. -ST, MIBK-ST, PMA-ST and PGM-ST) and high-purity organosilica sol (PL-1-IPA, PL-2L-PGME and PL-2L-MEK) manufactured by Fuso Chemical.
These may be used not only alone but also plurally.

The modified metal oxide nanoparticles of the present invention can be obtained by the following production method.
That is, it is obtained by adding a silane coupling agent (FSC) having a fluoroalkyl group to metal oxide nanoparticles and reacting the silanols on the metal oxide nanoparticles with the silane coupling agent (FSC).
The silane coupling agent having a fluoroalkyl group is commercially available or can be obtained by reacting a commercially available fluorine-containing alcohol or fluorine-containing amine with a silane coupling agent having an isocyanate group {for example, compound (E)}. I can do it. Moreover, it can obtain by making a silane coupling agent {for example, a compound (F)} which has a fluorine-containing acrylate or a fluorine-containing methacrylate, and a thiol group react. Or it can obtain by making the alcohol or amine obtained by the method of Unexamined-Japanese-Patent No. 2011-020924 react with the silane coupling agent {For example, compound (E)} which has an isocyanate group.
NCOCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ (E)
HSCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (F)

Specific examples of the silane coupling agent (FSC) having a fluoroalkyl group include the following.
_{C 4 F 9 CH 2 CH 2} Si (OCH 3) 3
_{C 4 F 9 CH 2 CH 2} Si (OC 2 H 5) 3
C ₆ F ₁₃ CH ₂ CH ₂ Si (OCH ₃ ) _{3
C 6 F 13 CH 2 CH 2} Si (OC 2 H 5) 3
_{C 8 F 17 CH 2 CH 2} Si (OCH 3) 3
_{C 8 F 17 CH 2 CH 2} Si (OC 2 H 5) 3
CF ₃ CH ₂ OCONHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) _{3
C 4 F 9 CH 2 CH 2} OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
C ₆ F ₁₃ CH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) _{3
C 8 F 17 CH 2 CH 2} OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
C ₄ F ₉ SCH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
C ₆ F ₁₃ SCH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
C ₈ F ₁₇ SCH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) _{3
C 4 F 9 SOCH 2 CH 2} OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 6 F 13 SOCH 2 CH 2} OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 8 F 17 SOCH 2 CH 2} OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 4 F 9 SO 2 CH 2} CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 6 F 13 SO 2 CH 2} CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 8 F 17 SO 2 CH 2} CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
C ₄ F ₉ SCH ₂ CH ₂ HNCONHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
C ₆ F ₁₃ SCH ₂ CH ₂ HNCONHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
C ₈ F ₁₇ SCH ₂ CH ₂ HNCONHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) _{3
C 4 F 9 SOCH 2 CH 2} HNCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 6 F 13 SOCH 2 CH 2} HNCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 8 F 17 SOCH 2 CH 2} HNCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 4 F 9 SO 2 CH 2} CH 2 HNCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 6 F 13 SO 2 CH 2} CH 2 HNCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 8 F 17 SO 2 CH 2} CH 2 HNCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 4 F 9 SC 6 H 4} HNCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 6 F 13 SC 6 H 4} HNCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 8 F 17 SC 6 H 4} HNCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 4 F 9 SOC 6 H 4} HNCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 6 F 13 SOC 6 H 4} HNCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
C ₈ F ₁₇ SOC ₆ H ₄ HNCONHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) _{3
C 4 F 9 SO 2 C 6} H 4 HNCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 6 F 13 SO 2 C 6} H 4 HNCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 8 F 17 SO 2 C 6} H 4 HNCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 4 F 9 CH 2 CH 2} OCOCH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 4 F 9 CH 2 CH 2} OCOCH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
C ₆ F ₁₃ CH ₂ CH ₂ OCOCH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
C ₈ F ₁₇ CH ₂ CH ₂ OCOCH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) _{3
C 4 F 9 SC 6 H 4} OCH 2 C 6 H 4 CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 6 F 13 SC 6 H 4} OCH 2 C 6 H 4 CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 8 F 17 SC 6 H 4} OCH 2 C 6 H 4 CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 4 F 9 SOC 6 H 4} OCH 2 C 6 H 4 CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 6 F 13 SOC 6 H 4} OCH 2 C 6 H 4 CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
C ₈ F ₁₇ SOC ₆ H ₄ OCH ₂ C ₆ H ₄ CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) _{3
C 4 F 9 SO 2 C 6} H 4 OCH 2 C 6 H 4 CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 6 F 13 SO 2 C 6} H 4 OCH 2 C 6 H 4 CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 8 F 17 SO 2 C 6} H 4 OCH 2 C 6 H 4 CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 4 F 9 CH 2 CH 2} SC 6 H 4 OCH 2 C 6 H 4 CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 6 F 13 CH 2 CH 2} SC 6 H 4 OCH 2 C 6 H 4 CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 8 F 17 CH 2 CH 2} SC 6 H 4 OCH 2 C 6 H 4 CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 4 F 9 CH 2 CH 2} SOC 6 H 4 OCH 2 C 6 H 4 CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 6 F 13 CH 2 CH 2} SOC 6 H 4 OCH 2 C 6 H 4 CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 8 F 17 CH 2 CH 2} SOC 6 H 4 OCH 2 C 6 H 4 CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 4 F 9 CH 2 CH 2} SO 2 C 6 H 4 OCH 2 C 6 H 4 CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 6 F 13 CH 2 CH 2} SO 2 C 6 H 4 OCH 2 C 6 H 4 CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 8 F 17 CH 2 CH 2} SO 2 C 6 H 4 OCH 2 C 6 H 4 CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3

As a solvent in the case of reacting a metal oxide nanoparticle with a silane coupling agent (FSC) having a fluoroalkyl group, alcohol solvents: methanol, ethanol, isopropanol, n-butanol, t-butanol, pentanol, ethylene glycol , Propylene glycol, 1,4-butanediol, etc., ether solvents: diethyl ether, tetrahydrofuran, dioxane, etc., ketone solvents: acetone, methyl ethyl ketone, etc., aprotic solvents: dimethyl sulfoxide, N, N-dimethylformamide And mixed solvents thereof.
Among these, alcohol solvents are preferable, and these solvents can be used alone or in combination of two or more.

The concentration of the metal oxide nanoparticles of the raw material relative to the solvent is 1 to 50% by weight, preferably 1 to 30% by weight.

The amount of the silane coupling agent (FSC) having a fluoroalkyl group with respect to the metal oxide nanoparticles is 0.1 to 12 mmol, preferably 2.0 to 11 mmol, with respect to 1 g of the metal oxide nanoparticles.
If it is less than 0.1, the concentration of the fluoroalkyl group is too low, and the flame retardant effect and the water / oil repellent effect are lowered. If it exceeds 12, silanol on the metal oxide is insufficient and the silane coupling agents are A compound that self-condenses may be formed, which is not preferable.

Although the temperature at the time of adding the coupling agent (FSC) which has a fluoroalkyl group is not limited, the boiling point is preferable from normal temperature (about 20 degreeC).
Although the reaction temperature is not limited, the boiling point is preferably from room temperature (about 20 ° C.).
Although the reaction time is not limited, it is preferably 10 minutes to 48 hours, particularly preferably 6 hours to 24 hours.

The modified metal oxide nanoparticles of the present invention are preferably further modified with a functional group represented by the following formula (2).
^{_{X 2 - (R 2) m}} -Si (CH 3) n (-O-) 3-n (2)
{Wherein X ² is a linear or branched alkyl group having 1 to 20 carbon atoms, vinyl group, thiol group, amino group, chlorine atom, acrylic group, methacryl group, styryl group, phenyl group, glycidoxy group, 3, A functional group selected from the group consisting of a 4-epoxycyclohexyl group and a blocked isocyanate group, R ² is an alkylene group having 1 to 5 carbon atoms, m is 0 or 1, and n is 0 or 1. . }

The modified metal oxide nanoparticles of the present invention include a modified metal oxide nanoparticle modified with a functional group represented by formula (1) and a modified metal modified with a functional group represented by formula (2). It can also be used as a mixed composition with oxide nanoparticles.

In the above formula (2), examples of the linear or branched alkyl group having 1 to 20 carbon atoms of X ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, an octyl group, and an octadecyl group. Of these, methyl group, octyl group and octadecyl group are preferable in consideration of cost and raw material availability.
Examples of the alkylene group having 1 to 5 carbon atoms of R ² include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group. Of these, a propylene group is preferable in consideration of cost and raw material availability.

Specific examples of the functional group represented by the formula (2) include the following.
CH ₃ Si (—O—) ₃
CH ₃ Si (—O—) ₃
C ₈ H ₁₇ Si (—O—) ₃
C ₈ H ₁₇ Si (—O—) ₃
C ₁₈ H ₃₇ Si (—O—) ₃
C ₁₈ H ₃₇ Si (—O—) ₃
CH ₂ = CHSi _{(-O-) 3}
CH ₂ = CHSi _{(-O-) 3}
H ₂ NCH ₂ CH ₂ CH ₂ Si (—O—) ₃
H ₂ NCH ₂ CH ₂ CH ₂ Si (—O—) ₃
ClCH ₂ CH ₂ CH ₂ Si (—O—) ₃
SHCH ₂ CH ₂ CH ₂ Si (—O—) ₃
SHCH ₂ CH ₂ CH ₂ Si (CH ₃ ) (— O—) _{2
CH 2 = CHCOOCH 2 CH 2 CH} 2 Si (-O-) 3
_{CH 2 = C (CH 3)} COOCH 2 CH 2 CH 2 Si (-O-) 3
C ₆ H ₅ Si (—O—) ₃
(CH ₃ ) ₃ COCOCH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ Si (—O—) _{3
(CH 3) 3 COCOCH 2 CH} 2 SCH 2 CH 2 CH 2 (CH 3) Si (-O-) 2

Furthermore, the modified metal oxide nanoparticles modified with the functional group represented by the formula (2) can be obtained by the following production method.
That is, the following silane coupling agent (RSC) is added to the modified metal oxide nanoparticles modified with the functional group represented by the formula (1), and the silanol and the silane coupling agent on the metal oxide nanoparticles ( RSC). The silane coupling agent (RSC) undergoes a condensation reaction with the silanol of the metal oxide nanoparticles.
Moreover, the silane coupling agent (FSC) which has the said fluoroalkyl group, and a silane coupling agent (RSC) can also be made to react simultaneously with a metal oxide nanoparticle.

