Organopolysiloxane composition

Abstract

To provide a uniform and transparent organopolysiloxane composition having an amino group and a silanol group which is dissolved in a non-protic solvent and can improve compatibility with a hydrophobic organic material and a hydrophobic inorganic material while suppressing the generation of an alcohol when used as a silane coupling agent or a fiber treatment agent.SOLUTION: There is provided a transparent organopolysiloxane composition which is only composed 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, R1 represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms which may independently contain a hetero atom, R2 each independently represents a hydrogen atom, a methyl group or an ethyl group and a represents an integer of 2 to 70).SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to organopolysiloxane compositions. [Background technology]

[0002] Organosilicon compounds having a hydrolyzable silyl group and an organic group allow for the bonding of organic and inorganic materials, which are normally difficult to bond, because the silanol group generated by the 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 reacts with the organic material. This makes it possible to impart properties such as heat resistance, water resistance, weather resistance, improved mechanical strength, adhesion, dispersibility, hydrophobicity, and corrosion resistance to organic-inorganic composite materials. By utilizing these properties, the organosilicon compounds described above are used in a wide range of fields and applications, including silane coupling agents, resin additives, surface treatment agents, fiber treatment agents, adhesives, paint additives, and polymer modifiers.

[0003] Among the organosilicon compounds mentioned above, aminosilane compounds containing an amino group can improve the adhesion of organic-inorganic composite materials because the amino group exhibits high reactivity with various organic and inorganic materials. Examples of such aminosilane compounds include 3-aminopropyltrimethoxysilane (Patent Document 1). Furthermore, an example of an organopolysiloxane composition obtained by hydrolyzing this aminosilane compound is 3-aminopropylsilanetriol homopolymer (Patent Document 2). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 10-17578 [Patent Document 2] U.S. Patent Application Publication No. 2020 / 0068897 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, the aminosilane compound having an alkoxysilyl group described in Patent Document 1 generates a considerable amount of alcohol through hydrolysis of the alkoxysilyl group. In recent years, the reduction of volatile organic compounds (VOCs) has become a major theme in environmental issues closely related to global warming and health problems, and the above-mentioned aminosilane compound generates a large amount of alcohol, raising concerns about its environmental impact.

[0006] 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, and since the alcohol generated after hydrolysis can be removed, it is useful as one method for reducing the amount of alcohol generated from the above aminosilane compound. Furthermore, this organopolysiloxane composition has the advantage of having excellent reactivity with hydroxyl groups on the substrate surface because it is a silanol condensate having multiple silanol groups. That is, in the hydrolysis reaction of the above aminosilane compound, silanol groups condense together to produce silanol condensates with linear, branched, cyclic, and three-dimensional network structures. Since the condensation of silanol groups reaches equilibrium through the interaction of silanol groups and amino groups, multiple silanol groups exist in an uncondensed state in the silanol condensate. This allows multiple silanol groups to react with multiple hydroxyl groups on the substrate surface, thereby improving adhesion to organic-inorganic composite materials.

[0007] However, although the organopolysiloxane composition having amino groups and silanol groups described in Patent Document 2 can remove the generated alcohol, the solvents in which it is compatible are limited to protic solvents such as water or lower alcohols. Therefore, when using a non-protic solvent, it is not possible to prepare a uniform and transparent solution. That is, the silanol condensates contained in the above organopolysiloxane composition exhibit hydrophilicity due to the multiple silanol groups, and thus precipitate or separate as solids (crystalline substances) or liquids (oil-like substances) with low compatibility with non-protic solvents. In the case of heterogeneous and opaque solutions containing these solids or liquids, sufficient contact with various organic and inorganic materials becomes impossible, and the reactivity with hydroxyl groups on the substrate surface decreases. Furthermore, in the case of solutions containing protic solvents such as water or lower alcohols, the compatibility with hydrophobic organic and inorganic materials is low, making them unsuitable for applications in which these materials are blended.

[0008] Therefore, there is a need for the development of a uniform, transparent organopolysiloxane composition having amino and silanol groups that is soluble in aprotic solvents and, when used as a silane coupling agent or fiber treatment agent, can improve compatibility with hydrophobic organic and hydrophobic inorganic materials while suppressing alcohol generation.

[0009] The present invention has been made in view of the above circumstances, and aims to provide a uniform, transparent organopolysiloxane composition having amino groups and silanol groups that, when dissolved in a non-protic solvent and used as a silane coupling agent or fiber treatment agent, can suppress the generation of alcohols and improve compatibility with hydrophobic organic materials and hydrophobic inorganic materials. [Means for solving the problem]

[0010] The inventors, through diligent research to achieve the above objectives, discovered that a powdered silicone resin having amino groups and silanol groups dissolves in aprotic solvents through interaction with carboxylic acid compounds, forming a uniform and transparent solution (composition) without solid precipitation or liquid separation. Furthermore, they found that when this composition is used as a silane coupling agent or fiber treatment agent, no alcohol is generated, and its compatibility with hydrophobic organic and hydrophobic inorganic materials is improved, thus completing the invention.

[0011] In other words, the present invention is 1. A transparent organopolysiloxane composition consisting only of a powdered 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. [ka] (In the formula, R 1 Each of these independently represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, which may each contain a heteroatom, and R 2 (Each of these independently represents a hydrogen atom, a methyl group, or an ethyl group, and 'a' represents an integer between 2 and 70.) 2. An organopolysiloxane composition having an average particle size of 1 to 200 μm in volume-based median diameter obtained by dry laser diffraction of the silicone resin. 3. The silicone resin is an organopolysiloxane composition 1 or 2 which is a spray-dried particle. 4. One of the organopolysiloxane compositions 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 acid derivatives having 3 to 22 carbon atoms. 5. An organopolysiloxane composition of any 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. To provide. [Effects of the Invention]

[0012] The organopolysiloxane composition of the present invention can be prepared as a uniform and transparent solution in which no solid precipitation or liquid separation occurs. In addition, since the organopolysiloxane composition of the present invention shows high compatibility with hydrophobic organic materials and hydrophobic inorganic materials, when used as a silane coupling agent or a fiber treating agent, the adhesion with organic-inorganic composite materials can be enhanced.

Embodiments for Carrying Out the Invention

[0013] Hereinafter, the present invention will be specifically described. The organopolysiloxane composition of the present invention consists only of a powdery silicone resin (hereinafter referred to as "silicone resin (1)") represented by the following general formula (1), a carboxylic acid compound or a natural oil containing a carboxylic acid compound, and an aprotic solvent.

