JP2023036534A - Organopolysiloxane composition - Google Patents

Abstract

[PROBLEMS] To improve compatibility with hydrophobic organic materials and hydrophobic inorganic materials while suppressing the generation of alcohol when dissolved in an aprotic solvent and used as a silane coupling agent or fiber treatment agent. To provide a homogeneous and transparent organopolysiloxane composition having amino groups and silanol groups, capable of SOLUTION: A transparent organopolysiloxane composition comprising only a powdery silicone resin represented by the following general formula (1), a carboxylic acid compound or a natural oil containing a carboxylic acid compound, and an aprotic solvent. TIFF2023036534000006.tif3058 (Wherein, each R independently represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom; represents a hydrogen atom, a methyl group or an ethyl group, and a represents an integer of 2 to 70.) [Selection] None

Description

The present invention relates to organopolysiloxane compositions.

In the organosilicon compound having a hydrolyzable silyl group and an organic group, the silanol group generated by hydrolysis of the hydrolyzable silyl group forms a covalent bond with the hydroxyl group on the surface of the inorganic material, and the organic group further bonds with the organic material. Because it reacts, it makes it possible to combine organic materials and inorganic materials, which are usually difficult to combine. As a result, properties such as heat resistance, water resistance, weather resistance, improved mechanical strength, adhesion, dispersibility, hydrophobicity, and rust resistance can be imparted to the organic-inorganic composite material.
Utilizing these characteristics, the organosilicon compounds are used in a wide range of fields and applications such as silane coupling agents, resin additives, surface treatment agents, fiber treatment agents, adhesives, paint additives, polymer modifiers, etc. .

Among the above organosilicon compounds, aminosilane compounds having an amino group exhibit high reactivity with various organic and inorganic materials, so that the adhesion of the organic-inorganic composite material can be enhanced.
Examples of such aminosilane compounds include 3-aminopropyltrimethoxysilane (Patent Document 1). Further, examples of organopolysiloxane compositions obtained by hydrolyzing this aminosilane compound include 3-aminopropylsilanetriol homopolymer (Patent Document 2).

JP-A-10-17578 U.S. Patent Application Publication No. 2020/0068897

However, the aminosilane compound having an alkoxysilyl group described in Patent Document 1 generates a considerable amount of alcohol by hydrolysis of the alkoxysilyl group. In recent years, the reduction of volatile organic compounds (VOCs) has become a major theme in environmental issues that are deeply related to global warming and health problems. Concerned about load.

In this regard, the organopolysiloxane composition having an amino group and a silanol group described in Patent Document 2 is a silanol condensate produced by hydrolyzing an aminosilane compound having an alkoxysilyl group. Since it can be removed, it is useful as one method for reducing the amount of alcohol generated from the aminosilane compound.
Moreover, since this organopolysiloxane composition is a silanol condensate having a plurality of silanol groups, it also has the advantage of having excellent reactivity with the hydroxyl groups on the substrate surface. That is, in the hydrolysis reaction of the aminosilane compound, the silanol groups are condensed with each other to form a silanol condensate having a linear, branched, cyclic, or three-dimensional network structure. Since the condensation of silanol groups reaches an equilibrium due to the interaction between the silanol groups and the amino groups, the silanol condensate contains a plurality of silanol groups that are not condensed. This allows a plurality of silanol groups to react with a plurality of hydroxyl groups on the surface of the base material, thereby improving adhesion to the organic-inorganic composite material.

However, although the organopolysiloxane composition having an amino group and a silanol group described in Patent Document 2 can remove the generated alcohol, the solvent exhibiting compatibility is limited to protic solvents such as water or lower alcohols. Therefore, when using an aprotic solvent, a homogeneous and transparent solution cannot be prepared. That is, since the silanol condensate contained in the organopolysiloxane composition exhibits hydrophilicity due to a plurality of silanol groups, it has low compatibility with aprotic solvents. precipitates or separates as an oily substance). A heterogeneous and opaque solution containing these solids or liquids cannot sufficiently come into contact with various organic and inorganic materials, resulting in reduced reactivity with hydroxyl groups on the substrate surface. Further, in the case of a solution containing a protic solvent such as water or a lower alcohol, the compatibility with hydrophobic organic materials and hydrophobic inorganic materials is low, so it cannot be applied to applications where these are blended.

Therefore, it has solubility in aprotic solvents, and when used as a silane coupling agent or fiber treatment agent, improves compatibility with hydrophobic organic materials and hydrophobic inorganic materials while suppressing the generation of alcohol. It is desired to develop a homogeneous, transparent organopolysiloxane composition having amino groups and silanol groups, which can be

The present invention has been made in view of the above circumstances, and when dissolved in an aprotic solvent and used as a silane coupling agent or fiber treatment agent, while suppressing the generation of alcohol, a hydrophobic organic material and a hydrophobic It is an object of the present invention to provide a uniform and transparent organopolysiloxane composition having amino groups and silanol groups, which can improve compatibility with organic materials.

The inventors of the present invention have made intensive studies to achieve the above object, and found that a powdery silicone resin having an amino group and a silanol group dissolves in an aprotic solvent due to interaction with a carboxylic acid compound. , to form a uniform and transparent solution (composition) that does not cause deposition of solids or separation of liquids, and that when this composition is used as a silane coupling agent or a fiber treatment agent, no alcohol is generated, and The inventors have found that the compatibility with hydrophobic organic materials and hydrophobic inorganic materials is improved, and completed the invention.

（式中、Ｒ¹は、それぞれ独立してヘテロ原子を含んでいてもよい、置換または非置換の炭素数１～２０の２価炭化水素基を表し、Ｒ²は、それぞれ独立して、水素原子、メチル基またはエチル基を表し、ａは、２～７０の整数を表す。）
２． 前記シリコーンレジンの乾式レーザー回析法による平均粒子径が、体積基準メジアン径で１～２００μｍである１のオルガノポリシロキサン組成物、
３． 前記シリコーンレジンが、スプレードライ粒子である１または２のオルガノポリシロキサン組成物、
４． 前記カルボン酸化合物が、炭素数１～１１の飽和モノカルボン酸化合物および炭素数３～２２の不飽和モノカルボン酸化物から選ばれる１種または２種以上である１～３のいずれかのオルガノポリシロキサン組成物、
５． 前記非プロトン性溶媒が、飽和脂肪族炭化水素系溶媒、不飽和脂肪族炭化水素系溶媒、芳香族炭化水素系溶媒およびケトン系溶媒から選ばれる１種または２種以上である１～４のいずれかのオルガノポリシロキサン組成物
を提供する。 That is, the present invention
1. A transparent organopolysiloxane composition consisting only of a powdery silicone resin represented by the following general formula (1), a carboxylic acid compound or a natural oil containing a carboxylic acid compound, and an aprotic solvent,

(wherein each R ¹ independently represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom; each R ² independently represents a hydrogen represents an atom, a methyl group or an ethyl group, and a represents an integer of 2 to 70.)
2. 1. The organopolysiloxane composition of 1, wherein the average particle size of the silicone resin measured by a dry laser diffraction method is 1 to 200 μm in volume-based median size;
3. The organopolysiloxane composition of 1 or 2, wherein the silicone resin is spray-dried particles;
4. 1 to 3, wherein the carboxylic acid compound is one or more selected from saturated monocarboxylic acid compounds having 1 to 11 carbon atoms and unsaturated monocarboxylic oxides having 3 to 22 carbon atoms; a siloxane composition,
5. Any one of 1 to 4, wherein the aprotic solvent is one or more selected from saturated aliphatic hydrocarbon solvents, unsaturated aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents and ketone solvents. An organopolysiloxane composition is provided.

The organopolysiloxane compositions of the present invention can be prepared as homogeneous, clear solutions with no precipitation of solids or separation of liquids.
In addition, the organopolysiloxane composition of the present invention exhibits high compatibility with hydrophobic organic materials and hydrophobic inorganic materials. It is possible to increase the adhesion with.

The present invention will be specifically described below.
The organopolysiloxane composition of the present invention comprises a powdery silicone resin represented by the following general formula (1) (hereinafter referred to as "silicone resin (1)"), a carboxylic acid compound or a natural oil containing a carboxylic acid compound and It consists only of an aprotic solvent.

