JP2011137050A - Reactive polysiloxane composition excellent in preservation stability - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve the preservation stability of reactive polysiloxane represented by formula (1) having a reactive functional group and soluble in a solvent, since a known condensate of a silicon compound having a reactive group and soluble in a solvent has such problems that, it is insolubilized with time while preserving the condensate and a polymer is precipitated from a solution or is gelatinized. <P>SOLUTION: The precipitation or gelation of a polymer has been known to easily occur when an alcohol-based solvent was used as a solvent in the conventional silicon compound condensate, whereas it is found that, in the reactive polysiloxane represented by formula (1), the case in which the reactive polysiloxane is preserved as a solution of a solvent containing an alcohol-based solvent, is superior in stability to the case in which it is preserved as a solid and to the case in which it is a solution of a solvent containing no alcohol-based solvent, and the invention is thus accomplished. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a composition suitable for long-term storage, which comprises a polysiloxane having a reactive functional group and soluble in a solvent, and a specific solvent, and the reactive polysiloxane is at least one of the curable composition. As a part, a hardened film having excellent heat resistance is provided.

  Not only the reactive polysiloxane composition of the present invention, but also industrially used chemical materials are desirably excellent in storage stability, and it is necessary that the physical properties do not change even after long-term storage. Generally speaking, polysiloxanes having reactive functional groups undergo side reactions such as partial cross-linking during storage, so that the solubility in the solvent decreases, making it difficult to dissolve in the solvent or the solution. In the case of storing in, the insolubilized component may be precipitated from the solution.

  For example, Patent Document 1 describes that a polysiloxane macromonomer having a reactive group may undergo condensation over time to cause gelation or the like. In addition, although solvents such as alcohols, ketones, ethers and the like can be used in the production process, it is preferable to remove the solvent from the system during or after the process, or by-product alcohol or solvent remains. It is described that there is a possibility that the polymer precipitates.

  Patent Document 2 discloses a method for producing an organosilicon compound containing a compound similar to the reactive organosilicon compound of the present invention, but polysiloxanes with many residual alkoxy groups tend to gel with time. Is described. In addition, alcohol solvents are exemplified as the reaction solvent, but after the reaction, the reaction is performed by a volatile component removal step or a washing step using an organic solvent such as ketone, ether, hydrocarbon, ester, etc., which does not exemplify the alcohol solvent. It has been suggested that alcoholic solvents as solvents are removed.

  Furthermore, in Patent Document 2, it is described that the produced silicon compound can be made into a solution with a cleaning organic solvent that does not exemplify an alcohol solvent, but in all examples, the silicon compound contains an organic solvent. Isolated as an evaporated solid. It is disclosed that the stability evaluation was performed by dissolving in propylene glycol monomethyl ether acetate (PGMEA).

  That is, an organosilicon compound having a reactive group and its application to a curable composition are known, and a problem that gelation easily occurs when there are many residual alkoxy groups is known. It is not known about the effect of improving the storage stability when the alcohol solvent is contained in the solvent, and conversely, since the precipitation of the polymer occurs when the alcohol solvent is used as the solvent, it was used as a reaction solvent for the condensation reaction. The alcohol was thought to be removed in the final step.

JP-A-6-32903 WO2009 / 131038 International Publication Pamphlet

  Condensates of silicon compounds that have reactive groups and are soluble in solvents have been known, but over time the condensates are insolubilized while the condensates are stored, and the polymer precipitates or gels from solution. There was a problem. An object of the present invention is to improve the storage stability of a reactive polysiloxane having a reactive functional group and soluble in a solvent.

〔式（１）中、Ｒ⁰はメタクリロイル基、アクリロイル基、オキセタニル基の中から選択される少なくとも一つを含む有機基であり、Ｒ⁰は同一であっても異なっても良く、Ｒ¹は炭素数１〜１０の中から選択される少なくとも一つを含む有機基であり、Ｒ²およびＲ³は炭素数１〜１０のアルキル基、または炭素−炭素不飽和基を有する炭素数２〜１０の有機基であり、Ｒ⁴は炭素数１〜１０のアルキル基であり、Ｒ⁵は炭素数１〜６のアルキル基であり、wおよびｚは正の数であり、ａ，ｘおよびｙは０または正の数である。また、０≦ａ／ｗ≦３、０≦ｘ／（ａ＋ｗ）≦２であり、０≦ｙ／（ａ＋ｗ）≦２であり、０．０１≦ｚ／（ａ＋ｗ＋ｘ＋ｙ）≦１である。〕 The present invention provides a reactive polysiloxane composition having excellent storage stability when the reactive polysiloxane represented by the general formula (1) is dissolved in an organic solvent containing at least 1% by weight of an alcohol solvent, We found out that the invention was completed.