[0014]

Chemical formula

[0015] In the general formula (1), R 1 each independently represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, which may contain a hetero atom. The above R 1The divalent hydrocarbon group may be linear, branched, or cyclic, and specific examples include methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadecamethylene, Linear alkylene groups such as eicosamethylene groups; branched alkylene groups such as isopropylene, isobutylene, sec-butylene, tert-butylene, isopentylene, isohexylene, isoheptylene, isooctylene, isononylene, isodecylene, isounddecylene, isododecylene, isotridecylene, isotetradecylene, isopentadecylene, isohexadecylen, isoheptadecylen, isooctadecylen, isononadecylene, isoicosilene groups, etc. Cyclic alkylene groups such as cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, cyclodecylene, cycloundecylene, cyclododecylene, cyclotridecylene, cyclotetradecylene, cyclopentadecylene, cyclohexadecylene, cycloheptadecylene, cyclooctadecylene, cyclononadecilen, cycloicosilene, etc.; etenylene, propenylene Examples include alkenylene groups such as butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonylene, decenylene, undecenylene, dodecenylene, tridecenylene, tetradecenylene, pentadecenylene, hexadecenylene, heptadecenylene, octadecenylene, nonadecenylene, and icocenylene groups; arylene groups such as phenylene and naphthylene groups; and aralkylene groups such as methylenephenylene and methylenephenylmethylene groups. 1 Examples of divalent hydrocarbon groups containing heteroatoms include alkyleneaminoalkylene groups, alkyleneoxyalkylene groups, alkylentioalkylene groups, etc., and these alkylene groups can be independently the same as those exemplified above for linear, branched, and cyclic alkylene groups.

[0016] Furthermore, some or all of the hydrogen atoms of these divalent hydrocarbon groups may be substituted with other substituents. Specific examples of these substituents include alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, and (iso)propoxy groups; 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; cyano, amino, ester, ether, carbonyl, acyl, and sulfide groups. One or more of these substituents can be used in combination. The substitution positions of these substituents are not particularly limited, nor is the number of substituents limited.

[0017] Among these, R 1 Preferably, the alkylene group is an unsubstituted linear, branched, or cyclic alkylene group having 1 to 8 carbon atoms; an alkenylene group; an arylene group; an aralkylene group; an alkylene-aminoalkylene group; an alkylene-oxyalkylene group; or an alkylenthioalkylene group. Particularly preferred from the viewpoint of the availability of precursor raw materials, an unsubstituted linear or branched alkylene group having 1 to 6 carbon atoms; an alkylene-aminoalkylene group is more preferred, and methylene group, dimethylene group, trimethylene group, isopropylene group, methylene-aminomethylene group, methylene-amino-methylene group, methylene-amino-trimethylene group, dimethylene-aminomethylene group, dimethylene-amino-methylene group, dimethylene-amino-trimethylene group, trimethylene-aminomethylene group, trimethylene-amino-methylene group, trimethylene-amino-methylene group, trimethylene-amino-trimethylene group.

[0018] In general formula (1), R 2 Each of these independently represents a hydrogen atom, a methyl group, or an ethyl group, but a hydrogen atom or a methyl group is preferred, and a hydrogen atom is particularly preferred from the viewpoint of the availability of precursor raw materials.

[0019] In general formula (1), a is an integer between 2 and 70, but is preferably 2 to 60, more preferably 2 to 50, and even more preferably 2 to 40, particularly from the viewpoint of compatibility with aprotic solvents. In general formula (1), a is an integer between 2 and 70, but is preferably 2 to 60, more preferably 2 to 50, even more preferably 2 to 40, still more preferably 5 to 40, still still more preferably 15 to 40, and most preferably 20 to 40, especially from the viewpoint of compatibility with aprotic solvents. Furthermore, the range of 'a' in general formula (1) can be determined by measuring the amine value of the silicone resin (1). Here, the amine value is a value that indicates the amount of organic amine in the sample, and is calculated by measuring the mg of potassium hydroxide (KOH) equivalent to the amount of acid required to neutralize the amino group of the organic amine contained in 1 g of the sample using potentiometric titration.

[0020] Specific examples of silicone resin (1) include: silicone resins having primary amino groups such as 1-aminomethylsilanetriol homopolymer, 2-aminoethylsilanetriol homopolymer, 2-aminoisopropylsilanetriol homopolymer, and 3-aminopropylsilanetriol homopolymer; silicone resins having secondary amino groups such as N-methyl-1-aminomethylsilanetriol homopolymer, N-methyl-2-aminoethylsilanetriol homopolymer, N-methyl-2-aminoisopropylsilanetriol homopolymer, and N-methyl-3-aminopropylsilanetriol homopolymer; and silicone resins having tertiary amino groups such as N,N-dimethyl-1-aminomethylsilanetriol homopolymer, N,N-dimethyl-2-aminoethylsilanetriol homopolymer, N,N-dimethyl-2-aminoisopropylsilanetriol homopolymer, and N,N-dimethyl-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-amino Examples include silicone resins having diamino groups, such as methylsilanetriol homopolymer, N-(2-aminoisopropyl)-2-aminoethylsilanetriol homopolymer, N-(2-aminoisopropyl)-2-aminoisopropylsilanetriol homopolymer, N-(2-aminoisopropyl)-3-aminopropylsilanetriol homopolymer, N-(3-aminopropyl)-1-aminomethylsilanetriol homopolymer, N-(3-aminopropyl)-2-aminoethylsilanetriol homopolymer, N-(3-aminopropyl)-2-aminoisopropylsilanetriol homopolymer, and N-(3-aminopropyl)-3-aminopropylsilanetriol homopolymer.

[0021] Among these, particularly when used as a silane coupling agent or fiber treatment agent, from the viewpoint of reacting with multiple hydroxyl groups on the substrate surface to enhance adhesion with organic materials, 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 N-(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-aminopropylsilanetriol homopolymer, N-(3-aminopropyl)-1-aminomethylsilanetriol homopolymer, N-(3-aminopropyl)-2-aminoethylsilanetriol homopolymer, N-(3-aminopropyl)-2-aminoisopropylsilanetriol homopolymer, and N-(3-aminopropyl)-3-aminopropylsilanetriol homopolymer are preferred.

[0022] The silicone resin (1) used in this invention is a powder-like solid. The particle shape of the silicone resin (1) may be spherical, polyhedral, spindle-shaped, needle-shaped, plate-shaped, or any other shape, but a spherical shape is preferred from the viewpoint of ease of handling. In this invention, "spherical" does not mean that the particle shape is only a perfect sphere, but also includes ellipsoids. The particle shape is confirmed by observing the particles with an optical microscope or electron microscope.

[0023] The average particle size of the silicone resin (1) is preferably 1 to 200 μm, more preferably 10 to 150 μm, and even more preferably 30 to 100 μm, from the viewpoint of promoting interaction with carboxylic acid compounds. The average particle size refers to the volume-based median diameter (D50) measured by dry laser diffraction. The volume-based median diameter is calculated using a laser diffraction particle size distribution analyzer Mastersizer 3000 (Malvern) by measuring the diameter corresponding to the 50% cumulative value of the volume-based cumulative particle size distribution curve using the dry method based on Fraunhofer diffraction theory, under conditions of a dispersion pressure of 2 bar and a scattering intensity of 2-10%.

[0024] The loosened 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, and even more preferably 0.3 to 0.9 g / mL, from the viewpoint of promoting interaction with carboxylic acid compounds. The bulk density is calculated by filling a 100 ml container, whose mass has been measured in advance, with powdered silicone resin until it overflows (without vibrating the container or compressing the sample), leveling off the powder that has risen above the top surface of the container using a leveling plate, measuring the mass of the contents, and calculating the mass per 1 ml.

[0025] The above-mentioned silicone resin (1) is typically produced by hydrolyzing an aminosilane compound having an alkoxysilyl group represented by the following general formula (2).