In general formula (1), each R ¹ is independently substituted with 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, which may contain a heteroatom, or represents an unsubstituted divalent hydrocarbon group.
The divalent hydrocarbon group for R ¹ may be linear, branched or cyclic, and specific examples include methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, Linear alkylene groups such as methylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadecamethylene and icosamethylene groups isopropylene, isobutylene, sec-butylene, tert-butylene, isopentylene, isohexylene, isoheptylene, isooctylene, isononylene, isodecylene, isoundecylene, isododecylene, isotridecylene, isotetradecylene, isopentadecylene, isohexadecylene, isohepta Branched alkylene groups such as decylene, isooctadecylene, isononadecylene, and isoicosylene groups; Cyclic alkylene groups such as silene, cyclotetradecylene, cyclopentadecylene, cyclohexadecylene, cycloheptadecylene, cyclooctadecylene, cyclononadecylene, and cycloicosylene; ethenylene, propenylene, butenylene, pentenylene, hexenylene, Alkenylene groups such as heptenylene, octenylene, nonylene, decenylene, undecenylene, dodecenylene, tridecenylene, tetradecenylene, pentadecenylene, hexadecenylene, heptadecenylene, octadecenylene, nonadecenylene, and icosenylene groups; arylene groups such as phenylene and naphthylene groups; methylenephenylene, methylenephenylene methylene groups, etc. and an aralkylene group. In addition, the bivalent hydrocarbon group containing a heteroatom for R ¹ includes an alkyleneaminoalkylene group, an alkyleneoxyalkylene group, an alkylenethioalkylene group, and the like, and these alkylene groups each independently include the linear Examples include the same groups as those exemplified for the linear, branched, and cyclic alkylene groups.

Some or all of the hydrogen atoms of these divalent hydrocarbon groups may be substituted with other substituents, and specific examples of these substituents include methoxy, ethoxy, (iso)propoxy groups, and the like. Alkoxy groups having 1 to 4 carbon atoms; Halogen atoms such as fluorine, chlorine and bromine; Aryl groups such as phenyl, tolyl and xylyl groups; Aralkyl groups such as benzyl and phenethyl groups; group, carbonyl group, acyl group, sulfide group and the like, and one or more of these may be used in combination. The substitution position of these substituents is not particularly limited, and the number of substituents is also not limited.

Among these, R ¹ is an unsubstituted straight, branched or cyclic alkylene group having 1 to 8 carbon atoms; an alkenylene group; an arylene group; an aralkylene group; an alkyleneaminoalkylene group; An alkylenethioalkylene group is preferred, particularly from the viewpoint of availability of precursor raw materials, an unsubstituted, linear or branched alkylene group having 1 to 6 carbon atoms; an alkyleneaminoalkylene group is more preferred, and a methylene group , dimethylene group, trimethylene group, isopropylene group, methyleneaminomethylene group, methyleneaminodimethylene group, methyleneaminotrimethylene group, dimethyleneaminomethylene group, dimethyleneaminodimethylene group, dimethyleneaminotrimethylene group, trimethylene Aminomethylene group, trimethyleneaminodimethylene group and trimethyleneaminotrimethylene group are more preferred.

In the general formula (1), each R ² independently represents a hydrogen atom, a methyl group or an ethyl group, preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom from the viewpoint of availability of precursor raw materials. .

In the general formula (1), a is an integer of 2 to 70, preferably 2 to 60, more preferably 2 to 50, even more preferably 2, especially from the viewpoint of compatibility with an aprotic solvent. ~40.
In the general formula (1), a is an integer of 2 to 70, preferably 2 to 60, more preferably 2 to 50, even more preferably 2, especially from the viewpoint of compatibility with an aprotic solvent. to 40, more preferably 5 to 40, even more preferably 15 to 40, particularly preferably 20 to 40.
The range of a in formula (1) can be determined by measuring the amine value of silicone resin (1). Here, the amine value is a value that indicates the amount of organic amine in a sample. Calculated by measuring mg of potassium oxide (KOH).

Specific examples of the silicone resin (1) include primary amino acids such as 1-aminomethylsilanetriol homopolymer, 2-aminoethylsilanetriol homopolymer, 2-aminoisopropylsilanetriol homopolymer, and 3-aminopropylsilanetriol homopolymer. Silicone resins having groups; N-methyl-1-aminomethylsilanetriol homopolymer, N-methyl-2-aminoethylsilanetriol homopolymer, N-methyl-2-aminoisopropylsilanetriol homopolymer, N-methyl-3 -Silicone resins having secondary amino groups such as aminopropylsilanetriol homopolymer; N,N-dimethyl-1-aminomethylsilanetriol homopolymer, N,N-dimethyl-2-aminoethylsilanetriol homopolymer, N, Silicone resins having a tertiary amino group such as N-dimethyl-2-aminoisopropylsilanetriol homopolymer, N,N-dimethyl-3-aminopropylsilanetriol homopolymer; N-(1-aminomethyl)-1-amino Methylsilanetriol Homopolymer, N-(1-Aminomethyl)-2-Aminoethylsilanetriol Homopolymer, N-(1-Aminomethyl)-2-Aminoisopropylsilanetriol Homopolymer, N-(1-Aminomethyl) -3-aminopropylsilanetriol homopolymer, N-(2-aminoethyl)-1-aminomethylsilanetriol homopolymer, N-(2-aminoethyl)-2-aminoethylsilanetriol homopolymer, N-(2 -aminoethyl)-2-aminoisopropylsilanetriol homopolymer, N-(2-aminoethyl)-3-aminopropylsilanetriol homopolymer, N-(2-aminoisopropyl)-1-aminomethylsilanetriol homopolymer, N-(2-aminoisopropyl)-2-aminoethylsilanetriol homopolymer, N-(2-aminoisopropyl)-2-aminoisopropylsilanetriol homopolymer, N-(2-aminoisopropyl)-3-aminopropylsilane Triol Homopolymer, N-(3-Aminopropyl)-1-Aminomethylsilanetriol Homopolymer, N-(3-Aminopropyl)-2-Aminoethylsilanetriol Homopolymer, N-(3-Aminopropyl)-2 - aminoisopropylsilanetriol homopolymer, N- Silicone resins having diamino groups such as (3-aminopropyl)-3-aminopropylsilanetriol homopolymers can be used.

Among these, when used as a silane coupling agent or fiber treatment agent, 1-aminomethylsilanetriol homopolymer, 2- Aminoethylsilanetriol homopolymer, 2-aminoisopropylsilanetriol homopolymer, 3-aminopropylsilanetriol homopolymer, N-(1-aminomethyl)-1-aminomethylsilanetriol homopolymer, N-(1-aminomethyl )-2-aminoethylsilanetriol homopolymer, N-(1-aminomethyl)-2-aminoisopropylsilanetriol homopolymer, N-(1-aminomethyl)-3-aminopropylsilanetriol homopolymer, N-( 2-aminoethyl)-1-aminomethylsilanetriol homopolymer, N-(2-aminoethyl)-2-aminoethylsilanetriol homopolymer, N-(2-aminoethyl)-2-aminoisopropylsilanetriol homopolymer , N-(2-aminoethyl)-3-aminopropylsilanetriol homopolymer, N-(2-aminoisopropyl)-1-aminomethylsilanetriol homopolymer, N-(2-aminoisopropyl)-2-aminoethyl Silanetriol Homopolymer, N-(2-Aminoisopropyl)-2-Aminoisopropylsilanetriol Homopolymer, N-(2-Aminoisopropyl)-3-AminopropylSilantriol Homopolymer, N-(3-Aminopropyl)- 1-aminomethylsilanetriol homopolymer, N-(3-aminopropyl)-2-aminoethylsilanetriol homopolymer, N-(3-aminopropyl)-2-aminoisopropylsilanetriol homopolymer, N-(3- Aminopropyl)-3-aminopropylsilanetriol homopolymer is preferred.

The silicone resin (1) used in the present invention is a powdery solid.
The particle shape of the silicone resin (1) may be spherical, polyhedral, spindle-shaped, needle-shaped, plate-shaped, etc., but a spherical shape is preferable from the viewpoint of ease of handling. In the present invention, the term "spherical" means that the shape of particles includes not only true spheres but also ellipsoids. The shape of the particles is confirmed by observing the particles with an optical microscope, an electron microscope, or the like.

The average particle size of the silicone resin (1) is preferably 1 to 200 μm, more preferably 10 to 150 μm, still more preferably 30 to 100 μm, from the viewpoint of promotion of interaction with the carboxylic acid compound.
The average particle size means a volume-based median size (D50) measured by a dry laser diffraction method. The volume-based median diameter is measured by a dry method according to Fraunhofer diffraction theory using a laser diffraction particle size distribution analyzer Mastersizer 3000 (manufactured by Malvern) under the conditions of a dispersion pressure of 2 bar and a scattering intensity of 2 to 10%. It is calculated by measuring the diameter corresponding to the 50% cumulative value of the standard cumulative particle size distribution curve.