In [Equation (1), R ⁰ is an organic group containing at least one selected methacryloyl group, an acryloyl group, from the oxetanyl group, R ⁰ may be the same or different, R ¹ is It is an organic group containing at least one selected from 1 to 10 carbon atoms, and R ² and R ³ are each an alkyl group having 1 to 10 carbon atoms or a carbon number 2 to 10 having a carbon-carbon unsaturated group. R ⁴ is an alkyl group having 1 to 10 carbon atoms, R ⁵ is an alkyl group having 1 to 6 carbon atoms, w and z are positive numbers, and a, x and y are 0 or a positive number. Further, 0 ≦ a / w ≦ 3, 0 ≦ x / (a + w) ≦ 2, 0 ≦ y / (a + w) ≦ 2, and 0.01 ≦ z / (a + w + x + y) ≦ 1. ]

  The reactive polysiloxane of the present invention is a liquid that can be easily applied to applications such as a coating agent, and has excellent storage stability, so that it can be stored for a long time without changing its physical properties, and can be transported or used for other materials. Is easy to mix.

  The present invention will be described in detail below. In the present specification, “(meth) acryl” means acryl and methacryl, and “(meth) acrylate” means acrylate and methacrylate. The “(meth) acryloyl group” means an acryloyl group and a methacryloyl group.

<Reactive polysiloxane>
The reactive polysiloxane in the present invention has a structure represented by the general formula (1).

In [Equation (1), R ⁰ is an organic group containing at least one selected methacryloyl group, an acryloyl group, from the oxetanyl group, R ⁰ may be the same or different, R ¹ is It is an organic group containing at least one selected from 1 to 10 carbon atoms, and R ² and R ³ are each an alkyl group having 1 to 10 carbon atoms or a carbon number 2 to 10 having a carbon-carbon unsaturated group. R ⁴ is an alkyl group having 1 to 10 carbon atoms, R ⁵ is an alkyl group having 1 to 6 carbon atoms, w and z are positive numbers, and a, x and y are 0 or a positive number. Further, 0 ≦ a / w ≦ 3, 0 ≦ x / (a + w) ≦ 2, 0 ≦ y / (a + w) ≦ 2, and 0.01 ≦ z / (a + w + x + y) ≦ 1. ]

〔一般式（２）において、Ｒ⁶は水素原子又はメチル基であり、Ｒ⁶は同一であっても異なっても良く、Ｒ⁷は炭素数１〜６のアルキレン基であり、Ｒ⁷は同一であっても異なっても良い。〕 R ^{0 in the} general formula (1) is preferably an organic group selected from the following general formula (2) or (3).

[In General Formula (2), R ⁶ is a hydrogen atom or a methyl group, R ⁶ may be the same or different, R ⁷ is an alkylene group having 1 to 6 carbon atoms, and R ⁷ is the same. Or different. ]

〔一般式（３）において、Ｒ⁸は水素原子又は炭素数１〜６のアルキル基であり、Ｒ⁸は同一であっても異なっても良く、Ｒ⁹は炭素数１〜６のアルキレン基であり、Ｒ⁹は同一であっても異なっても良い。〕

[In General Formula (3), R ⁸ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁸ may be the same or different, and R ⁹ is an alkylene group having 1 to 6 carbon atoms. Yes, R ⁹ may be the same or different. ]

In the formulas (2) and (3), preferred R ⁷ and R ⁸ are both propylene groups, because the compounds that form such organic functional groups are easily available or synthesized. Preferred R ⁶ is a methyl group, and preferred R ⁸ is an ethyl group.
When R ⁰ is a structure of formula (2), the reactive polysiloxane can be imparted with radical polymerizability, and when R ⁰ is formula (3), it can be imparted with cationic polymerizability. ⁰ may share the structure of the formula (2) and the structure of the formula (3) in the same polymer chain, or has a structure of the formula (2) and a polymer having the structure of the formula (2). You may use together with a polymer. It is more preferable to use a reactive polysiloxane having at least the structure of formula (2).