[0026] [ka]

[0027] In general formula (2), R 1 and R 2 are the same as the substituents exemplified above. R 3 each 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 above-mentioned monovalent hydrocarbon group of R 3 may be linear, branched or cyclic. Specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl groups; branched alkyl groups such as sec-propyl, sec-butyl, tert-butyl, sec-pentyl, tert-pentyl, sec-hexyl, tert-hexyl, sec-heptyl, tert-heptyl, sec-octyl, tert-octyl, sec-nonyl, tert-nonyl, sec-decyl, tert-decyl groups; cyclic alkyl groups such as cyclopentyl, cyclohexyl groups; alkenyl groups such as vinyl, allyl, butenyl, methallyl groups; aryl groups such as phenyl, tolyl, xylyl groups; aralkyl groups such as benzyl, phenethyl groups, etc.

[0028] Note that some or all of the hydrogen atoms of these monovalent hydrocarbon groups may be substituted with other substituents. Specific examples of this substituent include the same substituents as those in the case where some or all of the hydrogen atoms of the divalent hydrocarbon group of R 1 may be substituted with other substituents, and one or more of these can be used in combination. The substitution positions of these substituents are not particularly limited, and the number of substituents is also not limited.

[0029] Among these, R 3 is preferably an unsubstituted linear alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or an ethyl group from the viewpoint of easy availability.

[0030] Specific examples of aminosilane compounds having an alkoxysilyl group include trialkoxysilane compounds having a primary amino group such as 1-aminomethyltrimethoxysilane, 1-aminomethyltriethoxysilane, 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 2-aminoisopropyltrimethoxysilane, 2-aminoisopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane; N-methyl-1-aminomethyltrimethoxysilane, N-methyl-1-aminomethyltriethoxysilane Trialkoxysilane compounds having a secondary amino group, such as xysilane, N-methyl-2-aminoethyltrimethoxysilane, N-methyl-2-aminoethyltriethoxysilane, N-methyl-2-aminoisopropyltrimethoxysilane, N-methyl-2-aminoisopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-methyl-3-aminopropyltriethoxysilane; N,N-dimethyl-1-aminomethyltrimethoxysilane, N,N-dimethyl-1-aminomethyltriethoxysilane, N,N-dimethyl-2-aminomethyltriethoxysilane Trialkoxysilane compounds having a tertiary amino group, such as noethyltrimethoxysilane, N,N-dimethyl-2-aminoethyltriethoxysilane, N,N-dimethyl-2-aminoisopropyltrimethoxysilane, N,N-dimethyl-2-aminoisopropyltriethoxysilane, N,N-dimethyl-3-aminopropyltrimethoxysilane, and N,N-dimethyl-3-aminopropyltriethoxysilane; N-(1-aminomethyl)-1-aminomethyltrimethoxysilane, N-(1-aminomethyl)-1-aminomethyltriethoxysilane, N-(1- Minomethyl)-2-aminoethyltrimethoxysilane, N-(1-aminomethyl)-2-aminoethyltriethoxysilane, N-(1-aminomethyl)-2-aminoisopropyltrimethoxysilane, 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-aminoisopropyl)-1-aminomethyltrimethoxysilane, N-(2-aminoisopropyl)-1-aminomethyltriethoxysilane, N-(2-aminoisopropyl)-2-aminoethyltrimethoxysilane, N-(2-aminoisopropyl)-2-aminoisopropyltrimethoxysilane, N-(2-aminoisopropyl)-2-aminoisopropyltrimethoxysilane, N-(2-aminoisopropyl)-2 Examples include trialkoxysilane compounds having a diamino group, such as -aminoisopropyltriethoxysilane, N-(2-aminoisopropyl)-3-aminopropyltrimethoxysilane, N-(2-aminoisopropyl)-3-aminopropyltriethoxysilane, 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, and N-(3-aminopropyl)-3-aminopropyltriethoxysilane.

[0031] Among these, when used as a silane coupling agent or fiber treatment agent, from the viewpoint of reacting with multiple hydroxyl groups on the substrate surface to improve adhesion with organic materials, 1-aminomethyltrimethoxysilane, 1-aminomethyltriethoxysilane, 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 2-aminoisopropyltrimethoxysilane, 2-aminoisopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(1-aminomethyl)-1-aminomethyltri Methoxysilane, N-(1-aminomethyl)-1-aminomethyltriethoxysilane, N-(1-aminomethyl)-2-aminoethyltrimethoxysilane, N-(1-aminomethyl)-2-aminoethyltriethoxysilane, N-(1-aminomethyl)-2-aminoisopropyltrimethoxysilane, 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, 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-aminoisopropyl)-3-aminopropyltriethoxysilane, 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, and N-(3-aminopropyl)-3-aminopropyltriethoxysilane are preferred.

[0032] In the hydrolysis of aminosilane compounds containing alkoxysilyl groups, a corresponding amount of alcohol is generated. Furthermore, depending on the amount of water added during hydrolysis, the resulting product may also contain water. As described above, the organopolysiloxane composition of the present invention is a homogeneous and transparent solution in which the silicone resin (1) is dissolved in an aprotic solvent. Therefore, from the viewpoint of compatibility with aprotic solvents, it is preferable that the silicone resin (1) is obtained by removing alcohol and water from the hydrolysis solution.

[0033] There are no particular limitations on the method for removing alcohol and water from the hydrolysis solution; methods such as centrifugation, heat drying, chromatography, recrystallization, distillation, extraction, decantation, liquid-liquid separation, and filtration can be employed. Among these, heat drying is preferred from the viewpoint of productivity.

[0034] Furthermore, specific examples of methods for manufacturing powdered silicone resin include heating and pulverizing a standing hydrolyzed solution, heating and stirring the hydrolyzed solution to induce fluidity, spray drying (spray drying method) in which the hydrolyzed solution is sprayed into a high-temperature airflow such as a spray dryer and dispersed, and methods utilizing a fluid heat transfer medium.

[0035] The spray-drying method is a granulation method that obtains powder-like solids (particles) by breaking down (spraying) a solution containing a solid and a solvent into small droplets, and then bringing them into contact with a high-temperature airflow in a drying chamber to instantaneously evaporate the solvent. The driving force for solvent evaporation is generally obtained by lowering the partial pressure of the solvent compared to the vapor pressure of the solvent at the temperature at which the droplet dries. Preferred embodiments include a method of mixing the droplet with a high-temperature drying gas, and a method of maintaining an incomplete vacuum in the solvent removal device.

[0036] The above solution can be sprayed into a drying chamber at a wide range of flow rates and temperatures. Furthermore, when pressurized during spraying, it can be sprayed at a wide range of pressures. Generally, the evaporation rate of the solvent increases with increasing the specific surface area of ​​the droplet. Therefore, the diameter of the sprayed droplets is preferably less than 500 μm, more preferably less than 400 μm, and even more preferably between 5 and 200 μm. Furthermore, the flow rate, temperature, and pressure that enable such spraying are also preferred. The solution supply flow rate is preferably 1 to 500 kg / h, more preferably 5 to 100 kg / h, and even more preferably 10 to 50 kg / h. The temperature at the inlet of the drying chamber is preferably 100 to 250°C, more preferably 110 to 220°C, and even more preferably 120 to 200°C. The drying chamber outlet temperature is preferably 0 to 100°C, more preferably 0 to 95°C, and even more preferably 0 to 90°C. The solution supply pressure is preferably 100 to 50,000 kPa, more preferably 200 to 10,000 kPa, and even more preferably 300 to 5,000 kPa.