The following are mentioned as an example of a silane coupling agent (RSC).
CH ₃ Si (OCH ₃ ) ₃
CH ₃ Si (OC ₂ H ₅ ) ₃
C ₈ H ₁₇ Si (OCH ₃ ) ₃
C ₈ H ₁₇ Si (OC ₂ H ₅ ) ₃
C ₁₈ H ₃₇ Si (OCH ₃ ) ₃
C ₁₈ H ₃₇ Si (OC ₂ H ₅ ) ₃
CH ₂ = CHSi (OCH ₃ ) _{3
CH 2 = CHSi (OC 2 H} 5) 3
H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
H ₂ NCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
ClCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
SHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
SHCH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) _{2
CH 2 = CHCOOCH 2 CH 2 CH} 2 Si (OCH 3) 3
_{CH 2 = C (CH 3)} COOCH 2 CH 2 CH 2 Si (OCH 3) 3
C ₆ H ₅ Si (OCH ₃ ) ₃
C ₆ H ₅ Si (OC ₂ H ₅ ) ₃
(CH ₃ ) ₃ COCOCH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(CH ₃ ) ₃ COCOCH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ (CH ₃ ) Si (OCH ₃ ) _{2
(C 2 H 5 OOC) 2} CH-CONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3

The amount of the silane coupling agent (RSC) added is usually 0.01 to 12.0 mmol, preferably 0.1 to 12.0 mmol, with respect to 1 g of the raw material metal oxide nanoparticles.
Within the above range, the characteristics (for example, dispersibility) of the silicon compound can be more exhibited.

Although the temperature at the time of adding a silane coupling agent (RSC) is not limited, a boiling point is preferable from normal temperature (about 20 degreeC).
Although the reaction temperature is not limited, the boiling point is preferably from room temperature (about 20 ° C.).
Although the reaction time is not limited, it is preferably 2 to 48 hours, particularly preferably 8 to 24 hours.

The modified metal oxide nanoparticles of the present invention are preferably further modified with a functional group represented by the following formula (3).

^{_{MOS (= O) 2 -R 3}} -Si (CH 3) n (-O-) 3-n (3)
{In the formula, M represents a hydrogen ion, an alkyl group having 1 to 4 carbon atoms, a metal ion or an ammonium (NR ⁴ ₄ ) group, and R ³ represents an alkylene group having 1 to 10 carbon atoms (in this alkylene chain, a urethane bond or may contain urea _{linkages), - C 6 H 4 (} CH 2) 2 S (CH 2) 3 -, - C 6 H 4 (CH 2) 2 SO (CH 2) 3 - or -C ₆ H ₄ (CH ₂ ) ₂ SO ₂ (CH ₂ ) ₃ —, R ⁴ is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, which may be the same or different, and n represents 0 or 1. }

The modified metal oxide nanoparticles of the present invention include a modified metal oxide nanoparticle modified with a functional group represented by formula (1) and a modified metal modified with a functional group represented by formula (3). Mixed composition with oxide nanoparticles or modified metal oxide nanoparticles modified with functional group represented by formula (1) and modified metal oxide modified with functional group represented by formula (2) It can also be used as a mixed composition of nanoparticles and modified metal oxide nanoparticles modified with a functional group represented by formula (3).

In the above formula (3), examples of the alkylene group having 1 to 10 carbon atoms of R ³ include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group. Of these, a propylene group is preferred in consideration of cost and raw material availability.
Also _{-C 6 H 4 (CH 2)} 2 S (CH 2) 3 - and _{C 6 H 4 (CH 2)} 2 SO 2 (CH 2) 3 - is preferable.

Examples of M include hydrogen ions, alkyl groups having 1 to 4 carbon atoms, metal ions (alkali metal ions, alkaline earth metal ions, silver ions, copper ions, nickel ions, etc.) or ammonium (NR ² ₄ ) ions. In view of flame retardancy, alkali metal ions and alkaline earth metal ions are preferable.

R ⁴ of the ammonium ion includes a hydrogen atom and an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom and an alkyl group having 1 to 2 carbon atoms (methyl group and ethyl group).

Examples of alkali metal ions and alkaline earth metal ions include lithium ions, sodium ions, potassium ions, cesium ions, magnesium ions, and calcium ions.
Of these, alkali metal ions are preferred, and potassium ions are particularly preferred.

  Specific examples of the functional group represented by the formula (3) include the following.

HOSO ₂ —CH ₂ CH ₂ CH ₂ Si (—O—) ₃
LiOSO ₂ —CH ₂ CH ₂ CH ₂ Si (—O—) ₃
NaOSO ₂ —CH ₂ CH ₂ CH ₂ Si (—O—) ₃
KOSO ₂ —CH ₂ CH ₂ CH ₂ Si (—O—) ₃
NH ₄ OSO ₂ —CH ₂ CH ₂ CH ₂ Si (—O—) ₃
N (CH ₃ ) ₄ OSO ₂ —CH ₂ CH ₂ CH ₂ Si (—O—) _{3
NH (C 2 H 5) 3} OSO 2 -CH 2 CH 2 CH 2 Si (-O-) 3
AgOSO ₂ —CH ₂ CH ₂ CH ₂ Si (—O—) ₃
HOSO ₂ —CH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ Si (—O—) ₃
LiOSO ₂ —CH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ Si (—O—) ₃
NaOSO ₂ —CH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ Si (—O—) ₃
KOSO ₂ —CH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ Si (—O—) ₃
NH ₄ OSO ₂ —CH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ Si (—O—) ₃
N (CH ₃ ) ₄ OSO ₂ —CH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ Si (—O—) _{3
NH (C 2 H 5) 3} OSO 2 -CH 2 CH 2 OCONHCH 2 CH 2 CH 2 Si (-O-) 3
HOSO ₂ —CH ₂ CH ₂ NHCONHCH ₂ CH ₂ CH ₂ Si (—O—) ₃
LiOSO ₂ —CH ₂ CH ₂ NHCONHCH ₂ CH ₂ CH ₂ Si (—O—) ₃
NaOSO ₂ —CH ₂ CH ₂ NHCONHCH ₂ CH ₂ CH ₂ Si (—O—) ₃
KOSO ₂ —CH ₂ CH ₂ NHCONHCH ₂ CH ₂ CH ₂ Si (—O—) ₃
NH ₄ OSO ₂ —CH ₂ CH ₂ NHCONHCH ₂ CH ₂ CH ₂ Si (—O—) ₃
N (CH ₃ ) ₄ OSO ₂ —CH ₂ CH ₂ NHCONHCH ₂ CH ₂ CH ₂ Si (—O—) _{3
NH (C 2 H 5) 3} OSO 2 -CH 2 CH 2 NHCONHCH 2 CH 2 CH 2 Si (-O-) 3
_{HOSO 2 -C 6 H 4 NHCONHCH 2} CH 2 CH 2 Si (-O-) 3
_{LiOSO 2 -C 6 H 4 NHCONHCH 2} CH 2 CH 2 Si (-O-) 3
_{NaOSO 2 -C 6 H 4 NHCONHCH 2} CH 2 CH 2 Si (-O-) 3
_{KOSO 2 -C 6 H 4 NHCONHCH 2} CH 2 CH 2 Si (-O-) 3
NH ₄ OSO ₂ —C ₆ H ₄ NHCONHCH ₂ CH ₂ CH ₂ Si (—O—) _{3
N (CH 3) 4 OSO 2} -C 6 H 4 NHCONHCH 2 CH 2 CH 2 Si (-O-) 3
_{NH (C 2 H 5) 3} OSO 2 -C 6 H 4 NHCONHCH 2 CH 2 CH 2 Si (-O-) 3