The loose bulk density of the silicone resin (1) is preferably 0.2 to 0.9 g/mL, more preferably 0.25 to 0.9 g/mL, from the viewpoint of promotion of interaction with the carboxylic acid compound. Even more preferably 0.3 to 0.9 g/mL.
The bulk density was measured by pouring powdery silicone resin into a 100 ml container whose mass had been measured in advance until it overflowed (without vibrating the measurement container or compressing the sample at this time). Calculated by scraping the raised powder with a scraping board, measuring the mass of the content, and calculating the mass per mL.

The above silicone resin (1) is usually produced by hydrolyzing an aminosilane compound having an alkoxysilyl group represented by the following general formula (2).

In general formula (2), R ¹ and R ² include the same substituents as exemplified above. Each R ³ independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 2 carbon atoms.
The monovalent hydrocarbon group for R ³ may be linear, branched or cyclic, and specific examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl. , n-heptyl, n-octyl, n-nonyl, n-decyl groups; sec-propyl, sec-butyl, tert-butyl, sec-pentyl, tert-pentyl, sec-hexyl, tert -branched alkyl groups such as hexyl, sec-heptyl, tert-heptyl, sec-octyl, tert-octyl, sec-nonyl, tert-nonyl, sec-decyl and tert-decyl groups; Cyclic alkyl groups; alkenyl groups such as vinyl, allyl, butenyl and methallyl groups; aryl groups such as phenyl, tolyl and xylyl groups; and aralkyl groups such as benzyl and phenethyl groups.

Some or all of the hydrogen atoms of these monovalent hydrocarbon groups may be substituted with other substituents, and specific examples of these substituents include hydrogen atoms of the divalent hydrocarbon group of R ¹ Substituents similar to the substituents in which some or all of the atoms may be substituted with other substituents may be mentioned, and one or more of these may be used in combination. The substitution position of these substituents is not particularly limited, and the number of substituents is also not limited.

Among these, R ³ is preferably an unsubstituted straight-chain alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or an ethyl group from the viewpoint of availability.

Specific examples of aminosilane compounds having an alkoxysilyl group include 1-aminomethyltrimethoxysilane, 1-aminomethyltriethoxysilane, 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 2-aminoisopropyltri trialkoxysilane compounds having a primary amino group such as methoxysilane, 2-aminoisopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane; N-methyl-1-aminomethyltrimethoxysilane, N-methyl-1-aminomethyltriethoxysilane, N-methyl-2-aminoethyltrimethoxysilane, N-methyl-2-aminoethyltriethoxysilane, N-methyl-2-aminoisopropyltrimethoxysilane, N- trialkoxysilane compounds having a secondary amino group such as methyl-2-aminoisopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-methyl-3-aminopropyltriethoxysilane; Dimethyl-1-aminomethyltrimethoxysilane, N,N-dimethyl-1-aminomethyltriethoxysilane, N,N-dimethyl-2-aminoethyltrimethoxysilane, N,N-dimethyl-2-aminoethyltriethoxy Silane, N,N-dimethyl-2-aminoisopropyltrimethoxysilane, N,N-dimethyl-2-aminoisopropyltriethoxysilane, N,N-dimethyl-3-aminopropyltrimethoxysilane, N,N-dimethyl- Trialkoxysilane compounds having a tertiary amino group such as 3-aminopropyltriethoxysilane; N-(1-aminomethyl)-1-aminomethyltrimethoxysilane, N-(1-aminomethyl)-1-aminomethyl Triethoxysilane, N-(1-aminomethyl)-2-aminoethyltrimethoxysilane, N-(1-aminomethyl)-2-aminoethyltriethoxysilane, N-(1-aminomethyl)-2-amino Isopropyltrimethoxysilane, N-(1-aminomethyl)-2-aminoisopropyltriethoxysilane, N-(1-aminomethyl)-3-aminopropyltrimethoxysilane, N-(1-aminomethyl)-3- aminopropyltriethoxysilane, N-(2-aminoethyl)-1-aminomethyltrimethoxysilane, N-(2-aminoethyl)-1-aminomethyltriethoxysilane, N-(2-aminoethyl)-2-aminoethyltrimethoxysilane, N-(2-aminoethyl)-2-aminoethyltriethoxysilane, N-(2-aminoethyl)-2-aminoisopropyltrimethoxysilane , N-(2-aminoethyl)-2-aminoisopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane Silane, N-(2-aminoisopropyl)-1-aminomethyltrimethoxysilane, N-(2-aminoisopropyl)-1-aminomethyltriethoxysilane, N-(2-aminoisopropyl)-2-aminoethyltri Methoxysilane, N-(2-aminoisopropyl)-2-aminoethyltriethoxysilane, N-(2-aminoisopropyl)-2-aminoisopropyltrimethoxysilane, N-(2-aminoisopropyl)-2-aminoisopropyl Triethoxysilane, N-(2-aminoisopropyl)-3-aminopropyltrimethoxysilane, N-(2-aminoisopropyl)-3-aminopropyltriethoxysilane, N-(3-aminopropyl)-1-amino methyltrimethoxysilane, N-(3-aminopropyl)-1-aminomethyltriethoxysilane, N-(3-aminopropyl)-2-aminoethyltrimethoxysilane, N-(3-aminopropyl)-2- Aminoethyltriethoxysilane, N-(3-aminopropyl)-2-aminoisopropyltrimethoxysilane, N-(3-aminopropyl)-2-aminoisopropyltriethoxysilane, N-(3-aminopropyl)-3 -aminopropyltrimethoxysilane, N-(3-aminopropyl)-3-aminopropyltriethoxysilane, and other trialkoxysilane compounds having a diamino group.

Among these, 1-aminomethyltrimethoxysilane and 1-amino are particularly useful as silane coupling agents and fiber treatment agents, from the viewpoint of enhancing adhesion to organic materials by reacting with a plurality of hydroxyl groups on the substrate surface. methyltriethoxysilane, 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 2-aminoisopropyltrimethoxysilane, 2-aminoisopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane Ethoxysilane, N-(1-aminomethyl)-1-aminomethyltrimethoxysilane, N-(1-aminomethyl)-1-aminomethyltriethoxysilane, N-(1-aminomethyl)-2-aminoethyl Trimethoxysilane, N-(1-aminomethyl)-2-aminoethyltriethoxysilane, N-(1-aminomethyl)-2-aminoisopropyltrimethoxysilane, N-(1-aminomethyl)-2-amino Isopropyltriethoxysilane, N-(1-aminomethyl)-3-aminopropyltrimethoxysilane, N-(1-aminomethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-1- Aminomethyltrimethoxysilane, N-(2-aminoethyl)-1-aminomethyltriethoxysilane, N-(2-aminoethyl)-2-aminoethyltrimethoxysilane, N-(2-aminoethyl)-2 -aminoethyltriethoxysilane, N-(2-aminoethyl)-2-aminoisopropyltrimethoxysilane, N-(2-aminoethyl)-2-aminoisopropyltriethoxysilane, N-(2-aminoethyl)- 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoisopropyl)-1-aminomethyltrimethoxysilane, N-(2-aminoisopropyl) -1-aminomethyltriethoxysilane, N-(2-aminoisopropyl)-2-aminoethyltrimethoxysilane, N-(2-aminoisopropyl)-2-aminoethyltriethoxysilane, N-(2-aminoisopropyl) )-2-aminoisopropyltrimethoxysilane, N-(2-aminoisopropyl)-2-aminoisopropyltriethoxysilane, N-(2-aminoisopropyl)-3-aminopropyltrimethoxysilane, N-(2-amino isopropyl)-3-aminop Lopyltriethoxysilane, N-(3-aminopropyl)-1-aminomethyltrimethoxysilane, N-(3-aminopropyl)-1-aminomethyltriethoxysilane, N-(3-aminopropyl)-2 -aminoethyltrimethoxysilane, N-(3-aminopropyl)-2-aminoethyltriethoxysilane, N-(3-aminopropyl)-2-aminoisopropyltrimethoxysilane, N-(3-aminopropyl)- 2-aminoisopropyltriethoxysilane, N-(3-aminopropyl)-3-aminopropyltrimethoxysilane, N-(3-aminopropyl)-3-aminopropyltriethoxysilane are preferred.