[0037] When a method is used to manufacture powdered silicone resin by heating and pulverizing a hydrolyzed solution that has been left to stand using a vacuum dryer or the like, residual solvent and water remain, which reduces adhesion to organic-inorganic composite materials when used as a silane coupling agent or fiber treatment agent. In contrast, the spray-drying method results in an extremely large specific surface area of ​​the sprayed particles, allowing for efficient evaporation and removal of the solvent and water. As a result, the solvent and water content is lower than that produced by other methods of powdering, giving powdered silicone resin produced by the spray-drying method the advantage of superior adhesion to organic-inorganic composite materials. Therefore, from the viewpoint of controlling the content of solvent and water, as well as controlling physical properties such as average particle size and bulk density, spray-dried particles obtained by the spray-drying method are preferred for the silicone resin used in this invention.

[0038] The content of silicone resin (1) in the organopolysiloxane composition is not particularly limited as long as it reacts with multiple hydroxyl groups on the substrate surface to improve 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 even more preferably 0.1 to 10% by mass relative to the organopolysiloxane composition.

[0039] The carboxylic acid compound used in the organopolysiloxane composition of the present invention is not particularly limited, but one or more selected from saturated monocarboxylic acid compounds having 1 to 11 carbon atoms and unsaturated monocarboxylic acid derivatives having 3 to 22 carbon atoms are preferred. Specific examples include saturated monocarboxylic acid compounds with 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, heptenic acid, octenic acid, nonenic acid, 10-hydroxy-2-decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, myristoleic acid, pentadecenoic acid, hexadecenoic acid, hexadecadienoic acid, hexadecatetrienoic acid, hexadecatetetraenoic acid, palmitoleic acid, sapienic acid, heptadecenoic acid, heptadecadienoic acid, heptadecatetrienoic acid, heptadecatetetraenoic acid Examples include acids, unsaturated monocarboxylic acid compounds with 3 to 22 carbon atoms such as octadecenoic acid, octadecadienoic acid, octadecatrioenoic acid, octadecatetetraenoic acid, oleic acid, ricinoleic acid, vaccenic acid, linoleic acid, linolenic acid, nonadecenoic acid, nonadecadienoic acid, nonadecatrioenoic acid, nonadecatetetraenoic 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, etc. These carboxylic acid compounds may be used individually or in combination of two or more.

[0040] Furthermore, the organopolysiloxane composition of the present invention may also use natural oils containing these carboxylic acid compounds. Specific examples of natural oils include almond oil, Astrocaryum murumuru seed butter, avocado oil, linseed oil, flaxseed oil, argania spinosa kernel oil, apricot kernel oil, olive fruit oil, cocoa butter, rosehip fruit oil, canola oil, apricot kernel oil, kukui nut oil, blackcurrant seed oil, corn oil, sesame oil, wheat germ oil, rice bran oil, rice germ oil, pomegranate seed oil, safflower oil, shea butter, Sclerocarya birrea seed oil, soybean oil, tea seed oil, evening primrose oil, and camellia seed oil. Examples include seed oil, theobroma grandiflorum seed butter, 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, and moringa seed oil.

[0041] Among these, particularly in terms of availability, 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, heptenic acid, octenoic acid, nonenic acid, 10-hydroxy-2-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, octadecatriene Acids, octadecatetraenoic acid, oleic acid, ricinoleic acid, vaccenic acid, linoleic acid, linolenic acid, nonadecenoic acid, nonadecadienoic acid, nonadecatrienoic acid, nonadecatetraenoic acid, eicosenoic acid, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, eicosapentaenoic acid, gadoleic acid, arachidonic acid, docosenoic acid, docosadienic acid, docosatrienoic acid, docosatetraenoic acid, docosahexaenoic acid, and erucic acid are preferred, and 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.

[0042] The above carboxylic acid compound 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) that has formed a salt, amide bond, or ester bond has improved hydrophobicity due to the hydrocarbon group of the carboxylic acid compound, and therefore its compatibility with aprotic solvents is improved. As described above, the organopolysiloxane composition of the present invention is a homogeneous 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, it is preferable to use a monocarboxylic acid compound that does not form a crosslinking structure as the carboxylic acid compound. Furthermore, 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 the aprotic solvent.

[0043] 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. However, from the viewpoint of productivity, it is 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 relative to the organopolysiloxane composition.

[0044] Specific examples of aprotic solvents used in the organopolysiloxane composition of the present invention include saturated aliphatic hydrocarbon solvents such as 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, and squalane; pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, Examples of solvents include unsaturated aliphatic hydrocarbon solvents such as antadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, and squalene; aromatic hydrocarbon solvents 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 such as acetonitrile and N,N-dimethylformamide; and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used individually or in combination of two or more.

[0045] Among these, one or more selected from saturated aliphatic hydrocarbon solvents, unsaturated aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and ketone solvents are preferred, particularly from the viewpoint of compatibility with hydrophobic organic materials and hydrophobic inorganic materials, and one or more selected from saturated aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents are more preferred.

[0046] 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. However, from the viewpoint of productivity, it is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, and even more preferably 20 to 80% by mass relative to the organopolysiloxane composition.

[0047] The organopolysiloxane composition of the present invention consists only of a silicone resin (1), a carboxylic acid compound or a natural oil containing the same, and an aprotic solvent, forming a homogeneous and transparent solution without solid precipitation or liquid separation.

[0048] The method for producing the organopolysiloxane composition is not particularly limited as long as the silicone resin (1) dissolves in an aprotic solvent. Any of the following methods may be used: adding the silicone resin (1) to a solution containing a carboxylic acid compound and an aprotic solvent; adding the solution containing the silicone resin (1) and a carboxylic acid compound to an aprotic solvent; adding the solution containing the silicone resin (1) and an aprotic solvent to a carboxylic acid compound; adding the carboxylic acid compound to a solution containing the silicone resin (1) and an aprotic solvent; adding the solution containing the carboxylic acid compound and an aprotic solvent to the silicone resin (1); adding the aprotic solvent to a solution containing the silicone resin (1) and a carboxylic acid compound; or simultaneously mixing the silicone resin (1), the carboxylic acid compound, and the aprotic solvent. However, from the viewpoint of productivity, the method of simultaneously mixing the silicone resin (1), the carboxylic acid compound, and the aprotic solvent is preferred.

[0049] From the viewpoint of productivity, the mixing temperature is preferably 20 to 100°C, more preferably 20 to 60°C, and even more preferably 20 to 40°C. The mixing time is preferably 1 to 72 hours, more preferably 1 to 48 hours, and even more preferably 1 to 24 hours, from the viewpoint of productivity, but can be set appropriately in relation to the above preparation temperature.

[0050] As described above, the organopolysiloxane composition of the present invention is a homogeneous and transparent composition consisting of three components: a silicone resin (1), a carboxylic acid compound or a natural oil containing the same, and an aprotic solvent. This organopolysiloxane composition can be used for various applications by adding other additives. In this case, the composition with the other additives may be uniform and transparent, similar to the organopolysiloxane composition of the present invention, or it may become non-uniform and opaque as a result of the addition of the other additives, and solid precipitation or liquid separation may occur.