_{HOSO 2 -CH 2 CH 2 CH 2} SiCH 3 (-O-) 2
_{LiOSO 2 -CH 2 CH 2 CH 2} SiCH 3 (-O-) 2
_{NaOSO 2 -CH 2 CH 2 CH 2} SiCH 3 (-O-) 2
_{KOSO 2 -CH 2 CH 2 CH 2} SiCH 3 (-O-) 2
NH ₄ OSO ₂ —CH ₂ CH ₂ CH ₂ SiCH ₃ (—O—) ₂
NH (CH ₃ ) ₃ OSO ₂ —CH ₂ CH ₂ CH ₂ SiCH ₃ (—O—) _{2
NH (C 2 H 5) 3} OSO 2 -CH 2 CH 2 CH 2 SiCH 3 (-O-) 2
HOSO ₂ —CH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ SiCH ₃ (—O—) ₂
LiOSO ₂ —CH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ SiCH ₃ (—O—) ₂
NaOSO ₂ —CH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ SiCH ₃ (—O—) _{2
KOSO 2 -CH 2 CH 2 OCONHCH 2} CH 2 CH 2 SiCH 3 (-O-) 2
NH ₄ OSO ₂ —CH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ SiCH ₃ (—O—) _{2
NH (CH 3) 3 OSO 2} -CH 2 CH 2 OCONHCH 2 CH 2 CH 2 SiCH 3 (-O-) 2
_{NH (C 2 H 5) 3} OSO 2 -CH 2 CH 2 OCONHCH 2 CH 2 CH 2 SiCH 3 (-O-) 2
HOSO ₂ —CH ₂ CH ₂ NHCONHCH ₂ CH ₂ CH ₂ SiCH ₃ (—O—) ₂
LiOSO ₂ —CH ₂ CH ₂ NHCONHCH ₂ CH ₂ CH ₂ SiCH ₃ (—O—) ₂
NaOSO ₂ —CH ₂ CH ₂ NHCONHCH ₂ CH ₂ CH ₂ SiCH ₃ (—O—) _{2
KOSO 2 -CH 2 CH 2 NHCONHCH 2} CH 2 CH 2 SiCH 3 (-O-) 2
NH ₄ OSO ₂ —CH ₂ CH ₂ NHCONHCH ₂ CH ₂ CH ₂ SiCH ₃ (—O—) ₂
NH (CH ₃ ) ₃ OSO ₂ —CH ₂ CH ₂ NHCONHCH ₂ CH ₂ CH ₂ SiCH ₃ (—O—) _{2
NH (C 2 H 5) 3} OSO 2 -CH 2 CH 2 NHCONHCH 2 CH 2 CH 2 SiCH 3 (-O-) 2
_{HOSO 2 -C 6 H 4 NHCONHCH 2} CH 2 CH 2 SiCH 3 (-O-) 2
_{LiOSO 2 -C 6 H 4 NHCONHCH 2} CH 2 CH 2 SiCH 3 (-O-) 2
_{NaOSO 2 -C 6 H 4 NHCONHCH 2} CH 2 CH 2 SiCH 3 (-O-) 2
_{KOSO 2 -C 6 H 4 NHCONHCH 2} CH 2 CH 2 SiCH 3 (-O-) 2
NH ₄ OSO ₂ —C ₆ H ₄ NHCONHCH ₂ CH ₂ CH ₂ SiCH ₃ (—O—) _{2
NH (CH 3) 3 OSO 2} -C 6 H 4 NHCONHCH 2 CH 2 CH 2 SiCH 3 (-O-) 2
_{NH (C 2 H 5) 3} OSO 2 -C 6 H 4 NHCONHCH 2 CH 2 CH 2 SiCH 3 (-O-) 2

LiOSO ₂ —C ₆ H ₄ CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ SiCH ₃ (—O—) _{2
NaOSO 2 -C 6 H 4 CH 2} CH 2 SCH 2 CH 2 CH 2 SiCH 3 (-O-) 2
_{KOSO 2 -C 6 H 4 CH 2} CH 2 SCH 2 CH 2 CH 2 SiCH 3 (-O-) 2
_{LiOSO 2 -C 6 H 4 CH 2} CH 2 SOCH 2 CH 2 CH 2 SiCH 3 (-O-) 2
_{NaOSO 2 -C 6 H 4 CH 2} CH 2 SOCH 2 CH 2 CH 2 SiCH 3 (-O-) 2
_{KOSO 2 -C 6 H 4 CH 2} CH 2 SOCH 2 CH 2 CH 2 SiCH 3 (-O-) 2
LiOSO ₂ —C ₆ H ₄ CH ₂ CH ₂ SO ₂ CH ₂ CH ₂ CH ₂ SiCH ₃ (—O—) _{2
NaOSO 2 -C 6 H 4 CH 2} CH 2 SO 2 CH 2 CH 2 CH 2 SiCH 3 (-O-) 2
_{KOSO 2 -C 6 H 4 CH 2} CH 2 SO 2 CH 2 CH 2 CH 2 SiCH 3 (-O-) 2

Furthermore, the modified metal oxide nanoparticles modified with the functional group represented by the formula (3) are obtained by the following method.
That is, the modified metal oxide nanoparticle solution modified with the functional group represented by the above formula (1) or the above formula (1) and the above formula (2) has a functional group that can be chemically converted to a sulfonic acid group. It can be obtained by adding a silane coupling agent represented by the following formula (SC1) or (SC2) and causing a condensation reaction with silanol of the metal oxide nanoparticles.

That is, a silane coupling agent represented by the following formula (SC1) or (SC2) having a functional group that can be chemically converted to a sulfonic acid group is added to the metal oxide nanoparticles, and then on the metal oxide nanoparticles. After reacting silanol and the silane coupling agent, the thiol group is converted to a sulfonic acid group by a peroxide, and then neutralized with a metal salt if necessary. Or it can obtain by making the said thiol group and the compound represented by a following formula (SC3) react.
Also, by reacting a silane coupling agent obtained by reacting a compound represented by the following formula (SC3) with a compound represented by the following formula (SC1) or (SC2) with silanol on the metal oxide nanoparticles. Can also be obtained.
_{^{HS-R 5 -Si (CH 3}} ) n (-Y 2) 3-n (SC1)
_{^{(Y 2 -) 3-n}} (CH 3) Si-R 5 -S-S-R 5 -Si (CH 3) n (-Y 2) 3-n (SC2)
{In the formula, R ⁵ is an alkylene group having 1 to 10 carbon atoms (this alkylene chain may contain a urethane bond or a urea bond), and Y ² may be the same or different. -4 alkoxy group or hydroxyl group, n represents 0 or 1. }
_{MOS (= O) 2 -C 6} H 4 -CH = CH 2 (SC3)
{Wherein, M represents a hydrogen ion, an alkyl group having 1 to 4 carbon atoms, a metal ion, or an ammonium (NR ⁴ ₄ ) group}

  Specific examples of the silane coupling agent represented by the formula (SC1) or (SC2) include the following.

HSCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) _{3
CH 3 CH (HS) CH 2} Si (OC 2 H 5) 3,
HSCH ₂ CH ₂ Si (OCH ₃ ) ₃
HSCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
HSCH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
HSCH ₂ CH ₂ NHCONHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
HSC ₆ H ₄ NHCONHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) _{3
(OC 2 H 5) 3 SiCH} 2 CH 2 CH 2 -S-S-CH 2 CH 2 CH 2 Si (OC 2 H 5) 3

Among these, a compound having a urethane bond or urea bond can be obtained by reacting a silane coupling agent having an isocyanate group with 2-mercaptoethanol, 2-mercaptoethylamine, and 4-mercaptoaniline.

Specific examples of the compound represented by the formula (SC3) include the following.
_{LiOS (= O) 2 -C 6} H 4 -CH = CH 2
_{NaOS (= O) 2 -C 6} H 4 -CH = CH 2
_{KOS (= O) 2 -C 6} H 4 -CH = CH 2
_{C 2 H 5 OS (= O} ) 2 -C 6 H 4 -CH = CH 2
_{(C 2 H 5) 4 NOS} (= O) 2 -C 6 H 4 -CH = CH 2

Solvents for reacting metal oxide nanoparticles with silane coupling agents (SC1 or SC2) are alcohol solvents: methanol, ethanol, isopropanol, n-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol. And 1,4-butanediol, ether solvents: diethyl ether, tetrahydrofuran and dioxane, ketone solvents: acetone and methyl ethyl ketone, aprotic solvents: dimethyl sulfoxide, N, N-dimethylformamide and the like And the like.
Among these, alcohol solvents are preferable, and these solvents can be used alone or in combination of two or more.

The amount of the silane coupling agent (SC1 or SC2) with respect to the metal oxide nanoparticles is 0.1 to 12 mmol, preferably 2.0 to 11 mmol, with respect to 1 g of the metal oxide nanoparticles.
When the concentration is less than 0.1, the concentration of the sulfonic acid group is too low, and the flame retardancy performance is lowered. When the concentration exceeds 12, the compound in which the silanol on the metal oxide is insufficient and the silane coupling agents are self-condensed. It may be generated and is not preferable.

The temperature at which the silane coupling agent (SC1 or SC2) is added is not limited, but the boiling point is preferably from room temperature (about 20 ° C.).
Although the reaction temperature is not limited, the boiling point is preferably from room temperature (about 20 ° C.).
Although the reaction time is not limited, it is preferably 10 minutes to 48 hours, particularly preferably 6 hours to 24 hours.

Examples of the peroxide include organic peroxides (peracetic acid, m-chloroperbenzoic acid, benzoyl peroxide, etc.) and inorganic peroxides (ozone, hydrogen peroxide, calcium peroxide, etc.). Of these, hydrogen peroxide and peracetic acid are preferred, and hydrogen peroxide is particularly preferred.
The peroxide can be added at one time or divided into the production process of the previous step {the step of bonding the silane coupling agent (SC1 or SC2) to the metal oxide nanoparticles}.

The amount of the peroxide used is 200 to 5000 mol%, preferably 300 to 5000 mol%, more preferably 300 to 2000 mol%, based on the silane coupling agent (SC1 or SC2).

Although the temperature at the time of adding a peroxide is not limited, Room temperature (about 20 degreeC) is preferable.
Although the reaction temperature is not limited, the boiling point is preferably from room temperature (about 20 ° C.).
Although the reaction time is not limited, it is preferably 10 minutes to 48 hours, particularly preferably 6 hours to 24 hours.

Metal salts include hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, etc.), acetate salts (lithium acetate, sodium acetate, potassium acetate, etc.), metals Examples thereof include oxides (such as silver oxide), ammonia, trimethylamine, triethylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and potassium tert-butoxide.

There is no particular limitation on the temperature when neutralizing with the metal salt, and it may be usually performed at room temperature.