R ¹ in the general formula (1) is an organic group containing at least one selected from 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms and 7 to 10 carbon atoms. It is selected from an aralkyl group or an organic group having an aryl group having 6 to 10 carbon atoms, and may be the same or different.

N in the general formula (1) is 0 or 1. When n is 0, the monomer unit represented by the subscript w in the general formula (1) has three Si—O— bonds, and is also called “T structure”. In addition, when n is 1, the monomer unit represented by the subscript of w has two Si—O— bonds, and is also called “D structure”.
In the reactive polysiloxane represented by the general formula (1), the proportion of the inorganic portion and the organic portion described later is not limited, but in order to increase the proportion of the inorganic portion, a T structure in which n is 0. In order to improve the solubility of the reactive polysiloxane in an organic solvent, it is preferable to have a D structure where n is 1. Monomer units of T structure and D structure may be shared in the same molecule, or different ones for each molecule may be used in combination. The abundance ratio of the T structure and the D structure can be determined by the monomer charge ratio when producing the reactive polysiloxane, and is appropriately selected depending on the use of the reactive polysiloxane. In the present invention, the average value of n is preferably n = 0 to 0.5, more preferably n = 0 to 0.3.

In the general formula (1), R ² and R ³ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an organic group having 2 to 10 carbon atoms having a carbon-carbon unsaturated group capable of hydrosilylation reaction. R ² is preferably a methyl group, a phenyl group, or both a methyl group and a phenyl group, and more preferably a methyl group having a small steric hindrance.

R ³ is preferably a methyl group, an ethyl group, a propyl group, or a phenyl group, more preferably a methyl group. R ⁴ is preferably a methyl group, an ethyl group or a propyl group, more preferably a methyl group. R ⁵ is preferably a methyl group, an ethyl group, or a propyl group, more preferably a propyl group, and more preferably a 1-propyl group.

The reactive polysiloxane of the present invention can be produced by cohydrolyzing and condensing a hydrolyzable monomer having a structure of each monomer unit. Examples of the hydrolyzable group include a halogeno group and an alkoxy group, but the hydrolyzable group is preferable because it has good hydrolyzability and does not by-produce an acid, and an alkoxy group having 1 to 3 carbon atoms is more preferable. A step in which a hydrolyzable monomer having a structure of each monomer unit is appropriately charged at a suitable composition ratio, and is preferably subjected to hydrolysis copolycondensation under acidic or alkaline conditions, more preferably under alkaline conditions (hereinafter, “ In addition to the “first step”, the following steps may be further included.
(Second step) A step of neutralizing the reaction solution obtained in the first step with an alkali or an acid.
(Third step) A step of removing volatile components from the neutralized liquid obtained in the second step.
(Fourth step) A step of mixing and contacting the concentrate obtained in the third step with the cleaning organic solvent to dissolve at least the reactive polysiloxane in the cleaning organic solvent.
(Fifth step) A step of obtaining an organic solution containing reactive polysiloxane after washing the organic liquid obtained in the fourth step with water.
(Sixth Step) A step of removing volatile components from the organic solution obtained in the fifth step.
(Seventh step) A step of dissolving the reactive polysiloxane isolated in the sixth step in a solvent containing an alcohol solvent.

  As described above, when the reactive polysiloxane of the present invention is produced by condensation of a hydrolyzable monomer, the condensation rate can be 92% or more, more preferably 95% or more, and still more preferably 98 in molar units. % Or more. It is most preferable that substantially all of the siloxane bond-forming groups (including hydrolyzable groups) are condensed, but the upper limit of the condensation rate is usually 99.9%. Therefore, the hydrolyzable group which is not condensed in the reactive polysiloxane of the present invention may remain in any of the structures of the formula (1). The residual ratio of the hydrolyzable group is preferably 8% or less, more preferably 2% or less in terms of molar units.