[0051] Other additives include solid, semi-solid, or liquid oils commonly used in cosmetics, water, alcohols, water-soluble polymers, film-forming agents, surfactants, oil-soluble gelling agents, organically modified clay minerals, powders, antiperspirants, UV absorbers, UV absorbers and scatterers, humectants, preservatives, antibacterial agents, fragrances, salts, antioxidants, pH adjusters, chelating agents, cooling agents, anti-inflammatory agents, skin beautifying ingredients (whitening agents, cell activators, skin roughness improvers, blood circulation promoters, skin astringents, anti-seborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, inclusion compounds, and hair solidifying agents. Specific examples of additives are given below, but the present invention is not limited thereto.

[0052] Examples of solid, semi-solid, or liquid oils include hydrocarbon oils, higher alcohols, ester oils, glyceride oils, silicone oils, and fluorinated oils.

[0053] Examples of hydrocarbon oils include ozokerite, α-olefin oligomers, light isoparaffins, isododecane, isohexadecane, light liquid isoparaffins, squalane, synthetic squalane, vegetable squalane, squalene, ceresin, paraffin, paraffin wax, polyethylene wax, polyethylene / polypropylene wax, (ethylene / propylene / styrene) copolymer, (butylene / propylene / styrene) copolymer, liquid paraffin, liquid isoparaffin, pristane, polyisobutylene, hydrogenated polyisobutene, microcrystalline wax, and petrolatum.

[0054] Examples of 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, phytosterols, POE cholesterol ether, monostearyl glycerin ether (batyl alcohol), and monooleyl glyceryl ether (cerakyl alcohol).

[0055] As for ester oils, diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, N-alkyl glycol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate, octyldodecyl gum ester, oleyl oleate, octyldodecyl oleate, decyl oleate, neopentyl glycol dioctanoate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate, butyl acetate, isocetyl stearate, Examples include butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isononyl isononanoate, isotridecyl isononanoate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesteryl 12-hydroxystearylate, 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, isopropyl lauroyl sarcosinate, and diisostearyl malate.

[0056] Examples of glyceride oils include acetoglyceryl, glyceryl triisooctanoate, glyceryl triisostearate, glyceryl triisopalmitate, glyceryl tribehenate, glyceryl monostearate, glyceryl di-2-heptylundecanoate, glyceryl trimyristate, and diglyceryl isostearate myristate. Silicone oils include low-viscosity to high-viscosity linear or branched organopolysiloxanes such as dimethylpolysiloxane, tritrimethylsiloxymethylsilane, caprylyl methicone, phenyl trimethicone, tetrakithtrimethylsiloxysilane, methylphenylpolysiloxane, methylhexylpolysiloxane, methylhydrogenpolysiloxane, and dimethylsiloxane-methylphenylsiloxane copolymers; octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetrahydrogencyclotetrasiloxane, and tetramethyltetraphenylcyclotetrasiloxane. Examples include cyclic organopolysiloxanes such as lasiloxane; amino-modified organopolysiloxanes, pyrrolidone-modified organopolysiloxanes, pyrrolidone carboxylic acid-modified organopolysiloxanes, highly polymerized gum-like dimethylpolysiloxanes, gum-like amino-modified organopolysiloxanes, gum-like dimethylsiloxane-methylphenylsiloxane copolymers, and other silicone rubbers and cyclic organopolysiloxane solutions of silicone gums and rubbers; higher alkoxy-modified silicones such as stearoxysilicones; higher fatty acid-modified silicones, alkyl-modified silicones, long-chain alkyl-modified silicones, amino acid-modified silicones, fluorine-modified silicones, and the like. Examples of fluorinated oils include perfluoropolyethers, perfluorodecalins, and perfluorooctane.

[0057] Examples of alcohols include lower alcohols such as ethanol and isopropanol; sugar alcohols such as sorbitol and maltose; sterols such as cholesterol, sitosterol, phytosterol, and lanosterol; and polyhydric alcohols such as butylene glycol, propylene glycol, dibutylene glycol, and pentylene glycol.

[0058] Water-soluble polymers include plant-derived polymers such as gum arabic, tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), starch (rice, corn, potato, wheat, etc.), algae colloid, trant gum, and locust bean gum; microbial polymers such as xanthan gum, dextran, succinoglucan, and pullulan; animal-derived polymers such as collagen, casein, albumin, and gelatin; starch-based polymers such as carboxymethyl starch and methylhydroxypropyl starch; methylcellulose, ethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, nitrocellulose, and sodium cellulose sulfate. Examples include cellulosic polymers such as sodium carboxymethylcellulose, crystalline cellulose, and cellulose powder; alginic acid polymers such as sodium alginate and propylene glycol alginate; vinyl polymers such as polyvinyl methyl ether and carboxyvinyl polymer; acrylic polymers such as polyoxyethylene polymers, polyoxyethylene polyoxypropylene copolymer polymers, sodium polyacrylate, polyethyl acrylate, polyacrylamide, and acryloyldimethyl taurate salt copolymer; other synthetic water-soluble polymers such as polyethyleneimine and cationic polymers; and inorganic water-soluble polymers such as bentonite, aluminum magnesium silicate, montmorillonite, bydelite, nontronite, saponite, hectorite, and anhydrous silicic acid.

[0059] Examples of film-forming agents include latexes such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, and alkyl polyacrylate; cellulose derivatives such as dextrin, alkylcellulose, and nitrocellulose; silicone-modified polysaccharide compounds such as tri(trimethylsiloxy)silylpropylcarbamate pullulan; acrylic-silicone graft copolymers such as (alkyl acrylate / dimethicone) copolymer; silicone resins such as trimethylsiloxysilicate; silicone-based resins such as silicone-modified polynorbornene and fluorine-modified silicone resins; fluororesins, aromatic hydrocarbon resins, polymer emulsion resins, terpene resins, polybutene, polyisoprene, alkyd resins, polyvinylpyrrolidone-modified polymers, rosin-modified resins, and polyurethanes.

[0060] Examples of surfactants include anionic surfactants such as sodium stearate and triethanolamine palmitate, alkyl ether carboxylic acids and their salts, condensate salts of amino acids and fatty acids, alkanesulfonates, alkenesulfonates, sulfonates of fatty acid esters, sulfonates of fatty acid amides, formalin condensate sulfonates, alkyl sulfate salts, secondary higher alcohol sulfate salts, alkyl and allyl ether sulfate salts, sulfate salts of fatty acid esters, sulfate salts of fatty acid alkylolamides, sulfate salts of belladonna oil, alkyl phosphates, ether phosphates, alkylallyl ether phosphates, amide phosphates, N-acyl lactates, N-acyl sarcosine salts, and N-acyl amino acid-based surfactants; cationic surfactants such as alkylamine salts, amine salts of polyamines and amino alcohol fatty acid derivatives, alkyl quaternary ammonium salts, aromatic quaternary ammonium salts, pyridium salts, and imidazolium salts;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, Examples include nonionic surfactants such as polyoxyethylene phytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, linear or branched polyoxyalkylene-modified organopolysiloxane, linear or branched polyoxyalkylene-alkyl-comodified organopolysiloxane, linear or branched polyglycerin-modified organopolysiloxane, linear or branched polyglycerin-alkyl-comodified organopolysiloxane, alkanolamides, sugar ethers, and sugar amides; and amphoteric surfactants such as betaine, phosphatidylcholine, aminocarboxylates, imidazoline derivatives, and amidoamine-type surfactants.