The metal salt to be added may be added as it is, or may be added after dilution with a solvent (for example, water).

Solvents for reacting the thiol group of the silane coupling agent or the thiol group on the metal oxide nanoparticles with the compound represented by the formula (SC3) include water, alcohol solvents: methanol, ethanol, isopropanol, n- Butanol, t-butanol, pentanol, ethylene glycol, propylene glycol, 1,4-butanediol and the like, ether solvents: diethyl ether, tetrahydrofuran, dioxane and the like, ketone solvents: acetone, methyl ethyl ketone, and the like, aprotic solvents: Examples thereof include dimethyl sulfoxide, N, N-dimethylformamide, and mixed solvents thereof.
Among these, water, alcohol solvents and mixed solvents thereof are preferable.

When the thiol group of the silane coupling agent or the thiol group on the metal oxide nanoparticles is reacted with the compound represented by the formula (SC3), it is preferable to use a catalyst. As the catalyst, α, α′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4dimethylvaleronitrile) Dimethyl 2,2′-azobis (2-methylpropionate), 2,2′-azobis (methylbutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2-azobis [ N- (2-propenyl) -2-methylpropionamide], 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide) ) And 2,2′-azobis (N-cyclohexyl-2-methylpropionamide and the like azo initiators, tert-butylperoxy-2-ethylhexanoate, tert -Hexylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoyl) Peroxy) hexane, tert-butylperoxypivalate, tert-hexylperoxypivalate, tert-butylperoxyneodecanoate, benzoyl peroxide, dilauroyl peroxide, di (3,5,5-trimethylhexa) Noyl) peroxide, tert-butyl hydroperoxide, 1,1,3,3-tetamethylbutyl hydroperoxide, tert-butyl cumyl peroxide, di-tert-hexyl peroxide, diisopropyl peroxydicarbonate and di- 2-ethylhexylpa Peroxide initiators such as dicarbonate and the like.

Although the temperature at the time of adding a catalyst is not limited, The boiling point is preferable from normal temperature (about 20 degreeC).
Although the reaction temperature is not limited, the boiling point is preferably from room temperature (about 20 ° C.).
Although the reaction time is not limited, it is preferably 10 minutes to 48 hours, particularly preferably 6 hours to 24 hours.

The amount of the catalyst used is 0.01 to 10 mol%, preferably 0.1 to 5 mol%, more preferably 1 to 5 mol%, based on the compound represented by the formula (SC3).

The molar ratio of the compound represented by the formula (SC3) to the compound having a thiol group is usually 0.95 to 1.05, preferably 0.98 to 1.02, and particularly preferably 0.99 to 1.01. is there.
In addition, in the case of the thiol group couple | bonded on the metal oxide nanoparticle, the molar ratio with respect to the couple | bonded thiol group is represented.

The modified metal oxide nanoparticles of the present invention modified with the functional group represented by the formula (1) and, if necessary, the formula (2) and / or the formula (3) can be obtained as a solution when produced by the above production method. .
The obtained solution is useful as a water / oil repellent capable of coating the structure.

In addition, in order to improve the film formability, the above solution is mixed with metal alkoxides {for example, tetraethoxysilane, tetramethoxysilane, tetraethoxytitanium, tetrabutoxyzirconium, tetrakis (2,4-pentanedionato) zirconium, tetrakis (2, 4-pentandionato) titanium, (bis (2,4-pentandionato) bis (2-propanolato) titanium, triisopropylaluminum, etc.}, metal alkoxide oligomers (for example, methyl silicate manufactured by Colcoat Co., Ltd.) Ethyl silicate, etc.), metal oxide sol {for example, alcoholic silica sol manufactured by Colcoat Co., Ltd. (Colcoat P and Colcoat N-103X etc.) and silica sol manufactured by Nissan Chemical Co., Ltd. (Snowtex and organosilica sol etc.)}, metal oxide Fine particles (E.g., Nippon Aerosil Co., Ltd. Aerosil 300 or Aerosil R974, etc.) may be added or the like.

The solid obtained by removing the solvent obtained from the solution is useful as a water and oil repellent that can be added to the structure.

When the metal alkoxide is included, the content (% by weight) of the metal alkoxide is 5 to 1000% based on the total weight of the compounds represented by the formulas (1) to (3), preferably 5 to 800%. More preferably, it is 10 to 800%.

  When the metal alkoxide oligomer is included, the content (% by weight) of the metal alkoxide oligomer is preferably 5 to 1000% based on the total weight of the compounds represented by the formulas (1) to (3). Is from 5 to 800%, more preferably from 10 to 800%.

  When the metal oxide fine particles are included, the content (% by weight) of the metal oxide fine particles is 5 to 1000% based on the total weight of the compounds represented by the formulas (1) to (3), preferably 5 It is -800%, More preferably, it is 10-800%.

  When the metal oxide sol is included, the content (% by weight) of the metal oxide sol is 5 to 1000% based on the total weight of the compounds represented by the formulas (1) to (3), preferably 5 It is -800%, More preferably, it is 10-800%.

Examples of the structure include fiber, resin, leather, fur, glass, ceramics, and metal.
Examples of the fiber include polyester fiber, nylon fiber, cellulose fiber, wool fiber, acrylic fiber, and silk fiber.

Examples of resins include acrylic resins (polymethyl methacrylate, etc.), polyester resins (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), ABS, polycarbonate (aromatic polycarbonates such as bisphenol and fluorene), polystyrene, epoxy, Unsaturated polyester, melamine, diallyl phthalate, polyimide, urethane, nylon, polyethylene, polypropylene, polyvinyl chloride, polybutadiene, polyisoprene, SBR, nitrile rubber, EPM, EPDM, epichlorohydrin rubber, neoprene rubber, porsulfide, butyl rubber, etc. and These alloys are mentioned.

Examples of the metal include iron, copper, aluminum, stainless steel, brass, magnesium and the like and alloys thereof.

The water / oil repellent of the present invention may contain a diluting solvent in order to improve workability (handleability, paintability, etc.). The diluent solvent is not limited as long as it does not react with the metal oxide nanoparticles of the present invention and disperses them. For example, ether {tetrahydrofuran and dioxane etc.}, alcohol {methyl alcohol, ethyl alcohol, n- Propyl alcohol, isopropyl alcohol and n-butyl alcohol etc.}, ketone {acetone, methyl ethyl ketone and methyl isobutyl ketone etc.}, aprotic solvent {N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and dimethyl Sulfoxide and the like} and water.

  The concentration of the water / oil repellent in the solution is usually from 0.001 to 10% by weight, preferably from 0.01 to 10% by weight, particularly preferably from 0.1 to 5% by weight.

When a solid obtained by removing the solvent obtained from the solution is added to the structure and used, the amount of the water / oil repellent to be added is usually 0.01% to 10% by weight with respect to the structure. Preferably it is 0.01 to 5 weight%, Most preferably, it is 0.1 to 5 weight%.

The flame retardant of the present invention contains modified oxide nanoparticles modified with the functional group represented by the formula (1) and, if necessary, the formula (2) and / or the formula (3).

Content (weight%) of the flame retardant of this invention with respect to resin is 0.01-5, Preferably it is 0.05-3, Most preferably, it is 0.1-2.

The modified oxide nanoparticles are usually obtained as a precipitate (solid) when produced by the above production method. It is useful as a flame retardant by pulverizing the obtained precipitate after filtration and drying.

Moreover, when precipitation does not arise, it can be dripped in a solvent compatible with water, such as acetone, tetrahydrofuran, and dioxane, and can be obtained as precipitation.

Alternatively, a solid flame retardant can also be obtained by spray drying or freeze drying.

Examples of resins include acrylic resins (polymethyl methacrylate, etc.), polyester resins (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), ABS, polycarbonate (aromatic polycarbonates such as bisphenol and fluorene), polystyrene, epoxy, Unsaturated polyester, melamine, diallyl phthalate, polyimide, urethane, nylon, polyethylene, polypropylene, polyvinyl chloride, polybutadiene, polyisoprene, SBR, nitrile rubber, EPM, EPDM, epichlorohydrin rubber, neoprene rubber, porsulfide, butyl rubber, etc. and These alloys are mentioned.

The flame retardant of the present invention may be used in combination with other flame retardants. Examples of other flame retardants include organic phosphate ester flame retardants, halogenated phosphate ester flame retardants, inorganic phosphorus flame retardants, halogenated bisphenol flame retardants, other halogen compound flame retardants, and antimony flame retardants. Examples include flame retardants, nitrogen flame retardants, boric acid flame retardants, metal salt flame retardants, inorganic flame retardants, silicon flame retardants, and sulfonic acid flame retardants. Any one of these may be used alone. Alternatively, a plurality of types can be mixed and used.

Examples of the organic phosphate ester flame retardant include triphenyl phosphate, methyl neobenzyl phosphate, pentaerythritol diethyl diphosphate, methyl neopentyl phosphate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl high positive phosphate, dineo Examples include pentyl hypophosphite, phenyl pyrocatechol phosphite, ethyl pyrocatechol phosphate, and dipyrrocatechol high positive phosphate. Any one of these can be used alone or in combination.

Examples of the halogenated phosphate ester flame retardant include tris (β-chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (β-bromoethyl) phosphate, tris (dibromopropyl) phosphate, tris (chloropropyl) phosphate, Examples thereof include tris (dibromophenyl) phosphate, tris (tribromophenyl) phosphate, lith (tribromoneopentyl) phosphate, condensed polyphosphate, condensed polyphosphinate, and the like. Any one of these can be used alone or in combination.

Examples of the inorganic phosphorus flame retardant include red phosphorus and inorganic phosphate.
Any one of these can be used alone or in combination.