Hydrolysis of an aminosilane compound having an alkoxysilyl group generates a considerable amount of alcohol corresponding to the alkoxysilyl group. Moreover, water may be included depending on the amount of water added for hydrolysis.
As described above, the organopolysiloxane composition of the present invention is a uniform and transparent solution in which the silicone resin (1) is dissolved in an aprotic solvent. Therefore, from the viewpoint of compatibility with the aprotic solvent, The silicone resin (1) is preferably obtained by removing alcohol and water from a hydrolyzed solution.

The method for removing alcohol and water from the hydrolyzate is not particularly limited, and a removal method such as centrifugation, heat drying, chromatography, recrystallization, distillation, extraction, decantation, liquid separation, or filtration may be employed. can be done. Among these, heat drying is preferable from the viewpoint of productivity.

In addition, specific examples of the method for producing a powdery silicone resin include a method of heating and pulverizing the hydrolyzate that has been left standing, a method of heating the hydrolyzate to stir and flow, and a method of heating the hydrolyzate in a high-temperature air current such as a spray dryer. A spray drying method (spray drying method) in which the hydrolyzate is sprayed and dispersed, a method using a fluid heat medium, and the like.

In the spray drying method, a solution containing a solid and a solvent is decomposed (sprayed) into small droplets, which are brought into contact with a high-temperature air stream in a drying chamber to instantaneously evaporate the solvent, resulting in powdery solids (particles). ) is a granulation method to obtain.
The driving force for the evaporation of the solvent is generally obtained by lowering the partial pressure of the solvent relative to the vapor pressure of the solvent at the temperature at which the droplets are dried. Preferred embodiments include a method of mixing the droplets with a hot dry gas, a method of maintaining the pressure in the solvent remover at a partial vacuum, and the like.

The above solutions can be sprayed into the drying chamber at a wide range of flow rates and temperatures. Moreover, when pressurizing at the time of spraying, it is possible to spray in a wide range of pressures. In general, the evaporation rate of the solvent increases as the specific surface area of the droplet increases.
For this reason, the sprayed droplet size is preferably less than 500 μm, more preferably less than 400 μm, even more preferably between 5 and 200 μm. Also preferred are flow rates, temperatures, and pressures that allow such atomization.
The solution feed flow rate is preferably 1-500 kg/h, more preferably 5-100 kg/h, even more preferably 10-50 kg/h.
The drying chamber inlet temperature is preferably 100-250°C, more preferably 110-220°C, even more preferably 120-200°C.
The drying chamber exit temperature is preferably 0-100°C, more preferably 0-95°C, even more preferably 0-90°C.
The solution supply pressure is preferably 100-50,000 kPa, more preferably 200-10,000 kPa, even more preferably 300-5,000 kPa.

As a method for manufacturing powdered silicone resin, if a vacuum dryer or the like is used to heat and pulverize the hydrolyzate that has been allowed to stand still, the solvent and moisture will remain. When used as a treatment agent, the adhesion to the organic-inorganic composite material is reduced.
In contrast, in the spray drying method, the specific surface area of the sprayed particles is extremely large, so the solvent and water are efficiently evaporated and removed. As a result, the solvent and water content is less than when powdered by other methods, so the powdered silicone resin produced by the spray-drying method has the advantage of excellent adhesion to organic-inorganic composite materials. There is Therefore, the silicone resin used in the present invention is preferably spray-dried particles obtained by the spray-drying method, from the viewpoint of controlling the contents of the solvent and moisture, etc., and controlling the physical properties such as the average particle size and bulk density.

The content of the silicone resin (1) in the organopolysiloxane composition is particularly limited as long as it reacts with a plurality of hydroxyl groups on the surface of the base material to enhance adhesion when used as a silane coupling agent or fiber treatment agent. However, from the viewpoint of productivity, it is preferably 0.001 to 99% by mass, more preferably 0.01 to 50% by mass, and still more preferably 0.1 to 10% by mass, based on the organopolysiloxane composition. is.

The carboxylic acid compound used in the organopolysiloxane composition of the present invention is not particularly limited, but may be selected from saturated monocarboxylic acid compounds having 1 to 11 carbon atoms and unsaturated monocarboxylic oxides having 3 to 22 carbon atoms. One or two or more selected are preferred.
Specific examples thereof include saturated monocarboxylic acid compounds having 1 to 11 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, and undecylic acid; Acrylic acid, methacrylic acid, isocrotonic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, myristoleic acid, pentadecenoic acid, hexadecenoic acid, hexadecenoic acid Decadienoic acid, hexadecatrienoic acid, hexadecatetraenoic acid, palmitoleic acid, sapienic acid, heptadecenoic acid, heptadecadienoic acid, heptadecatrienoic acid, heptadecatetraenoic acid, octadecenoic acid, octadecadienoic acid, octadecadrienoic acid , octadecatetraenoic acid, oleic acid, ricinoleic acid, vaccenic acid, linoleic acid, linolenic acid, nonadecenic acid, nonadecadienoic acid, nonadecatrienoic acid, nonadecatetraenoic acid, eicosenoic acid, eicosadienoic acid, eicosatrienoic acid, eicosa Unsaturated monocarboxylic acid compounds having 3 to 22 carbon atoms such as tetraenoic acid, eicosapentaenoic acid, gadoleic acid, arachidonic acid, docosenoic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosahexaenoic acid, erucic acid, etc. These carboxylic acid compounds may be used singly or in combination of two or more.

Natural oils containing these carboxylic acid compounds may also be used in the organopolysiloxane composition of the present invention.
Specific examples of natural oils include almond oil, astropotassium murumuru seed fat, avocado oil, Amazuna seed oil, linseed oil, Argania spinosa kernel oil, apricot kernel oil, olive fruit oil, cocoa butter, caninabara fruit oil, and canola oil. , kukui nut oil, black currant seed oil, corn oil, sesame oil, wheat germ oil, rice bran oil, rice germ oil, pomegranate seed oil, safflower oil, shea butter, sclelocariavirea seed oil, soybean oil, tea Seed oil, evening primrose oil, camellia seed oil, theobroma grandiflorum seed oil, palm kernel fatty acid, palm kernel oil, palm oil, horse oil, hybrid safflower oil, hybrid sunflower oil, peanut oil, pistachio seed oil, castor oil, Sunflower seed oil, grape seed oil, hazelnut seed oil, jojoba seed oil, macadamia seed oil, mango seed oil, meadowfoam oil, Japanese wax, peach kernel oil, coconut fatty acid, coconut oil, peanut oil, borage seed oil, rosehip oil , horseradish seed oil, and the like.

Among these, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, acrylic acid, methacrylic acid, isocrotonic acid , pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, myristoleic acid, pentadecenoic acid, hexadecenoic acid, hexadecadienoic acid, hexadecatrienoic acid , hexadecatetraenoic acid, palmitoleic acid, sapienic acid, heptadecenoic acid, heptadecadienoic acid, heptadecatrienoic acid, heptadecatetraenoic acid, octadecenoic acid, octadecadienoic acid, octadecatrienoic acid, octadecatetraenoic acid, olein acid, ricinoleic acid, vaccenic acid, linoleic acid, linolenic acid, nonadecenic acid, nonadecadienoic acid, nonadecatrienoic acid, nonadecatetraenoic acid, eicosenoic acid, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, eicosapentaenoic acid, Gadoleic acid, arachidonic acid, docosenoic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosahexaenoic acid, erucic acid are preferred, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid , oleic acid, ricinoleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, and docosahexaenoic acid are more preferred.

The carboxylic acid compound described above interacts with the silicone resin (1). Specifically, the carboxyl group of the carboxylic acid compound reacts with the amino group of the silicone resin (1) to form a salt or amide bond, while also reacting with the silanol group to form an ester bond. The silicone resin (1) formed with a salt, an amide bond or an ester bond has improved hydrophobicity due to the hydrocarbon group of the carboxylic acid compound, and thus has improved compatibility with aprotic solvents.
As described above, the organopolysiloxane composition of the present invention is a uniform and transparent solution in which the silicone resin (1) is dissolved in an aprotic solvent. Therefore, from the viewpoint of compatibility with the aprotic solvent, As the carboxylic acid compound, it is preferable to use a monocarboxylic acid compound that does not form a crosslinked structure. From the viewpoint of promoting interaction with the silicone resin (1), it is preferable to use a liquid monocarboxylic acid compound that is compatible with an aprotic solvent.