[0061] Examples of oil-soluble gelling agents include metal 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 fatty acid esters such as dextrin palmitate, dextrin stearate, and dextrin 2-ethylhexanoate palmitate; sucrose fatty acid esters such as sucrose palmitate and sucrose stearate; fructooligosaccharide fatty acid esters such as fructooligosaccharide stearate and fructooligosaccharide 2-ethylhexanoate; and benzylidene derivatives of sorbitol such as monobenzylidene sorbitol and dibenzylidene sorbitol. Examples of organically modified clay minerals include dimethylbenzylddecylammonium montmorillonite clay and dimethyldioctadecylammonium montmorillonite clay.

[0062] Examples of powders include those commonly used in cosmetics, and any type can be used regardless of its shape (spherical, needle-shaped, plate-shaped, etc.), particle size (fuzzy, fine particles, pigment-grade, etc.), or particle structure (porous, non-porous, etc.). Examples include inorganic powders, organic powders, surfactant metal salt powders, colored pigments, pearl pigments, metal powder pigments, tar dyes, natural pigments, etc. Examples of inorganic powders include titanium dioxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite, synthetic mica, phlogopite, rose mica, biotite, lithium mica, silicic acid, anhydrous silicic acid, aluminum silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, barium silicate, strontium silicate, tungstate metal salts, hydroxyapatite, vermiculite, hydylite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride, silica, and the like. Examples of organic powders include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane, benzoguanamine powder, polymethylbenzoguanamine powder, tetrafluoroethylene powder, polymethyl methacrylate powder, cellulose, silk powder, nylon powder, nylon 12, nylon 6, silicone powder, styrene-acrylic acid copolymer, divinylbenzene-styrene copolymer, vinyl resin, urea resin, phenolic resin, fluororesin, silicon resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, microcrystalline fiber powder, starch powder, and lauroyl lysine. Examples of surfactant metal salt powders (metal soaps) include zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc cetyl phosphate, calcium cetyl phosphate, and sodium zinc cetyl phosphate.

[0063] Examples of 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 ochre; inorganic black pigments such as black iron oxide and carbon black; 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; lake-formed tar dyes; lake-formed natural dyes; and synthetic resin powders that are composites of these powders. Examples of pearl pigments include titanium dioxide-coated mica, titanium dioxide-coated mica, bismuth oxychloride, titanium dioxide-coated bismuth oxychloride, titanium dioxide-coated talc, fish scale foil, and titanium dioxide-coated colored mica. Examples of metal powder pigments include aluminum powder, copper powder, and stainless steel powder. Examples of tar dyes 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 No. 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 others. Examples of natural pigments include carminic acid, laccaic acid, calsamine, brazilin, and crocin.

[0064] These powders can also be compounded or treated with general oils, silicone oils, fluorine compounds, surfactants, etc., and one or more types of these can be used as needed, including those treated with alkyl groups having hydrolyzable silyl groups or hydrogen atoms directly bonded to silicon atoms, linear and / or branched organopolysiloxanes having hydrolyzable silyl groups or hydrogen atoms directly bonded to silicon atoms, linear and / or branched organopolysiloxanes having hydrolyzable silyl groups or hydrogen atoms directly bonded to silicon atoms and comodified with long-chain alkyl groups, linear and / or branched organopolysiloxanes having hydrolyzable silyl groups or hydrogen atoms directly bonded to silicon atoms and comodified with polyoxyalkylenes, and acrylic-silicone copolymers having hydrolyzable silyl groups or hydrogen atoms directly bonded to silicon atoms.

[0065] Examples of antiperspirants include aluminum chlorohydrate, aluminum chloride, aluminum sesquichlorohydrate, zirconyl hydroxychloride, aluminum zirconium hydroxychloride, and aluminum zirconium glycine complex.

[0066] Examples of UV absorbers include benzoic acid-based UV absorbers such as para-aminobenzoic acid; anthranilic acid-based UV absorbers such as methyl anthranilate; salicylic acid-based UV absorbers such as methyl salicylate, octyl salicylate, and trimethylcyclohexyl salicylate; cinnamic acid-based UV absorbers such as octyl para-methoxycinnamate; benzophenone-based UV absorbers such as 2,4-dihydroxybenzophenone; urocanic acid-based UV absorbers such as ethyl urocanate; dibenzoylmethane-based UV absorbers such as 4-t-butyl-4'-methoxydibenzoylmethane; phenylbenzimidazole sulfonic acid, triazine derivatives, and the like. Examples of ultraviolet absorbing and scattering agents include fine-particle titanium dioxide, fine-particle iron-containing titanium dioxide, fine-particle zinc oxide, fine-particle cerium oxide, and composites thereof, which are powders that absorb and scatter ultraviolet light. Dispersions in which these ultraviolet absorbing and scattering powders are pre-dispersed in an oil are also used.

[0067] Examples of humectants include glycerin, sorbitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, pentylene glycol, glucose, xylitol, maltitol, polyethylene glycol, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate, polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside, egg yolk lecithin, soy lecithin, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, and sphingophospholipids.

[0068] Examples of preservatives and antibacterial agents include alkyl parahydroxybenzoates, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, imidazolidinyl urea, salicylic acid, isopropylmethylphenol, carbolic acid, parachlormethacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, iodopropynyl butylcarbamate, polylysine, photosensitizer, silver, and plant extracts.

[0069] Examples of fragrances include natural and synthetic fragrances. Natural fragrances include plant-based fragrances isolated from flowers, leaves, wood, and fruit peels, as well as animal-based fragrances such as musk and civet. Examples of synthetic fragrances include hydrocarbons such as monoterpenes; alcohols such as aliphatic alcohols and aromatic alcohols; aldehydes such as terpene aldehydes and aromatic aldehydes; ketones such as alicyclic ketones; esters such as terpene esters; lactones, phenols, oxides, nitrogen-containing compounds, acetals, and the like.

[0070] Examples of salts include inorganic salts, organic acid salts, amine salts, and amino acid salts. 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. Examples of 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. Examples of 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, and even acid-alkali neutralization salts used in pharmaceutical formulations can also be used.

[0071] Examples of antioxidants include carotenoids, ascorbic acid and its salts, ascorbyl stearate, tocopherol, tocopheryl acetate, tocopherol, pt-butylphenol, butylhydroxyanisole, dibutylhydroxytoluene, phytic acid, ferulic acid, thiotaurine, hypotaurine, sulfites, erythorbic acid and its salts, chlorogenic acid, epicatechin, epigallocatechin, epigallocatechin gallate, apigenin, campherol, myricetin, and quercetin.

[0072] Examples of pH adjusters include potassium carbonate, sodium bicarbonate, and ammonium bicarbonate. Examples of chelating agents include alanine, sodium edetate, sodium polyphosphate, sodium metaphosphate, and phosphoric acid. Examples of cooling agents include L-menthol, camphor, and menthyl lactate. Examples of anti-inflammatory agents include allantoin, glycyrrhizic acid and its salts, glycyrrhetinic acid and stearyl glycyrrhetinate, tranexamic acid, and azulene.