Examples of the halogenated bisphenol flame retardant include tetrabromobisphenol A and its oligomer, bis (bromoethyl ether) tetrabromobisphenol A, and the like. Any one of these can be used alone or in combination.

Other halogen compound flame retardants include decabromodiphenyl ether, hexabromobenzene, hexabromocyclododecane, tetrabromophthalic anhydride, (tetrabrobismophenol) epoxy oligomer, hexabromobiphenyl ether, tribromophenol, dibromocresyl Examples thereof include glycidyl ether, decabromodiphenyl oxide, halogenated polycarbonate, halogenated polycarbonate copolymer, halogenated polystyrene, halogenated polyolefin, chlorinated paraffin, and perchlorocyclodecane. Any one of these can be used alone or in combination.

Examples of the antimony flame retardant include antimony trioxide, antimony tetroxide, antimony pentoxide, and sodium antimonate. Any one of these can be used alone or in combination.

Examples of the nitrogen-based flame retardant include melamine, alkyl group or aromatic substituted melamine, melamine cyanurate, isocyanurate, melamine phosphate, triazine, guanidine compound, urea, various cyanuric acid derivatives, and phosphazene compounds. Any one of these can be used alone or in combination.

Examples of the boric acid flame retardant include zinc borate, zinc metaborate, and barium metaborate. Any one of these can be used alone or in combination.

Examples of metal salt flame retardants include polystyrene sulfonic acid, copolymers of polystyrene sulfonic acid and other vinyl compounds (for example, polystyrene-polystyrene sulfonic acid copolymer and partially sulfonated polystyrene), and perfluoroalkanes. Examples thereof include alkali metal salts and alkaline earth metal salts such as sulfonic acid, alkylbenzene sulfonic acid, halogenated alkylbenzene sulfonic acid, alkyl sulfonic acid, and naphthalene sulfonic acid. Any one of these can be used alone or in combination.

Examples of inorganic flame retardants include inorganic metal compounds such as magnesium hydroxide, aluminum hydroxide, barium hydroxide, calcium hydroxide, dolomite, hydrotalcite, basic magnesium carbonate, zirconium hydride, and tin oxide hydrate. Hydrate, aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, nickel oxide, copper oxide, tungsten oxide, etc. Metal oxides such as metal oxides, aluminum, iron, copper, nickel, titanium, manganese, tin, zinc, molybdenum, cobalt, bismuth, chromium, tungsten, antimony, zinc carbonate, magnesium carbonate, calcium carbonate, and barium carbonate Such as carbonates That. Any one of these can be used alone or in combination.

The content (% by weight) of the other flame retardant used in combination with the resin varies depending on the type, the required level of flame retardancy, and the type of resin composition to which flame retardancy is to be imparted. It is 0-50, Preferably it is 0-30, More preferably, it is 0-10.

The flame retardant resin composition comprising the flame retardant and resin of the present invention includes, as other additives, for example, inorganic fillers, impact resistance improvers, antioxidants (hindered phenol-based, phosphorus-based, sulfur-based). , Antistatic agent, ultraviolet absorber (benzophenone, benzotriazole, hydroxyphenyltriazine, cyclic imino ester, cyanoacrylate), light stabilizer, plasticizer, compatibilizer, colorant (pigment, dye) , Light diffusing agent, light stabilizer, crystal nucleating agent, antibacterial agent, fluidity modifier, antibacterial agent, infrared absorber, phosphor, hydrolysis inhibitor, mold release agent, or surface treatment agent May be. Thereby, flame retardancy, injection moldability, impact resistance, appearance, heat resistance, weather resistance, color, rigidity, etc. are improved.

The inorganic filler is used for the purpose of improving the mechanical strength of the resin composition and further improving the flame retardancy. Examples of the inorganic filler include crystalline silica, fused silica, alumina, magnesia, talc, mica, kaolin, clay, diatomaceous earth, calcium silicate, titanium oxide, glass fiber, calcium fluoride, calcium sulfate, barium sulfate, and calcium phosphate. , Carbon fiber, carbon nanotube, potassium titanate fiber and the like. Any one of these can be used alone or in combination. Of these inorganic fillers, talc, mica, carbon, and glass are preferably used, and talc is more preferable.

Content (weight%) of the inorganic filler in a flame-retardant resin composition is 2.5-20, More preferably, it is 5-15. If it exceeds 20, the fluidity of the molten resin composition when the resin composition (for example, aromatic polycarbonate resin composition) is injection-molded may deteriorate, or the impact resistance may decrease. There is.

The impact resistance improver is added for the purpose of improving the impact resistance of the resin composition. The impact resistance improver alone is effective, for example, in improving the toughness and elongation of the polycarbonate resin, and in the mixed system of the polycarbonate resin and the AS resin, they are compatible with each other or partially react. To improve the compatibility and improve the mechanical properties and moldability of the resin mixture.

As the impact resistance improver, it is possible to use materials usually used for resin modification (rubber-like elastic bodies, thermoplastic elastomers, compatibilizers, etc.). For example, ABS resin, HIPS resin, styrene-butadiene rubber (SBR), methyl methacrylate-styrene resin, methyl methacrylate-butadiene-styrene (MBS) resin, isoprene-styrene rubber, isoprene rubber, polybutadiene (PB), butadiene- Rubber-like elastic bodies such as acrylic rubber, isoprene-acrylic rubber, ethylene-propylene rubber, and others, polystyrene (SBC), vinyl chloride (TPVC), polyolefin (TPO), polyurethane (PU), polyester (TPEE), nitrile, polyamide (TPAE), fluorine, chlorinated polyethylene (CPE), syndiotactic-1,2-polybutadiene, trans-1,4-isoprene, silicone, chlorinated ethylene copolymer crosslinked Body alloy It may be mentioned thermoplastic elastomers such as esters halogen-based polymer alloy. More specifically, styrene-ethylene-butadiene-styrene copolymer (SEBS: hydrogenated styrene-based thermoplastic elastomer), styrene-ethylene-propylene-styrene copolymer (SEPS: hydrogenated styrene-based thermoplastic elastomer), Styrene-butadiene-styrene copolymer (SBS), styrene-hydrogenated butadiene-styrene copolymer, styrene-isoprene-styrene block copolymer (SIS), styrene-vinyloxazoline copolymer, epoxidized styrene elastomer, etc. Polystyrene grafted with styrene and acrylonitrile-butadiene polymer, petroleum resin obtained by polymerization of C5-C9 fraction, surface modification product by polymer of fine rubber particles, core shell with graft layer outside particulate rubber Of type撃耐 improver rubber component a butadiene rubber, the acrylic rubber, a silicone - can be exemplified as a preferable combination such as those of acrylic composite rubber.

Among these impact resistance improvers, ABS resin, HIPS resin, and styrene-based thermoplastic elastomer are particularly preferable. Examples of the styrene-based thermoplastic elastomer include SEBS, SEPS, SBS, styrene-hydrogenated butadiene-styrene copolymer, Examples include SIS, styrene-vinyloxazoline copolymer, and epoxidized styrene elastomer. Of these, SEBS is most preferred.

In addition, the impact resistance improving agent mentioned above may be used independently, and may be used in combination of multiple types.

The content (% by weight) of the impact resistance improver in the flame retardant resin composition is 0.2 to 10, more preferably 0.5 to 7.5, and further preferably 1 to 5%. It is.
If it exceeds 10, the flame retardancy and flowability of the resin composition (for example, an aromatic polycarbonate resin composition) will decrease.

The resin composition can be produced, for example, as follows. First, the resin material and various additives are mixed. At this time, for example, it is dispersed substantially uniformly by a kneading apparatus such as a tumbler, a reblender, a mixer, an extruder, or a kneader. Next, the mixture is subjected to a predetermined shape such as home appliances, automobiles, information by a molding method such as injection molding, injection compression molding, extrusion molding, blow molding, vacuum molding, press molding, foam molding, or supercritical molding. The resin composition can be obtained by molding into shapes of housings and parts of various products such as equipment, office equipment, telephones, stationery, furniture, and textiles.

Hereinafter, the present invention will be specifically described with reference to examples. The examples are illustrative of the invention and are not limiting.

Example 1
1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane (Amax Co., Ltd.) 2.0 g (5 mmol), 3- (trimethoxysilyl) propane-1-thiol (Chisso Corporation) 2.5 g (12. 8 mmol), phenyltrimethoxysilane (Tokyo Kasei Co., Ltd.) 1.68 g (8.5 mmol) was dissolved in 10 g of ethanol, 15.0 g of organosilica sol (manufactured by Nissan Chemical Co., 30% methanol solution), water 2 0.5 g was added and heated to reflux for 24 hours. After cooling, 9 g (79.4 mmol) of hydrogen peroxide solution (manufactured by Santoku Chemical Co., Ltd., 30% aqueous solution) was added and heated under reflux for 24 hours, so that C ₆ F ₁₃ CH ₂ CH ₂ —Si (—O—) A silica sol ethanol solution modified with _three groups, HO ₃ SCH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group and C ₆ H ₅ —Si (—O—) ₃ was obtained. C ₆ After filtering the dropped resulting precipitate in the solution of potassium hydroxide in isopropanol (0.5 N potassium hydroxide ethanol solution / isopropanol = 30 g / 100 g), isopropanol, by washed with acetone dry milled Modified with F ₁₃ CH ₂ CH ₂ —Si (—O—) ₃ group, KO ₃ SCH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group and C ₆ H ₅ —Si (—O—) ₃ 8.3 g of silica nanoparticles were obtained.