The content of the carboxylic acid compound in the organopolysiloxane composition is not particularly limited as long as the organopolysiloxane composition becomes a homogeneous and transparent solution. , preferably 0.001 to 99% by mass, more preferably 0.01 to 50% by mass, and even more preferably 0.1 to 10% by mass.

Specific examples of the aprotic solvent used in the organopolysiloxane composition of the present invention include pentane, isopentane, cyclopentane, hexane, isohexane, cyclohexane, heptane, isoheptane, octane, isooctane, nonane, isononane, decane, isodecane, Dodecane, isododecane, tetradecane, isotetradecane, hexadecane, isohexadecane, octadecane, isooctadecane, eicosane, isoeicosane, liquid paraffin, liquid isoparaffin, saturated aliphatic hydrocarbon solvents such as squalane; pentene, hexene, heptene, octene, nonene, Unsaturated aliphatic hydrocarbon solvents such as decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, and squalene; aromatics such as benzene, toluene, xylene, ethylbenzene, mesitylene, styrene, and tetralin ketone solvents such as acetone and methyl isobutyl ketone; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents; chlorinated hydrocarbon solvents such as dichloromethane and chloroform;

Among these, from the viewpoint of compatibility with hydrophobic organic materials and hydrophobic inorganic materials, saturated aliphatic hydrocarbon solvents, unsaturated aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents and ketone solvents One or two or more selected from solvents are preferable, and one or two or more selected from saturated aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents are more preferable.

The content of the aprotic solvent in the organopolysiloxane composition is not particularly limited as long as the organopolysiloxane composition becomes a homogeneous and transparent solution. On the other hand, it is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, and still more preferably 20 to 80% by mass.

The organopolysiloxane composition of the present invention comprises only the silicone resin (1), a carboxylic acid compound or a natural oil containing the same, and an aprotic solvent, and is uniform and transparent without precipitation of solids or separation of liquids. form a clear solution.

The method for producing the organopolysiloxane composition is not particularly limited as long as the silicone resin (1) is soluble in the aprotic solvent, and a method of adding the silicone resin (1) to a solution containing a carboxylic acid compound and an aprotic solvent. a method of adding a solution containing silicone resin (1) and a carboxylic acid compound to an aprotic solvent; a method of adding a solution containing silicone resin (1) and an aprotic solvent to a carboxylic acid compound; a method of adding a solution containing a resin (1) and an aprotic solvent; a method of adding a solution containing a carboxylic acid compound and an aprotic solvent to a silicone resin (1); Either a method of adding to a solution containing a carboxylic acid compound, or a method of mixing the silicone resin (1) with the carboxylic acid compound and an aprotic solvent at the same time may be used. A method in which the compound and the aprotic solvent are mixed simultaneously is preferred.

The mixing temperature is preferably 20 to 100°C, more preferably 20 to 60°C, and even more preferably 20 to 40°C, from the viewpoint of productivity.
The mixing time is preferably 1 to 72 hours, more preferably 1 to 48 hours, and still more preferably 1 to 24 hours from the viewpoint of productivity, but may be set appropriately in relation to the preparation temperature. .

The organopolysiloxane composition of the present invention is, as described above, a uniform and transparent composition comprising three components: the silicone resin (1), the carboxylic acid compound or a natural oil containing it, and the aprotic solvent. The polysiloxane composition can be used for various purposes by adding other additives.
In this case, the composition to which other additives are added may be homogeneous and transparent like the organopolysiloxane composition of the present invention, or may become non-uniform and opaque as a result of adding other additives. Precipitation of solids or separation of liquids may occur.

Other additives include solid, semi-solid, or liquid oils, water, alcohols, water-soluble polymers, film-forming agents, surfactants, oil-soluble gelling agents, and organic modifiers that are commonly used in cosmetics. Clay minerals, powders, antiperspirants, UV absorbers, UV absorbing scattering agents, moisturizers, preservatives, antibacterial agents, fragrances, salts, antioxidants, pH adjusters, chelating agents, cooling agents, anti-inflammatory agents, Skin-beautifying ingredients (whitening agents, cell activators, rough skin ameliorators, blood circulation promoters, skin astringents, antiseborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, inclusion compounds, hair solidifying agents, etc. is mentioned.
Specific examples of additives are listed below, but the present invention is not limited to these.

Examples of solid, semi-solid or liquid oils include hydrocarbon oils, higher alcohols, ester oils, glyceride oils, silicone oils and fluorinated oils.

Hydrocarbon oils include ozokerite, α-olefin oligomer, light isoparaffin, isododecane, isohexadecane, light liquid isoparaffin, squalane, synthetic squalane, vegetable squalane, squalene, ceresin, paraffin, paraffin wax, polyethylene wax, and polyethylene/polypropylene wax. , (ethylene/propylene/styrene) copolymer, (butylene/propylene/styrene) copolymer, liquid paraffin, liquid isoparaffin, pristane, polyisobutylene, hydrogenated polyisobutene, microcrystalline wax, petrolatum, and the like.

Higher alcohols include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, Cholesterol, phytosterol, POE cholesterol ether, monostearyl glycerin ether (batyl alcohol), monooleyl glyceryl ether (selachyl alcohol) and the like.

Ester oils include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, N-alkyl glycol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, di-2-ethyl Ethylene glycol hexanoate, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate, octyldodecyl gum ester, oleyl oleate, octyldodecyl oleate , decyl oleate, neopentyl glycol dioctoate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate, butyl acetate, isocetyl stearate, butyl stearate, diisopropyl sebacate, sebacic acid Di-2-ethylhexyl, cetyl lactate, myristyl lactate, isononyl isononanoate, isotridecyl isononanoate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, 12-hydroxystearic acid Cholesteryl, dipentaerythritol fatty acid ester, isopropyl myristate, octyldodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, hexyl laurate, N-lauroyl-L-glutamic acid- 2-octyldodecyl ester, lauroyl sarcosine isopropyl ester, diisostearyl malate and the like.

Glyceride oils include acetoglyceryl, glyceryl triisooctanoate, glyceryl triisostearate, glyceryl triisopalmitate, glyceryl tribehenate, glyceryl monostearate, glyceryl di-2-heptylundecanoate, glyceryl trimyristate, isostearin myristate. and diglyceryl acid.
Examples of silicone oils include dimethylpolysiloxane, trimethylsiloxymethylsilane, caprylylmethicone, phenyltrimethicone, tetrakistrimethylsiloxysilane, methylphenylpolysiloxane, methylhexylpolysiloxane, methylhydrogenpolysiloxane, dimethylsiloxane/methylphenylsiloxane. Low to high viscosity linear or branched organopolysiloxanes such as copolymers; octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetrahydrogencyclotetrasiloxane, tetramethyl Cyclic organopolysiloxane such as tetraphenylcyclotetrasiloxane; amino-modified organopolysiloxane, pyrrolidone-modified organopolysiloxane, pyrrolidonecarboxylic acid-modified organopolysiloxane, highly polymerized gum-like dimethylpolysiloxane, gum-like amino-modified organopolysiloxane, Silicone rubbers such as gum-like dimethylsiloxane/methylphenylsiloxane copolymers and cyclic organopolysiloxane solutions of silicone gums and rubbers; higher alkoxy-modified silicones such as stearyl silicone; higher fatty acid-modified silicones, alkyl-modified silicones, long-chain alkyl Modified silicone, amino acid-modified silicone, fluorine-modified silicone and the like can be mentioned.
Fluorinated oils include perfluoropolyether, perfluorodecalin, perfluorooctane, and the like.

Alcohols include lower alcohols such as ethanol and isopropanol; sugar alcohols such as sorbitol and maltose; sterols such as cholesterol, sitosterol, phytosterol and lanosterol; Alcohol etc. are mentioned.

Water-soluble polymers include gum arabic, tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), starch (rice, corn, potato, wheat, etc.), algecolloid, tranto gum, locust. Plant-based polymers such as bean gum; Microbial-based polymers such as xanthan gum, dextran, succinoglucan and pullulan; Animal-based polymers such as collagen, casein, albumin and gelatin; Starches such as carboxymethyl starch and methylhydroxypropyl starch Cellulose-based polymer; methylcellulose, ethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, nitrocellulose, sodium cellulose sulfate, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder; sodium alginate, propylene alginate Alginate-based polymers such as glycol ester; vinyl-based polymers such as polyvinyl methyl ether and carboxyvinyl polymer; polyoxyethylene-based polymers, polyoxyethylene-polyoxypropylene copolymer-based polymers, sodium polyacrylate, polyethyl acrylate , polyacrylamide, acrylic polymers such as acryloyldimethyltaurate copolymers; other synthetic water-soluble polymers such as polyethylene imine, cationic polymers; bentonite, aluminum magnesium silicate, montmorillonite, beidellite, nontronite, saponite, hectorite, Examples thereof include inorganic water-soluble polymers such as silicic anhydride.