[0073] Ingredients for beautifying the skin include whitening agents such as placental extract, arbutin, glutathione, and saxifrage extract; cell activators such as royal jelly, photosensitizer, cholesterol derivatives, and calf blood extract; skin roughness improving agents, blood circulation promoting agents such as nonylic acid valenylamide, benzyl nicotinate, β-butoxyethyl nicotinate, capsaicin, gingerol, cantharis tincture, ichthammol, caffeine, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandelate, cinnarizine, trazoline, acetylcholine, verapamil, cepharanthine, and γ-oryzanol; skin astringents such as zinc oxide and tannic acid; and anti-seborrheic agents such as sulfur and thianthol.

[0074] Vitamins include vitamin A derivatives such as vitamin A oil, retinol, retinyl acetate, and retinyl palmitate; vitamin B2 derivatives such as riboflavin, riboflavin butyrate, and flavin adenine nucleotide; vitamin B6 derivatives such as pyridoxine hydrochloride, pyridoxine dioctanoate, and pyridoxine tripalmitate; vitamin B derivatives such as vitamin B12 and its derivatives; vitamin B15 and its derivatives; L-ascorbic acid, L-ascorbic acid dipalmitate, sodium L-ascorbic acid-2-sulfate, and dipotassium L-ascorbic acid phosphate. Examples include vitamin C derivatives such as ergocalciferol and cholecalciferol, vitamin D derivatives such as α-tocopherol, β-tocopherol, γ-tocopherol, dl-α-tocopherol acetate, dl-α-tocopherol nicotinate, and dl-α-tocopherol succinate, nicotinic acid derivatives such as nicotinic acid, benzyl nicotinate, and nicotinamide, vitamin H, vitamin P, calcium pantothenate, D-pantothenyl alcohol, pantothenyl ethyl ether, acetylpantothenyl ethyl ether, and other pantothenic acid derivatives, as well as biotin.

[0075] Examples of amino acids include glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, aspartic acid, glutamic acid, cystine, cysteine, methionine, and tryptophan. Examples of nucleic acids include deoxyribonucleic acid. Examples of hormones include estradiol and ethenylestradiol. Examples of inclusion compounds include cyclodextrins.

[0076] Examples of hair solidifying agents include amphoteric, anionic, cationic, and nonionic polymer compounds, such as polyvinylpyrrolidone polymers including polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers; acidic vinyl ether polymers including methyl vinyl ether / alkyl maleate half-ester copolymers; acidic polyvinyl acetate polymers including vinyl acetate / crotonic acid copolymers; acidic acrylic polymers including (meth)acrylic acid / alkyl (meth)acrylate copolymers and (meth)acrylic acid / alkyl (meth)acrylate / alkylacrylamide copolymers; and amphoteric acrylic polymers including N-methacryloylethyl-N,N-dimethylammonium·α-N-methylcarboxybetaine / alkyl (meth)acrylate copolymers and hydroxypropyl (meth)acrylate / butylaminoethyl methacrylate / octylamide acrylate copolymers. Naturally derived polymer compounds such as cellulose or its derivatives, keratin and collagen or their derivatives can also be suitably used.

[0077] By using the organopolysiloxane composition of the present invention to perform silane coupling treatment or fiber treatment on a substrate, the adhesion of the treated organic-inorganic composite material can be improved. The following describes a method for treating a substrate using the organopolysiloxane composition of the present invention. There are no particular limitations on the method of treating a substrate using the organopolysiloxane composition of the present invention. Examples include coating the substrate with the organopolysiloxane composition, entraining the organopolysiloxane composition with an inert gas and bringing the substrate into contact with this entrained gas, and directly mixing the organopolysiloxane composition together with the substrate using a mixer or mill. Among these, the method of coating the substrate with the organopolysiloxane composition is preferred from the viewpoint of simplicity. Methods for applying organopolysiloxane compositions include, for example, brush application, spray coating, wire bar application, blade application, roll coating, and dipping.

[0078] The conditions under which the organopolysiloxane composition of the present invention is applied to, contacted with, or mixed with a substrate are not particularly limited, as long as the conditions allow the silanol groups of the silicone resin (1) to react with the hydroxyl groups on the substrate surface. From the viewpoint of productivity, the processing 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, the processing 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 it can be set appropriately in relation to the processing temperature.

[0079] The substrate to be treated can be either an inorganic or organic material. Examples of inorganic materials include silicon compounds such as glass plates, glass fibers, 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; and carbonates such as calcium carbonate, zinc carbonate, and magnesium carbonate. Among these, silicon compounds and metal oxides are particularly preferred from the viewpoint of reactivity with the silanol group 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 phenolic resins; and oils and fats, surfactants, and liquid crystals. Among these, natural polymers and synthetic polymers are particularly preferred from the viewpoint of reactivity with the amino groups of the organopolysiloxane composition.

[0080] After treating a substrate with the organopolysiloxane composition of the present invention, excess organopolysiloxane composition can be removed by conventional methods such as washing and drying. Note that the post-treatment by washing and drying may be performed individually or in combination. [Examples]

[0081] The present invention will be described more specifically below 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 diameter is the volume-based median diameter (D90) measured by dry laser diffraction. The volume-based median diameter was measured using a laser diffraction particle size distribution analyzer Mastersizer 3000 (Malvern) by dry method according to Fraunhofer diffraction theory, under conditions of dispersion pressure of 2 bar and scattering intensity of 2-10%, and the diameter corresponding to the 50% cumulative value of the volume-based cumulative particle size distribution curve was measured. Furthermore, the interfacial shear strength τ [MPa] of the glass fiber epoxy resin composite material was calculated using the composite interface property evaluation device HM410 (manufactured by Toei Sangyo Co., Ltd.) by the microdroplet method, with the diameter of the glass fiber being D [μm], the length of the glass fiber embedded in the epoxy resin cured product being L [μm], and the load applied when pulling out the epoxy resin cured product in the axial direction of the glass fiber being F [mN], using the formula τ = F / πDL.

[0082] [1] Synthesis of powdered silicone resin by spray drying method [Synthesis Example 1] Synthesis of powdered 3-aminopropylsilanetriol homopolymer A 30% by mass aqueous solution of 3-aminopropylsilanetriol homopolymer was spray-dried to remove water from the aqueous solution (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 obtain a powdered 3-aminopropylsilanetriol homopolymer. The obtained powdered 3-aminopropylsilanetriol homopolymer was titrated by potentiometric titration, confirming an amine value of 480.7 KOH mg / g. Furthermore, dry laser diffraction measurements revealed an average particle size of 40.6 μm and a loose bulk density of 0.263 g / mL.

[0083] [2] Preparation of organopolysiloxane compositions [Example 1] To 100 parts by mass of toluene, an aprotic solvent, 1 part by mass of the powdered 3-aminopropylsilanetriol homopolymer prepared in Synthesis Example 1 and 10 parts by mass of butyric acid, a carboxylic acid compound, were added at room temperature and the mixture was stirred at room temperature for 24 hours. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, and a homogeneous pale yellow transparent liquid organopolysiloxane composition was obtained.