Example 2
1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane (Amax Co., Ltd.) 4.0 g (10 mmol), 3- (trimethoxysilyl) propane-1-thiol (Chisso Corp.) 1.67 g (8. 5 mmol), phenyltrimethoxysilane (Tokyo Kasei Co., Ltd.) 1.68 g (8.5 mmol) was dissolved in 10 g of ethanol, 15.0 g of organosilica sol (manufactured by Nissan Chemical Co., Ltd., 30% methanol solution), water 2 0.5 g was added and heated to reflux for 24 hours. After cooling, 6 g (52.9 mmol) of hydrogen peroxide solution (Santoku Chemical Co., Ltd., 30% aqueous solution) was added and heated under reflux for 24 hours, so that C ₆ F ₁₃ CH ₂ CH ₂ —Si (—O—) was obtained. A silica sol ethanol solution modified with _three groups, HO ₃ SCH ₂ CH ₂ CH ₂ —Si (O—) ₃ group and C ₆ H ₅ —Si (—O—) ₃ was obtained. This solution was dropped into an isopropanol solution of potassium hydroxide (0.5N potassium hydroxide ethanol solution / isopropanol = 30 g / 100 g), the resulting precipitate was filtered, washed with isopropanol and acetone, dried and pulverized to obtain 1H, Modified with C ₆ F ₁₃ CH ₂ CH ₂ —Si (—O—) ₃ group, KO ₃ SCH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group and C ₆ H ₅ —Si (—O—) ₃ 8.9 g of the prepared silica nanoparticles were obtained.

Example 3
(1) 10.0 g (51.0 mmol) of 3- (trimethoxysilyl) propane-1-thiol (Chisso Corporation), p-styrenesulfonic acid ethyl ester (Tosoh Organic Chemistry, purity 90%) 12.0 g ( 51.0 mmol) and 0.42 g (2.55 mmol) of azobisisobutyronitrile in 72 g of ethanol, the reaction system was purged with argon, and heated under reflux overnight to obtain the following compound (4). 94 g of ethanol solution was obtained.
_{C 2 H 5 O 3 S-} C 6 H 4 -CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3 (4)
(2) 31.5 g of the ethanol solution obtained in (1) and 3.97 g (0.05 mol) of 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (Amax Co., Ltd.) , 30% isopropanol solution) In addition to 15.0 g, 2.5 g of water is further added and heated under reflux for 24 hours, so that C ₂ H ₅ O ₃ SC ₆ H ₄ —CH ₂ CH ₂ SCH ₂ CH ₂ CH 53 g of ethanol silica sol modified with _2- Si (—O—) ₃ group and C ₆ F ₁₃ CH ₂ CH ₂ —Si (—O—) ₃ group was obtained.
(3) 26.5 g of ethanol silica sol obtained in (2) (containing 8.5 mmol as a structure derived from p-styrenesulfonic acid ethyl ester) and aqueous potassium hydroxide solution (2.24 g (34 mmol) of potassium hydroxide, water) 5 parts} was added and heated to reflux for 1 hour. The resulting precipitate was filtered, washed with ethyl alcohol and acetone, dried, and pulverized, so that KO ₃ S—C ₆ H ₄ —CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group and C 10.4 g of silica nanoparticles modified with ₆ F ₁₃ CH ₂ CH ₂ —Si (—O—) ₃ groups was obtained.

Example 4
26.5 g of ethanol silica sol obtained in (2) of Example 3 (containing 8.5 mmol as a structure derived from p-styrenesulfonic acid ethyl ester) and 3 g of hydrogen peroxide (manufactured by Santoku Chemical Co., Ltd., 30% aqueous solution) (26 mmol) was added and heated under reflux for 24 hours, and then an aqueous potassium hydroxide solution (2.24 g (34 mmol) of potassium hydroxide, 5 g of water) was added and heated under reflux for 1 hour. The resulting precipitate was filtered, washed with ethyl alcohol and acetone, dried, and then pulverized, whereby KO ₃ S—C ₆ H ₄ —CH ₂ CH ₂ SO ₂ CH ₂ CH ₂ CH ₂ —Si (—O—) ₃ groups And 6.0 g of silica nanoparticles modified with ₃ groups of C ₆ F ₁₃ CH ₂ CH ₂ —Si (—O—).

Example 5
After dissolving 2.6 g (0.05 mol) of 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (Amax Co., Ltd.) in 40.4 g of ethanol, organosilica sol (Nissan Chemical, 30% isopropanol solution) ) 6.0 g and 1.0 g of water were added and heated under reflux for 24 hours to obtain 50 g of an ethanol solution containing silica nanoparticles modified with C ₆ F ₁₃ CH ₂ CH ₂ —Si (—O—) ₃ groups.

Example 6
(1) After dissolving 5.2 g (0.1 mol) of 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (Amax Co., Ltd.) in 80.8 g of ethanol, organosilica sol (manufactured by Nissan Chemical Co., Ltd., 30 % Isopropanol solution) 12.0 g and water 2.0 g were added and heated under reflux for 24 hours to obtain 100.0 g of silica sol modified with C ₆ F ₁₃ CH ₂ CH ₂ —Si (—O—) ₃ groups.
(2) 3.81 g (0.05 mol) of 3,5-dimethylpyrazole and 12.35 g (0.05 mol) of 3-isocyanatopropyltriethoxysilane were dissolved in 100 g of dehydrated ethyl acetate and stirred at room temperature for 3 days. . After completion of the reaction, ethyl acetate was removed to obtain 16.8 g of a blocked isocyanate compound in which the isocyanate group of 3-isocyanatopropyltriethoxysilane was blocked with 3,5-dimethylpyrazole.
(3) The blocked isocyanate obtained in (2) was added to 49.0 g of an ethanol solution containing isopropanol silica sol modified with C ₆ F ₁₃ CH ₂ CH ₂ —Si (—O—) ₃ group obtained in (1). An ethanol solution 50 containing isopropanol silica sol modified with C ₆ F ₁₃ CH ₂ CH ₂ —Si (—O—) ₃ group and blocked isocyanate group by adding 1.0 g of compound and stirring at room temperature for 3 days 0.0 g was obtained.
(4) By diluting 50 g of the ethanol solution obtained in (3) with 100 g of water, isopropanol silica sol modified with ₃ groups of C ₆ F ₁₃ CH ₂ CH ₂ —Si (—O—) and a block isocyanate group An aqueous dispersion was obtained.

Example 7
(1) 3- (trimethoxysilyl) was added to 49.0 g of an ethanol solution containing isopropanol silica sol modified with C ₆ F ₁₃ CH ₂ CH ₂ —Si (—O—) ₃ group obtained in (1) of Example 6. ) By adding 1.0 g (5.1 mmol) of propane-1-thiol (Chisso Corporation) and stirring at room temperature for 3 days, ₃ groups of C ₆ F ₁₃ CH ₂ CH ₂ —Si (—O—) and 50.0 g of an ethanol solution containing isopropanol silica sol modified with HSCH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group was obtained.
(2) By mixing 12.5 g of the ethanol solution containing the isopropanol silica sol and 12.5 g of the ethanol solution containing the isopropanol silica sol obtained in (3) of Example 6 and diluting with 25 g of ethanol, C ₆ F ₁₃ 50.0 g of an ethanol solution containing isopropanol silica sol modified with CH ₂ CH ₂ —Si (—O—) ₃ group, blocked isocyanate group and HSCH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group is obtained. It was.

Example 8
(1) C ₈ synthesized according to Example 1 of International Publication No. 2009/087981 instead of 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (Amax Co., Ltd.) in (1) of Example 6 By performing the same operation using 3.6 g of F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ and 88.4 g of ethanol, C ₈ 100.0 g of an ethanol solution containing isopropanol silica sol modified with F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group was obtained.
(2) Isopropanol silica sol modified with C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group obtained in (1) By adding 1.0 g of the blocked isocyanate compound obtained in (2) of Example 6 to 49.0 g of the ethanol solution contained and stirring at room temperature for 3 days, C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH 20.0 g of an ethanol solution containing isopropanol silica sol modified with ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (—O—) ₃ groups and a blocked isocyanate group was obtained.
(3) The isopropanol silica sol modified with the C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group obtained in (1) is used. By adding 1.0 g (5.1 mmol) of 3- (trimethoxysilyl) propane-1-thiol (Chisso Corporation) to 49.0 g of the ethanol solution containing the mixture, the mixture was stirred at room temperature for 3 days, whereby C ₈ F ₁₇ − Isopropanol modified with ₃ groups CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (—O—) and ₃ groups HSCH ₂ CH ₂ CH ₂ —Si (—O—) An ethanol solution containing 50.0 g of silica sol was obtained.
(4) above (2) and _C 8 by diluting with ethanol solution respectively by mixing 12.5g ethanol 25.0g containing isopropanol silica sol obtained in _{(3) F 17 -CH 2 CH} 2 -OCO-CH _{2 CH 2 -S-CH 2 CH} 2 CH 2 -Si a _{(-O-) 3} group and blocked isocyanate group and _{HSCH 2 CH 2 CH 2 -Si (} -O-) isopropanol silica sol modified with ₃ groups An ethanol solution containing 50.0 g was obtained.