Examples of film-forming agents include latexes such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, and polyalkyl acrylate; dextrin, cellulose derivatives such as alkylcellulose and nitrocellulose; silicones such as tri(trimethylsiloxy)silylpropylcarbamate pullulan; Polysaccharide compounds; acrylic-silicone graft copolymers such as (alkyl acrylate/dimethicone) copolymers; silicone resins such as trimethylsiloxysilicate; silicone resins such as silicone-modified polynorbornene and fluorine-modified silicone resins; Examples include aromatic hydrocarbon resins, polymer emulsion resins, terpene resins, polybutene, polyisoprene, alkyd resins, polyvinylpyrrolidone-modified polymers, rosin-modified resins, and polyurethanes.

Surfactants include fatty acid soaps such as sodium stearate and triethanolamine palmitate, alkyl ether carboxylic acids and their salts, condensate salts of amino acids and fatty acids, alkanesulfonates, alkenesulfonates, and sulfones of fatty acid esters. acid salts, fatty acid amide sulfonates, formalin condensation sulfonates, alkyl sulfates, secondary higher alcohol sulfates, alkyl and allyl ether sulfates, fatty acid ester sulfates, fatty acid alkylolamides sulfuric acid ester salts, sulfuric acid ester salts such as funnel oil, alkyl phosphate, ether phosphate, alkyl allyl ether phosphate, amide phosphate, N-acyl lactate, N-acyl sarcosinate, N-acyl amino acid anionic surfactants such as system active agents; cationic surfactants such as alkylamine salts, amine salts such as polyamines and aminoalcohol fatty acid derivatives, alkyl quaternary ammonium salts, aromatic quaternary ammonium salts, pyridium salts, imidazolium salts, etc. Active agent; sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, methyl glucoside fatty acid ester, alkyl polyglucoside, polyoxyethylene alkyl ether, polyoxypropylene alkyl Ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, Polyoxyethylene hydrogenated castor oil, polyoxyethylene phytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, linear or branched polyoxyalkylene-modified organopolysiloxane, linear or branched polyoxyalkylene/alkyl co-modified organopolysiloxane, linear or branched polyglycerin-modified organopolysiloxane, linear or branched polyglycerin/alkyl co-modified organopolysiloxane, alkanolamide, sugar ether, Non-ion such as sugar amide Amphoteric surfactants; betaine, phosphatidylcholine, aminocarboxylates, imidazoline derivatives, amphoteric surfactants such as amidoamine type and the like.

Oil-soluble gelling agents include metallic soaps such as aluminum stearate, magnesium stearate and zinc myristate; amino acid derivatives such as N-lauroyl-L-glutamic acid and α,γ-di-n-butylamine; dextrin palmitate , dextrin stearate, dextrin 2-ethylhexanoic acid palmitate and other dextrin fatty acid esters; sucrose palmitate, sucrose fatty acid esters such as sucrose stearate; fructooligosaccharide stearate, fructooligosaccharide 2-ethyl Fructo-oligosaccharide fatty acid esters such as hexanoic acid esters; benzylidene derivatives of sorbitol such as monobenzylidene sorbitol and dibenzylidene sorbitol;
Examples of organically modified clay minerals include dimethylbenzyldodecylammonium-montmorillonite clay and dimethyldioctadecylammonium-montmorillonite clay.

Examples of the powder include those used in ordinary cosmetics, and the shape (spherical, needle-like, plate-like, etc.), particle size (fumed, fine particles, pigment grade, etc.), particle structure (porous, Nonporous, etc.) can be used, for example, inorganic powders, organic powders, surfactant metal salt powders, colored pigments, pearl pigments, metal powder pigments, tar pigments, Examples include powders selected from natural pigments and the like.
Inorganic powders include titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite, and synthetic mica. , phlogopite, red mica, biotite, lethia mica, silicic acid, silicic anhydride, aluminum silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, strontium silicate, metal tungstate, Hydroxyapatite, vermiculite, hydilite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride, silica and the like.
Organic powders include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane, benzoguanamine powder, polymethylbenzoguanamine powder, tetrafluoroethylene powder, polymethylmethacrylate powder, cellulose, silk powder, nylon powder, 12 Nylon, 6 nylon, silicone powder, styrene/acrylic acid copolymer, divinylbenzene/styrene copolymer, vinyl resin, urea resin, phenolic resin, fluorine resin, silicone resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin , microcrystalline fiber powder, starch powder, lauroyl lysine, and the like.
Surfactant metal salt powder (metal soap) includes zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc cetylphosphate, calcium cetylphosphate, zinc sodium cetylphosphate, and the like. mentioned.

Colored pigments include inorganic red pigments such as iron oxide, iron hydroxide, and iron titanate, inorganic brown pigments such as γ-iron oxide, inorganic yellow pigments such as yellow iron oxide and ocher, black iron oxide, carbon black, and the like. inorganic black pigments, inorganic purple pigments such as manganese violet and cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate, inorganic blue pigments such as Prussian blue and ultramarine blue, and tar pigments. natural pigments, lakes of natural pigments, and synthetic resin powders obtained by combining these powders.
Pearl pigments include titanium oxide-coated mica, titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish scale foil, and titanium oxide-coated colored mica.
Metal powder pigments include aluminum powder, copper powder, stainless steel powder and the like.
Tar pigments include Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 404 , Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, Orange No. 207, and the like.
Natural pigments include carminic acid, laccaic acid, calsamine, brazilin, crocin, and the like.

These powders may be compounded powders or treated with general oils, silicone oils, fluorine compounds, surfactants, etc., and may be directly bonded to hydrolyzable silyl groups or silicon atoms. linear and/or branched organopolysiloxanes having hydrolyzable silyl groups or hydrogen atoms directly bonded to silicon atoms, hydrolyzable silyl groups or silicon atoms Linear and/or branched organopolysiloxanes with directly bonded hydrogen atoms co-modified with long-chain alkyls, hydrolyzable silyl groups and polyoxyalkylenes with hydrogen atoms directly bonded to silicon atoms. Modified linear and/or branched organopolysiloxanes, acrylic-silicone copolymers having hydrolyzable silyl groups or hydrogen atoms directly bonded to silicon atoms, etc. may also be used, if necessary, one or more. can be used.

Antiperspirants include aluminum chlorohydrate, aluminum chloride, aluminum sesquichlorohydrate, zirconyl hydroxychloride, aluminum zirconium hydroxychloride, aluminum zirconium glycine complex and the like.

Examples of ultraviolet absorbers include benzoic acid-based ultraviolet absorbers such as para-aminobenzoic acid; anthranilic acid-based ultraviolet absorbers such as methyl anthranilate; salicylic acid-based ultraviolet absorbers such as methyl salicylate, octyl salicylate, and trimethylcyclohexyl salicylate; cinnamic acid UV absorbers such as octyl parmate; benzophenone UV absorbers such as 2,4-dihydroxybenzophenone; urocanic acid UV absorbers such as ethyl urocanate; 4-t-butyl-4'-methoxy- dibenzoylmethane-based ultraviolet absorbers such as dibenzoylmethane; phenylbenzimidazole sulfonic acid, triazine derivatives and the like.
Examples of ultraviolet absorbing and scattering agents include powders that absorb and scatter ultraviolet rays, such as fine particle titanium oxide, fine particle iron-containing titanium oxide, fine particle zinc oxide, fine particle cerium oxide, and composites thereof. A dispersion obtained by previously dispersing the body in an oil agent can also be used.

Moisturizers include glycerin, sorbitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, pentylene glycol, glucose, xylitol, maltitol, polyethylene glycol, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate, polyoxy Ethylene methyl glucoside, polyoxypropylene methyl glucoside, egg yolk lecithin, soybean lecithin, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, sphingophospholipids and the like.

Antiseptics and antibacterial agents include paraoxybenzoic acid alkyl ester, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, imidazolidinyl urea, salicylic acid, isopropylmethylphenol, phenolic acid, parachlormetacresol, and hexachlorophene. , benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, propynyl butylcarbamate iodide, polylysine, photosensitive element, silver, plant extract and the like.