[0084] [Example 2] The mixture was stirred in the same manner as in Example 1, except that the aprotic solvent was replaced with 100 parts by mass of isododecane. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, yielding a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[0085] [Example 3] The mixture was stirred in the same manner as in Example 1, except that the aprotic solvent was replaced with 100 parts by mass of isohexadecane. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, yielding a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[0086] [Example 4] The mixture was stirred in the same manner as in Example 1, except that the aprotic solvent was replaced with 100 parts by mass of squalane. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, yielding a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[0087] [Example 5] The mixture was stirred in the same manner as in Example 1, except that the aprotic solvent was replaced with 100 parts by mass of tetradecene. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, yielding a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[0088] [Example 6] The mixture was stirred in the same manner as in Example 1, except that the aprotic solvent was replaced with 100 parts by mass of squalene. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, yielding a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[0089] [Example 7] The mixture was stirred in the same manner as in Example 1, except that the aprotic solvent was replaced with 100 parts by mass of acetone. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, yielding a homogeneous brown transparent liquid organopolysiloxane composition.

[0090] [Example 8] The mixture was stirred in the same manner as in Example 1, except that the aprotic solvent was replaced with 100 parts by mass of tetrahydrofuran. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, yielding a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[0091] [Example 9] The mixture was stirred in the same manner as in Example 1, except that the carboxylic acid compound was replaced with 10 parts by mass of caproic acid. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, and a homogeneous pale yellow transparent liquid organopolysiloxane composition was obtained.

[0092] [Example 10] The mixture was stirred in the same manner as in Example 1, except that the carboxylic acid compound was replaced with 10 parts by mass of caprylic acid. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, yielding a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[0093] [Example 11] The mixture was stirred in the same manner as in Example 1, except that the carboxylic acid compound was replaced with 10 parts by mass of undecylic acid. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, yielding a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[0094] [Example 12] The mixture was stirred in the same manner as in Example 1, except that the carboxylic acid compound was replaced with 10 parts by mass of oleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, and a homogeneous pale yellow transparent liquid organopolysiloxane composition was obtained.

[0095] [Example 13] The mixture was stirred in the same manner as in Example 2, except that the carboxylic acid compound was replaced with 10 parts by mass of oleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, yielding a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[0096] [Example 14] The mixture was stirred in the same manner as in Example 3, except that the carboxylic acid compound was replaced with 10 parts by mass of oleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, and a homogeneous pale yellow transparent liquid organopolysiloxane composition was obtained.

[0097] [Example 15] The mixture was stirred in the same manner as in Example 4, except that the carboxylic acid compound was replaced with 10 parts by mass of oleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, yielding a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[0098] [Example 16] The mixture was stirred in the same manner as in Example 5, except that the carboxylic acid compound was replaced with 10 parts by mass of oleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, and a homogeneous pale yellow transparent liquid organopolysiloxane composition was obtained.

[0099] [Example 17] The mixture was stirred in the same manner as in Example 6, except that the carboxylic acid compound was replaced with 10 parts by mass of oleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, yielding a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[0100] [Example 18] The mixture was stirred in the same manner as in Example 7, except that the carboxylic acid compound was replaced with 10 parts by mass of oleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, yielding a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[0101] [Example 19] The mixture was stirred in the same manner as in Example 8, except that the carboxylic acid compound was replaced with 10 parts by mass of oleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, yielding a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[0102] [Example 20] The mixture was stirred in the same manner as in Example 1, except that the carboxylic acid compound was replaced with 10 parts by mass of linoleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, and a homogeneous pale yellow transparent liquid organopolysiloxane composition was obtained.

[0103] [Example 21] The mixture was stirred in the same manner as in Example 1, except that the carboxylic acid compound was replaced with 10 parts by mass of linolenic acid. During stirring, the 3-aminopropylsilanetriol homopolymer dissolved, yielding a homogeneous pale yellow transparent liquid organopolysiloxane composition.

[0104] [Comparative Example 1] The mixture was stirred in the same manner as in Example 1, except that a carboxylic acid compound was not used, but the 3-aminopropylsilanetriol homopolymer did not dissolve.

[0105] [Comparative Example 2] The mixture was stirred in the same manner as in Example 1, except that 1 part by mass of the powdered 3-aminopropylsilanetriol homopolymer prepared in Synthesis Example 1 was replaced with 1 part by mass of the bulk 3-aminopropylsilanetriol homopolymer prepared using a vacuum dryer and a pulverizer, but the 3-aminopropylsilanetriol homopolymer did not dissolve.

[0106] [Application Example 1] [1] Fiber treatment with organopolysiloxane composition Glass fibers (approximately 300 mm in length and 23 μm in diameter) were immersed in a solution of the organopolysiloxane composition obtained in Example 1 at 25°C for 30 minutes to treat the fibers. After that, the glass fibers were removed from the solution and dried at 70°C for 2 hours for post-treatment. [2] Molding of glass fiber epoxy resin composite materials The organopolysiloxane-treated glass fibers obtained above were coated with droplets of an epoxy resin composition consisting of epoxy resin (JER828, manufactured by Mitsubishi Chemical Corporation) and a curing agent (triethylenetetramine, manufactured by Tokyo Chemical Industry Co., Ltd.), with a diameter of approximately 100 μm, ensuring that the droplets did not come into contact with each other. Then, the glass fiber epoxy resin composite material was formed by heat curing in two stages: the first stage at 80°C for 1.5 hours, and the second stage at 100°C for 2 hours.

[0107] [Application Example 2] Fiber treatment and composite material molding were carried out in the same manner as in Application Example 1, except that the organopolysiloxane composition was changed to the solution of Example 2.

[0108] [Application Example 3] Fiber treatment and composite material molding were carried out in the same manner as in Application Example 1, except that the organopolysiloxane composition was changed to the solution of Example 12.

[0109] [Comparative Application Example 1] Using glass fibers (approximately 300 mm in length and 23 μm in diameter) that were not treated with an organopolysiloxane composition, a glass fiber epoxy resin composite material was molded in the same manner as in Application Example 1 [2].

[0110] [Performance evaluation] Using the composite interface property evaluation device HM410 (manufactured by Toei Sangyo Co., Ltd.), the interfacial shear strength τ [MPa] of the glass fiber epoxy resin composite materials molded in Application Examples 1-3 and Comparative Application Example 1 was measured by the microdroplet method. A higher value indicates better adhesion of the glass fiber epoxy resin composite material. The results are shown in Table 1.

[0111] [Table 1]

[0112] As shown in Table 1, in the glass fiber epoxy resin composite materials obtained in Application Examples 1 to 3, multiple silanol groups contained in the powdered silicone resin react with multiple hydroxyl groups on the surface of the glass fibers, and further amino groups react with the epoxy resin, resulting in improved adhesion with the glass fiber epoxy resin composite material.

Claims

1. It consists only of a powdered 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. A transparent organopolysiloxane composition having an average particle size of 1 to 200 μm in volume-based median diameter, determined by dry laser diffraction of the silicone resin. 【Chemistry 1】 (In the formula, R 1 Each of these independently represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, which may each contain a heteroatom, and R 2 (Each of these independently represents a hydrogen atom, a methyl group, or an ethyl group, and 'a' represents an integer from 2 to 70.)

2. The organopolysiloxane composition according to claim 1, wherein the silicone resin is spray-dried particles.

3. The organopolysiloxane composition according to claim 1 or 2, wherein the carboxylic acid compound is one or more selected from saturated monocarboxylic acid compounds having 1 to 11 carbon atoms and unsaturated monocarboxylic acid derivatives having 3 to 22 carbon atoms.

4. The organopolysiloxane composition according to claim 1 or 2, wherein the aprotic solvent is one or more selected from saturated aliphatic hydrocarbon solvents, unsaturated aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and ketone solvents.

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