Example 9
In Example 8 (1) to (4), instead of C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ , international Using 3.6 g of C ₈ F ₁₇ —CH ₂ CH ₂ —OCONH—CH ₂ CH ₂ CH ₂ —Si (OC ₂ H ₅ ) ₃ synthesized according to Example 3 of publication 2009/087981 and 88.4 g of ethanol. By performing the same operation, C ₈ F ₁₇ —CH ₂ CH ₂ —OCONH—CH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group and HSCH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group 50.0 g of ethanol solution containing isopropanol silica sol modified with

Example 10
In Example 8 (1) to (4), C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ instead of international publication C ₄ F ₉ —CH ₂ CH ₂ —OCO—CH (CH ₃ ) CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ 2.6 g synthesized according to Example 4 of 2009/087981 By performing the same operation using 89.4 g of ethanol, C ₄ F ₉ —CH ₂ CH ₂ —OCO—CH (CH ₃ ) CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (—O—) ₃ 50.0 g of an ethanol solution containing an isopropanol silica sol modified with a group, a blocked isocyanate group and a HSCH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group was obtained.

Example 11
In Example 8 (1) to (4), C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ instead of international publication Similarly, 2.6 g of C ₄ F ₉ —CH ₂ CH ₂ —OCONH—CH ₂ CH ₂ CH ₂ —Si (OC ₂ H ₅ ) ₃ synthesized according to Example 8 of 2009/087981 and 89.4 g of ethanol were used. C ₄ F ₉ —CH ₂ CH ₂ —OCONH—CH ₂ CH ₂ CH ₂ —Si (O—) ₃ group, blocked isocyanate group and HSCH ₂ CH ₂ CH ₂ —Si (—O -) 50.0 g of ethanol solution containing isopropanol silica sol modified with ₃ groups was obtained.

Example 12
In Example 8 (1) to (4), C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ instead of international publication Using C ₄ F ₉ —SCH ₂ CH ₂ OCONH—CH ₂ CH ₂ CH ₂ —Si (OC ₂ H ₅ ) ₃ 2.7 g synthesized according to Example 20 of 2009/087981 and 89.3 g ethanol C ₄ F ₉ —SCH ₂ CH ₂ OCONH—CH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group and blocked isocyanate group and HSCH ₂ CH ₂ CH ₂ —Si (—O— ) 50.0 g of ethanol solution containing isopropanol silica sol modified with ₃ groups was obtained.

Example 13
In Example 8 (1) to (4), instead of C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ , international Similarly using 2.7 g of C ₄ F ₉ —SCH ₂ CH ₂ NHCONH—CH ₂ CH ₂ CH ₂ —Si (OC ₂ H ₅ ) ₃ synthesized according to Example 23 of Publication 2009/087981 and 89.3 g of ethanol. C ₄ F ₉ —SCH ₂ CH ₂ NHCONH—CH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group, blocked isocyanate group and HSCH ₂ CH ₂ CH ₂ —Si (—O -) 50.0 g of ethanol solution containing isopropanol silica sol modified with ₃ groups was obtained.

Example 14
In Example 8 (1) to (4), C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ instead of international publication C ₄ F ₉ —SO ₂ —CH ₂ CH ₂ OCONH—CH ₂ CH ₂ CH ₂ —Si (OC ₂ H ₅ ) ₃ 2.9 g synthesized according to Example 44 of 2009/087981 and 89.1 g of ethanol were used. In the same manner, C ₄ F ₉ —SO ₂ —CH ₂ CH ₂ OCONH—CH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group, blocked isocyanate group and HSCH ₂ CH ₂ CH ₂ 50.0 g of an ethanol solution containing isopropanol silica sol modified with -Si (-O-) ₃ groups was obtained.

Example 15
In Example 8 (1) to (4), C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ instead of international publication _C was synthesized according to example 50 of WO _{2009/087981 4 F 9 -S-C 6} H 4 -OCH 2 -C 6 H 4 -CH 2 CH 2 -S-CH 2 CH 2 CH 2 -Si (OCH 3) _{3 3.3g, C 4 F 9 -S} -C 6 H 4 -OCH 2 -C 6 H 4 -CH 2 CH 2 -S-CH 2 CH 2 by the same procedure using ethanol 88.7g 50.0 g of an ethanol solution containing isopropanol silica sol modified with a CH ₂ —Si (—O—) ₃ group, a blocked isocyanate group and a HSCH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group was obtained.

Example 16
In Example 8 (1) to (4), C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ instead of international publication _C was synthesized according to example 52 of WO _{2009/087981 4 F 9 CH 2 CH 2} -S-C 6 H 4 -OCH 2 -C 6 H 4 -CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) ₃ 3.4 g, _C 4 by the same procedure using ethanol _{88.6g F 9 CH 2 CH 2 -S} -C 6 H 4 -OCH 2 -C 6 H 4 -CH 2 CH 2 SCH 2 CH ₂ CH ₂ Si _{(-O-) 3} groups and blocked isocyanate groups and _{HSCH 2 CH 2 CH 2 -Si (} -O-) ethanol solution 50 containing a modified isopropanol silica sol ₃ groups It was obtained 0g.

Example 17
In Example 8 (1) to (4), C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ instead of international publication C ₄ F ₉ —S—C ₆ H ₄ —NHCONH—CH ₂ CH ₂ CH ₂ —Si (OC ₂ H ₅ ) ₃ 3.0 g synthesized according to Example 53 of 2009/087981 and 89.0 g of ethanol were used. In the same manner, C ₄ F ₉ —S—C ₆ H ₄ —NHCONH—CH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group, blocked isocyanate group and HSCH ₂ CH ₂ CH ₂ 50.0 g of an ethanol solution containing isopropanol silica sol modified with -Si (-O-) ₃ groups was obtained.

Example 18
In Example 8 (1) to (4), C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ instead of international publication C ₄ F ₉ —SO ₂ —C ₆ H ₄ —OCH ₂ —C ₆ H ₄ —CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ synthesized according to Example 67 of 2009/087981. 4 g and 88.6 g of ethanol were used in the same manner to obtain C ₄ F ₉ —SO ₂ —C ₆ H ₄ —OCH ₂ —C ₆ H ₄ —CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ Si (— 50.0 g of an ethanol solution containing isopropanol silica sol modified with O-) ₃ groups, blocked isocyanate groups and HSCH ₂ CH ₂ CH ₂ —Si (—O—) ₃ groups was obtained.

Example 19
In Example 8 (1) to (4), C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ instead of international publication _C was synthesized according to example 68 of WO _{2009/087981 4 F 9 -CH 2 CH 2} -SO 2 -C 6 H 4 -OCH 2 -C 6 H 4 -CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH ₃ ) By performing the same operation using 3.6 g of ₃ and 88.4 g of ethanol, C ₄ F ₉ —CH ₂ CH ₂ —SO ₂ —C ₆ H ₄ —OCH ₂ —C ₆ H ₄ —CH ₂ CH ethanone containing _{2 SCH 2 CH 2 CH 2 Si} (-O-) 3 groups and blocked isocyanate groups and _{HSCH 2 CH 2 CH 2 -Si (} -O-) isopropanol silica sol modified with ₃ groups It was obtained Lumpur solution 50.0g.

Example 20
(1) 3-glycidoxypropyl was added to 49.0 g of an ethanol solution containing isopropanol silica sol modified with C ₆ F ₁₃ CH ₂ CH ₂ —Si (—O—) ₃ group obtained in (1) of Example 6. By adding 1.0 g (5.1 mmol) of trimethoxysilane (Chisso Corporation) and stirring at room temperature for 3 days, C ₆ F ₁₃ CH ₂ CH ₂ —Si (—O—) ₃ group and 3-glucidoxy 50.0 g of an ethanol solution containing isopropanol silica sol modified with a group was obtained.
(2) By mixing 12.5 g of the ethanol solution containing the above isopropanol silica sol and 12.5 g of the ethanol solution containing the isopropanol silica sol obtained in (1) of Example 7 and diluting with 25 g of ethanol, C ₆ F ₁₃ 50.0 g of an ethanol solution containing isopropanol silica sol modified with CH ₂ CH ₂ —Si (—O—) ₃ group, 3-glucidoxy group and HSCH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group was obtained. .
Example 21
(1) C ₈ synthesized according to Example 1 of International Publication No. 2009/087981 instead of 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (Amax Co., Ltd.) in (1) of Example 6 _{F 17 -CH 2 CH 2 -OCO-} CH 2 CH 2 -S-CH 2 CH 2 CH 2 -Si (OCH 3) 3 3.6g, hydrogen peroxide (Santoku Kagaku Kogyo Co., Ltd., 30% aqueous solution) The same operation was carried out using 2.0 g and 86.4 g of ethanol, whereby C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —SO ₂ —CH ₂ CH ₂ CH ₂ —Si (—O— ) 100.0 g of an ethanol solution containing isopropanol silica sol modified with ₃ groups was obtained.
(2) The isopropanol silica sol modified with the C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —SO ₂ —CH ₂ CH ₂ CH ₂ —Si (O—) ₃ group obtained in (1) is used. By adding 1.0 g of the blocked isocyanate compound obtained in (2) of Example 6 to 49.0 g of the ethanol solution contained and stirring at room temperature for 3 days, C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH 20.0 g of an ethanol solution containing isopropanol silica sol modified with ₂ CH ₂ —SO ₂ —CH ₂ CH ₂ CH ₂ —Si (—O—) ₃ groups and a blocked isocyanate group was obtained.
(3) The isopropanol silica sol modified with the C ₈ F ₁₇ —CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —SO ₂ —CH ₂ CH ₂ CH ₂ —Si (O—) ₃ group obtained in (1) is used. By adding 1.0 g (5.1 mmol) of 3- (trimethoxysilyl) propane-1-thiol (Chisso Corporation) to 49.0 g of the ethanol solution containing the mixture, the mixture was stirred at room temperature for 3 days, whereby C ₈ F ₁₇ − Modified with CH ₂ CH ₂ —OCO—CH ₂ CH ₂ —SO ₂ —CH ₂ CH ₂ CH ₂ —Si (—O—) ₃ and HSCH ₂ CH ₂ CH ₂ —Si (—O—) ₃ An ethanol solution containing 50.0 g of isopropanol silica sol was obtained.
(4) above (2) and _C 8 by diluting with ethanol solution respectively by mixing 12.5g ethanol 25.0g containing isopropanol silica sol obtained in _{(3) F 17 -CH 2 CH} 2 -OCO-CH Isopropanol silica sol modified with ₂ CH ₂ —SO ₂ —CH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group, blocked isocyanate group and HSCH ₂ CH ₂ CH ₂ —Si (—O—) ₃ group An ethanol solution containing 50.0 g was obtained.