Flavoring agents include natural and synthetic fragrances.
Natural fragrances include plant fragrances isolated from flowers, leaves, wood, pericarp, etc., and animal fragrances such as musk and civet.
Synthetic fragrances include hydrocarbons such as monoterpene; alcohols such as aliphatic alcohols and aromatic alcohols; aldehydes such as terpene aldehydes and aromatic aldehydes; ketones such as alicyclic ketones; Esters; lactones, phenols, oxides, nitrogen-containing compounds, acetals, and the like.

Salts include inorganic salts, organic acid salts, amine salts, amino acid salts and the like.
Examples of inorganic salts include sodium salts, potassium salts, magnesium salts, calcium salts, aluminum salts, zirconium salts and zinc salts of inorganic acids such as hydrochloric acid, sulfuric acid, carbonic acid and nitric acid.
Organic acid salts include salts of organic acids such as acetic acid, dehydroacetic acid, citric acid, malic acid, succinic acid, ascorbic acid and stearic acid.
Amine salts and amino acid salts include salts of amines such as triethanolamine and salts of amino acids such as glutamic acid. In addition, salts of hyaluronic acid, chondroitin sulfate, etc., and acid-alkali neutralized salts used in formulations can also be used.

Antioxidants include carotenoids, ascorbic acid and its salts, ascorbyl stearate, tocopherol, tocopherol acetate, tocopherol, pt-butylphenol, butylhydroxyanisole, dibutylhydroxytoluene, phytic acid, ferulic acid, thiotaurine, hypotaurine. , sulfite, erythorbic acid and its salts, chlorogenic acid, epicatechin, epigallocatechin, epigallocatechin gallate, apigenin, camperol, myricetin, quercetin and the like.

Potassium carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate, etc. are mentioned as a pH adjuster.
Chelating agents include alanine, sodium edetate, sodium polyphosphate, sodium metaphosphate, phosphoric acid and the like.
Cooling agents include L-menthol, camphor, menthyl lactate and the like.
Anti-inflammatory agents include allantoin, glycyrrhizic acid and its salts, glycyrrhetinic acid and stearyl glycyrrhetinate, tranexamic acid, azulene, and the like.

Skin-beautifying ingredients include whitening agents such as placenta extract, arbutin, glutathione, and saxifrage extract; cell activators such as royal jelly, photosensitizers, cholesterol derivatives, and calf blood extract; Nicotinic Acid Benzyl Ester, Nicotinic Acid β-Butoxyethyl Ester, Capsaicin, Zingerone, Cantharis Tincture, Ictamol, Caffeine, Tannic Acid, α-Borneol, Tocopherol Nicotinate, Inositol Hexanicotinate, Cyclanderate, Cinnarizine, Tolazoline, Examples include blood circulation promoters such as acetylcholine, verapamil, cepharanthine and γ-oryzanol, skin astringents such as zinc oxide and tannic acid, and antiseborrheic agents such as sulfur and thianthrol.

Examples of vitamins include vitamin A oil, vitamin A such as retinol, retinol acetate, and retinol palmitate, vitamin B2 such as riboflavin, riboflavin butyrate, and flavin adenine nucleotide, pyridoxine hydrochloride, pyridoxine dioctanoate, and pyridoxine tripalmi. Vitamin B6 such as Tate, Vitamin B12 and its derivatives, Vitamin B15 and its derivatives, L-ascorbic acid, L-ascorbic acid dipalmitate, L-ascorbic acid-2-sodium sulfate, L- Vitamin Cs such as dipotassium ascorbic acid phosphate diester, vitamin Ds such as ergocalciferol and cholecalciferol, α-tocopherol, β-tocopherol, γ-tocopherol, dl-α-tocopherol acetate, dl-α-nicotinic acid Tocopherol, vitamin E such as dl-α-tocopherol succinate, nicotinic acid, benzyl nicotinate, nicotinic acid such as nicotinamide, vitamin H, vitamin P, calcium pantothenate, D-pantothenyl alcohol, pantothenyl ethyl ether , pantothenic acids such as acetylpantothenyl ethyl ether, biotin and the like.

Amino acids include glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, aspartic acid, glutamic acid, cystine, cysteine, methionine, tryptophan, and the like.
Nucleic acids include deoxyribonucleic acid and the like.
Hormones include estradiol, ethenyl estradiol and the like.
The inclusion compound includes cyclodextrin and the like.

Examples of hair solidifying agents include amphoteric, anionic, cationic and nonionic polymer compounds, polyvinylpyrrolidone polymer compounds such as polyvinylpyrrolidone and vinylpyrrolidone/vinyl acetate copolymer, and methyl vinyl ether. / Acidic vinyl ether polymers such as maleic anhydride alkyl half ester copolymers, acidic polyvinyl acetate polymers such as vinyl acetate/crotonic acid copolymers, (meth)acrylic acid/alkyl (meth)acrylate copolymers coalescence, acidic acrylic polymer compounds such as (meth)acrylic acid/alkyl (meth)acrylate/alkylacrylamide copolymers, N-methacryloylethyl-N,N-dimethylammonium/α-N-methylcarboxybetaine/alkyl ( Examples include amphoteric acrylic polymer compounds such as meth)acrylate copolymers and hydroxypropyl (meth)acrylate/butylaminoethyl methacrylate/octylamide acrylic acid copolymers. Also, naturally occurring polymer compounds such as cellulose or derivatives thereof, keratin and collagen or derivatives thereof can be suitably used.

By subjecting a substrate to silane coupling treatment or fiber treatment using the organopolysiloxane composition of the present invention, the adhesion of the treated organic-inorganic composite material can be improved. A method for treating a substrate using the organopolysiloxane composition of the present invention is described below.
The method for treating a substrate with the organopolysiloxane composition of the present invention is not particularly limited. A method of entraining and bringing the base material into contact with the entrained gas, a method of directly mixing the base material and the organopolysiloxane composition with a mixer or a mill, and the like. Among these, the method of applying the organopolysiloxane composition is preferable from the viewpoint of simplicity.
Examples of the method of applying the organopolysiloxane composition include brush coating, spray coating, wire bar method, blade method, roll coating method and dipping method.

The conditions for applying, contacting, or mixing the organopolysiloxane composition of the present invention to a substrate are conditions in which the silanol groups of the silicone resin (1) react with the hydroxyl groups on the substrate surface. Not restricted.
The treatment temperature is preferably 0 to 100°C, more preferably 10 to 50°C, and even more preferably 20 to 30°C, from the viewpoint of productivity.
From the viewpoint of productivity, the treatment time is preferably 1 minute to 10 hours, more preferably 1 minute to 5 hours, and even more preferably 1 minute to 2 hours, but is appropriately set in relation to the treatment temperature. do it.

The substrates to be treated can be either inorganic or organic materials.
Examples of inorganic materials include silicon compounds such as glass plate, glass fiber, diatomaceous earth, calcium silicate, silica, silicon, talc, and mica; metal oxides such as zinc oxide, aluminum oxide, tin oxide, titanium oxide, iron oxide, and magnesium oxide. metal chlorides such as zinc chloride, aluminum chloride, tin chloride, titanium chloride, iron chloride and magnesium chloride; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; carbonates such as calcium carbonate, zinc carbonate and magnesium carbonate etc. Among these, silicon compounds and metal oxides are particularly preferred from the viewpoint of reactivity with the silanol groups of the organopolysiloxane composition.
Examples of organic materials include natural polymers such as rubber, paper, and cellulose; synthetic polymers such as acrylic resins, urethane resins, epoxy resins, and phenol resins; oils, surfactants, liquid crystals, and the like. Among these, natural polymers and synthetic polymers are particularly preferred from the viewpoint of reactivity with the amino groups of the organopolysiloxane composition.

After treating the substrate with the organopolysiloxane composition of the present invention, excess organopolysiloxane composition can be removed by conventional methods such as washing and drying. The post-treatments by washing and drying may be performed singly or in combination.

Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples, Examples, Comparative Examples and Application Examples, but the present invention is not limited to the following Examples.
The weight average particle size is a volume-based median size (D90) measured by a dry laser diffraction method. The volume-based median diameter is determined by a dry method using a laser diffraction particle size distribution measuring device Mastersizer 3000 (manufactured by Malvern) according to the Fraunhofer diffraction theory. Under the conditions, the diameter corresponding to the 50% cumulative value of the volume-based cumulative particle size distribution curve was measured.
In addition, the interfacial shear strength τ [MPa] of the glass fiber epoxy resin composite material was measured by the micro droplet method using a composite interface property evaluation device HM410 (manufactured by Toei Sangyo Co., Ltd.). ], the length of the glass fiber embedded in the cured epoxy resin is L [μm], the load when the cured epoxy resin is pulled out in the axial direction of the glass fiber is F [mN], and τ=F/πDL Calculated by the formula.