Comparative Example 1
1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (Amax Co., Ltd.) 2.6 g (0.01 mol) was dissolved in an ethanol solution (ethanol 45.9 g, water 1 g, acetic acid 0.5 g) for 24 hours. By refluxing, 50.0 g of an ethanol solution containing a hydrolyzate of 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane was obtained.

[Manufacture of resin pellets]
The modified silica nanoparticles obtained in Examples 1 to 4 and the polycarbonate resin (Panlite L-1225L: manufactured by Teijin Kasei Kogyo Co., Ltd.) were dry blended at the ratio shown in Table 2, and a twin-screw kneader (KZW15 manufactured by Technobel). 30MG), and kneaded under the conditions of a screw speed of 100 rpm, a discharge rate of 15 g / min, and a cylinder temperature of 200 to 230 ° C. The molten resin extruded in a strand shape was pelletized with a pelletizer to obtain pellets of a polycarbonate resin composition (a flame retardant resin composition).

[Preparation of test piece]
The pellet obtained by the above-described production method was preheated at 135 ° C. under reduced pressure (0.01 MPa) for 5 minutes by a vacuum hot press machine (manufactured by Tester Sangyo Co., Ltd.) and then pressed for 1 minute to give a thickness of 1.6 mm. A plate of polycarbonate resin composition was obtained. A UL94 test specimen having a length of 125 mm, a width of 13 mm, and a thickness of 1.6 mm was formed with a dumbbell cutter (Dumb Bell SDL-200) in which the stage was heated to 155 ° C. and the blade of the cutter was heated to 150 ° C.

[Flame retardance evaluation]
The flame retardancy evaluation of each polycarbonate resin composition was performed in accordance with the UL94 test defined by US Underwriters Laboratories (UL) for the test piece obtained by the above-described method. UL94V is a method for evaluating flame retardancy from the afterflame time after a 20-mm-high flame has been smoked for 10 seconds on a test piece of a predetermined size held vertically and the cotton ignition of absorbent cotton by drip. In order to have flame retardancy of −0, V−1 and V−2, it is necessary to satisfy the criteria shown in Table 1 below.

Here, the afterflame time is the time during which the test piece continues to be flammable after the ignition source is moved away. Further, the cotton ignition by drip is determined by whether or not the marking cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. Furthermore, when one of the five samples did not satisfy the above criteria, it was evaluated as Not V because V-2 was not satisfied. The results are shown in Table 2. In Table 2, the UL94 test results are indicated as “flame retardant”.

[Transparency evaluation]
When a polycarbonate resin composition plate having a thickness of 1.6 mm obtained by the above-described production method is visually observed, a polycarbonate composition having no or very little haze is indicated as “high”, and a haze is indicated as “having haze”. It was written in “Transparency” in 2.

[Water repellency evaluation]
(1) Slides {76 mm, 26 mm, 1.2 mm; immersed in 2-propanol saturated solution of sodium hydroxide for 24 hours, washed with water and dried (60 ° C., 2 hours)} Example 5 and comparison The solution (surface water repellent) obtained in Example 1 was applied to obtain a surface water-repellent slide glass that was heat-treated at 130 ° C. for 1 hour.
(2) A polyester cloth (100 mm square) was immersed in the solutions obtained in Example 6 and Comparative Example 1, and heat-treated at 130 ° C. for 1 hour to obtain a water-repellent polyester cloth.
(3) The ground iron plate (50 mm × 20 mm, thickness 1 mm) was coated with the solutions obtained in Examples 7 to 12 and Comparative Example 1, and heat-treated at 150 ° C. for 1 hour to obtain a water-repellent iron plate.
(4) The solution obtained in Examples 13 to 16 and Comparative Example 1 was applied to a polycarbonate plate (25 mm × 85 mm, thickness 1 mm) and heat-treated at 130 ° C. for 1 hour to obtain a water-repellent polycarbonate plate.
(5) Polyethylene terephthalate sheet (25 mm × 85 mm, thickness 100 μm) was applied with the solution obtained in Examples 17 to 21 and Comparative Example 1, and heat treated at 130 ° C. for 1 hour to make a water-repellent polyethylene terephthalate sheet. Got.

Contact angle measuring device {Kyowa Interface Chemical Co., Ltd., DROP MASTER 500, appropriate amount 2μL, measurement interval 1000ms, number of measurements 30 times} for any 5 locations on the surface of the surface water-repellent slide glass and water-repellent polyester cloth The contact angle (degree) was measured, and the average value was calculated. The results are shown in Table 3.

  From Table 2, it is clear that the flame retardant of the present invention has a large flame retardant effect, and from Table 3, the water repellent of the present invention has a higher water repellency than the conventional water repellent. In Examples 7 to 20, the water repellency did not decrease even when rubbed with a cloth. In Comparative Example 1, the water repellency was decreased when the structure was an iron plate, a polycarbonate plate or a polyethylene terephthalate sheet. It is clear that the water repellent of the present invention has good adhesion to the substrate and high durability.

The modified metal oxide sol of the present invention is suitable as a flame retardant and a water repellent because it has a large flame retardant effect and a water repellent effect, can be added or coated, and can be manufactured at low cost. Moreover, when coating as a water repellent, the adhesiveness with respect to a metal or a plastic is high.

Claims (14)

Modified metal oxide nanoparticles modified with a functional group represented by the following formula (1):
_{^{C m F 2m + 1 -X 1}} -R 1 -Y 1 -Si (CH 3) n (-O-) 3-n (1)
{In the formula, m is an integer from 1 to 12, ^{X 1} is a single _{bond, -S -, - SO -,} - SO 2 -, - CH 2 CH 2 S -, - CH 2 CH 2 SO- or - CH ₂ CH ₂ SO ₂ —, R ¹ is an alkylene group having 1 to 10 carbon atoms, a phenylene group or a phenyleneoxymethylene phenylene group; Y ¹ is a single bond, —OCONH (CH ₂ ) ₃ —, NHCONH ( _{CH 2) 3 -, - OCO} (CH 2) 2 S (CH 2) 3 -, - OCO (CH 2) 2 SO (CH 2) 3 -, - OCO (CH 2) 2 SO 2 (CH 2) 3 _{-, - OCOCH (CH 3)} CH 2 S (CH 2) 3 -, - OCOCH (CH 3) CH 2 SO (CH 2) 3 -, - OCOCH (CH 3) CH 2 SO 2 (CH 2) 3 - _{- (CH 2) 2 S (} CH 2) 3 - , — (CH ₂ ) ₂ SO (CH ₂ ) ₃ — or — (CH ₂ ) ₂ SO ₂ (CH ₂ ) ₃ —, and n represents 0 or 1. } The modified metal oxide nanoparticles according to claim 1, further modified with a functional group represented by the following formula (2).
_{^{X 2 - (R 2) m}} -Si (CH 3) n (-O-) 3-n (2)
{Wherein X ² is a linear or branched alkyl group having 1 to 20 carbon atoms, vinyl group, thiol group, amino group, chlorine atom, acrylic group, methacryl group, styryl group, phenyl group, glycidoxy group, 3, A functional group selected from the group consisting of a 4-epoxycyclohexyl group and a blocked isocyanate group, R ² is an alkylene group having 1 to 5 carbon atoms, m is 0 or 1, and n is 0 or 1. . } The modified metal oxide nanoparticles according to claim 1 or 2, further modified with a functional group represented by the following formula (3).
_{^{MOS (= O) 2 -R 3}} -Si (CH 3) n (-O-) 3-n (3)
{In the formula, M represents a hydrogen ion, an alkyl group having 1 to 4 carbon atoms, a metal ion or an ammonium (NR ⁴ ₄ ) group, and R ³ represents an alkylene group having 1 to 10 carbon atoms (in this alkylene chain, a urethane bond or may contain urea _{linkages), - C 6 H 4 (} CH 2) 2 S (CH 2) 3 -, - C 6 H 4 (CH 2) 2 SO (CH 2) 3 - or -C ₆ H ₄ (CH ₂ ) ₂ SO ₂ (CH ₂ ) ₃ —, R ⁴ is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, which may be the same or different, and n represents 0 or 1. }   The modified metal oxide nanoparticle according to any one of claims 1 to 3, wherein the metal oxide nanoparticle is an organosilica sol. A water / oil repellent containing the modified metal oxide nanoparticles according to claim 1. The water / oil repellent according to claim 5, wherein the form is a solution or a solid.   A structure containing or coated with the water / oil repellent according to claim 5 or 6.   The structure according to claim 7, wherein the structure is fiber, resin, leather, fur, glass, ceramics, or metal. The flame retardant containing the modified metal oxide nanoparticle in any one of Claims 1-4.   The flame retardant according to claim 9, wherein the form is a solution or a solid. A flame retardant resin composition comprising the flame retardant according to claim 9 or 10 and a resin.   The molded object formed by shape | molding the flame-retardant resin composition of Claim 11.   A structure containing or coated with the flame retardant according to claim 9 or 10. The structure according to claim 13, wherein the structure is fiber, resin, leather, fur, glass, ceramics, or metal.