[1] Synthesis of powdery silicone resin by spray drying [Synthesis Example 1] Synthesis of powdery 3-aminopropylsilanetriol homopolymer A 30% by weight aqueous solution of 3-aminopropylsilanetriol homopolymer was dried by spray drying. (solution supply flow rate 11 kg/h, drying chamber inlet temperature 140° C., drying chamber outlet temperature 85° C., solution supply pressure 100 kPa) to remove water from the aqueous solution to obtain a powdery 3-aminopropylsilanetriol homopolymer. rice field.
Potentiometric titration of the resulting powdery 3-aminopropylsilanetriol homopolymer confirmed that the amine value was 480.7 KOHmg/g. Moreover, it was confirmed that the average particle size was 40.6 μm and the loose bulk density was 0.263 g/mL by measuring with a dry laser diffraction method.

[2] Preparation of organopolysiloxane composition [Example 1]
To 100 parts by mass of toluene, which is an aprotic solvent, 1 part by mass of the powdery 3-aminopropylsilanetriol homopolymer prepared in Synthesis Example 1 and 10 parts by mass of butyric acid, which is a carboxylic acid compound, are added at room temperature, Stir at room temperature for 24 hours. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 2]
Stirring was carried out in the same manner as in Example 1, except that the aprotic solvent was changed to 100 parts by mass of isododecane. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 3]
Stirring was carried out in the same manner as in Example 1, except that the aprotic solvent was changed to 100 parts by mass of isohexadecane. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 4]
Stirring was carried out in the same manner as in Example 1, except that the aprotic solvent was changed to 100 parts by mass of squalane. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 5]
Stirring was carried out in the same manner as in Example 1, except that the aprotic solvent was changed to 100 parts by mass of tetradecene. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 6]
Stirring was carried out in the same manner as in Example 1, except that the aprotic solvent was changed to 100 parts by mass of squalene. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 7]
Stirring was carried out in the same manner as in Example 1, except that the aprotic solvent was changed to 100 parts by mass of acetone. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous brown transparent liquid organopolysiloxane composition.

[Example 8]
Stirring was carried out in the same manner as in Example 1, except that the aprotic solvent was changed to 100 parts by mass of tetrahydrofuran. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 9]
Stirring was carried out in the same manner as in Example 1, except that the carboxylic acid compound was changed to 10 parts by mass of caproic acid. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 10]
Stirring was carried out in the same manner as in Example 1, except that the carboxylic acid compound was changed to 10 parts by mass of caprylic acid. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 11]
Stirring was carried out in the same manner as in Example 1, except that the carboxylic acid compound was changed to 10 parts by mass of undecylic acid. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 12]
Stirring was carried out in the same manner as in Example 1, except that the carboxylic acid compound was changed to 10 parts by mass of oleic acid. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 13]
Stirring was carried out in the same manner as in Example 2, except that the carboxylic acid compound was changed to 10 parts by mass of oleic acid. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 14]
Stirring was carried out in the same manner as in Example 3, except that the carboxylic acid compound was changed to 10 parts by mass of oleic acid. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 15]
Stirring was carried out in the same manner as in Example 4, except that the carboxylic acid compound was changed to 10 parts by mass of oleic acid. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 16]
Stirring was carried out in the same manner as in Example 5, except that the carboxylic acid compound was changed to 10 parts by mass of oleic acid. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 17]
Stirring was carried out in the same manner as in Example 6, except that the carboxylic acid compound was changed to 10 parts by mass of oleic acid. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 18]
Stirring was carried out in the same manner as in Example 7, except that the carboxylic acid compound was changed to 10 parts by mass of oleic acid. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 19]
Stirring was carried out in the same manner as in Example 8, except that the carboxylic acid compound was changed to 10 parts by mass of oleic acid. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 20]
Stirring was carried out in the same manner as in Example 1, except that the carboxylic acid compound was changed to 10 parts by mass of linoleic acid. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Example 21]
Stirring was carried out in the same manner as in Example 1, except that the carboxylic acid compound was changed to 10 parts by mass of linolenic acid. During the stirring, the 3-aminopropylsilanetriol homopolymer was dissolved to obtain a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[Comparative Example 1]
The mixture was stirred in the same manner as in Example 1 except that no carboxylic acid compound was used, but the 3-aminopropylsilanetriol homopolymer did not dissolve.

[Comparative Example 2]
Except that 1 part by mass of powdery 3-aminopropylsilanetriol homopolymer prepared in Synthesis Example 1 was changed to 1 part by mass of lumpy 3-aminopropylsilanetriol homopolymer prepared using a vacuum dryer and a pulverizer. was stirred in the same manner as in Example 1, but the 3-aminopropylsilanetriol homopolymer did not dissolve.

[Application example 1]
[1] Fiber Treatment with Organopolysiloxane Composition Glass fibers (about 300 mm in length and about 23 μm in diameter) were immersed in the solution of the organopolysiloxane composition obtained in Example 1 at 25° C. for 30 minutes for fiber treatment. After that, the glass fibers were pulled up from the solution and dried at 70° C. for 2 hours for post-treatment.
[2] Molding of glass fiber epoxy resin composite material An epoxy resin (manufactured by Mitsubishi Chemical Corporation: JER828) and a curing agent (manufactured by Tokyo Chemical Industry Co., Ltd.: tri After attaching droplets of an epoxy resin composition composed of ethylenetetramine) having a diameter of about 100 μm so that the droplets do not contact each other, the first step is 80 ° C. for 1.5 hours, and the second step is 100 ° C. C. for 2 hours to form a glass fiber epoxy resin composite.

[Application example 2]
Fiber treatment and composite material molding were carried out in the same manner as in Application Example 1, except that the solution of Example 2 was used instead of the organopolysiloxane composition.

[Application example 3]
Fiber treatment and composite molding were carried out in the same manner as in Application Example 1, except that the solution of Example 12 was used instead of the organopolysiloxane composition.

[Comparative application example 1]
Using glass fibers (about 300 mm in length and about 23 μm in diameter) that were not treated with the organopolysiloxane composition, a glass fiber-epoxy resin composite material was molded in the same manner as in Application Example 1 [2].

[Performance evaluation]
Using a composite interface property evaluation device HM410 (manufactured by Toei Sangyo Co., Ltd.), the glass fiber epoxy resin composite materials molded in Application Examples 1 to 3 and Comparative Application Example 1 were measured by the microdroplet method to determine the interfacial shear strength τ. [MPa] was measured. The larger the numerical value, the better the adhesion of the glass fiber epoxy resin composite material. Table 1 shows the results.

As shown in Table 1, in the glass fiber epoxy resin composite materials obtained in Application Examples 1 to 3, a plurality of silanol groups contained in the powdery silicone resin reacted with a plurality of hydroxyl groups on the glass fiber surface, Furthermore, since the amino group reacts with the epoxy resin, it can be seen that the adhesion to the glass fiber epoxy resin composite material is improved.

Claims (5)

A transparent organopolysiloxane composition comprising only a powdery silicone resin represented by the following general formula (1), a carboxylic acid compound or a natural oil containing a carboxylic acid compound, and an aprotic solvent.

(wherein each R ¹ independently represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom; each R ² independently represents a hydrogen represents an atom, a methyl group or an ethyl group, and a represents an integer of 2 to 70.) 2. The organopolysiloxane composition according to claim 1, wherein the silicone resin has an average particle size of 1 to 200 μm in volume-based median size as measured by a dry laser diffraction method. 3. The organopolysiloxane composition according to claim 1, wherein said silicone resin is spray-dried particles. Any one of claims 1 to 3, wherein the carboxylic acid compound is one or more selected from saturated monocarboxylic acid compounds having 1 to 11 carbon atoms and unsaturated monocarboxylic oxides having 3 to 22 carbon atoms. The organopolysiloxane composition according to claim. Claims 1 to 4, wherein said aprotic solvent is one or more selected from saturated aliphatic hydrocarbon solvents, unsaturated aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents and ketone solvents. The organopolysiloxane composition according to any one of Claims 1 to 3.