  When the cleaning organic solvent used in the fourth step is an organic solvent containing an alcohol solvent used in the reactive polysiloxane composition of the present invention, it is used as a solvent for the reactive polysiloxane composition as it is. You can also Those subjected to the fifth to seventh steps are preferred because water-soluble impurities are reduced and storage stability is improved.

When the reactive polysiloxane has a siloxane bond-forming group (including a hydrolyzable group), the residual ratio should be calculated from the integrated intensity of each peak in the ¹ H-NMR (nuclear magnetic resonance spectrum) chart. Can do. In addition, “substantially all of the hydrolyzable groups are condensed” means that, for example, almost no peaks based on hydrolyzable groups are observed in the ¹ H-NMR chart of the obtained reactive polysiloxane. Can be confirmed.

  The number average molecular weight of the reactive polysiloxane is preferably 500 to 100,000, more preferably 1,000 to 50,000, still more preferably 2, in terms of standard polystyrene by gel permeation chromatography (GPC) analysis. 000 to 20,000.

<Reactive polysiloxane composition>
The reactive polysiloxane composition of the present invention is represented by the above general formula (1), and further contains a reactive polysiloxane which may contain a residual siloxane bond-forming group such as a hydrolyzable group derived from the raw material, and an alcohol solvent. However, it may further contain other components as long as the storage stability is not impaired. Other components include polymerizable unsaturated compounds, radical polymerization inhibitors, antioxidants, ultraviolet absorbers, light stabilizers, leveling agents, organic polymers, fillers, metal particles, pigments, polymerization initiators, sensitizers, An organic solvent etc. are mentioned.

  Examples of the polymerizable unsaturated compound include adjusting the physical properties such as hardness, mechanical strength, chemical resistance and adhesion of a cured product formed from the curable composition of the present invention, and adhesion to a substrate. A compound having an acryloyl group or a methacryloyl group (hereinafter referred to as “(meth) acrylate compound”) for the purpose of obtaining a cured film having excellent properties and adjusting the viscosity and curability of the curable composition. Etc. are preferably used.

  As said (meth) acrylate compound, monofunctional (meth) acrylate, polyfunctional (meth) acrylate, urethane (meth) acrylate, etc. are mentioned. These may be used alone or in combination of two or more.

Examples of the radical polymerization inhibitor include phenolic compounds such as hydroquinone and hydroquinone monomethyl ether.
Examples of the antioxidant include hinders such as 2,6-di-tert-butyl-4-methylphenol and pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate). Examples include dophenol-based antioxidants, sulfur-based secondary antioxidants such as 4,6-bis (octylthiomethyl) -o-cresol, and phosphorus-based secondary antioxidants. These may be used alone or in combination of two or more.
By using the radical polymerization inhibitor and the antioxidant, the storage stability and thermal stability of the reactive polysiloxane composition can be improved.
When the reactive polysiloxane composition contains a radical polymerization inhibitor, the content of the radical polymerization inhibitor is preferably 1 to 10, with respect to 1,000,000 parts by mass of the reactive polysiloxane. 000 parts by mass, more preferably 10 to 2,000 parts by mass, still more preferably 100 to 500 parts by mass.
When the reactive polysiloxane composition contains an antioxidant, the content of the antioxidant is preferably 1 to 10,000 mass with respect to 1,000,000 mass parts of the reactive polysiloxane. Parts, more preferably 10 to 2,000 parts by mass, still more preferably 100 to 500 parts by mass.

Examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, Hydroxyphenyl triazine UV absorbers such as 3,5-triazine, and benzotriazoles such as 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol Examples include ultraviolet absorbents, inorganic fine particles that absorb ultraviolet rays such as titanium oxide fine particles and zinc oxide fine particles. These may be used alone or in combination of two or more. Examples of the light stabilizer include hindered amine light stabilizers such as bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate.
By using the ultraviolet absorber and the light stabilizer, UV resistance and weather resistance can be enhanced.

Examples of the leveling agent include silicone polymers and fluorine atom-containing polymers.
By using the leveling agent, the leveling property when the curable composition is applied can be improved.

  Examples of the organic polymer include (meth) acrylic polymers, and preferable constituent monomers include methyl methacrylate, cyclohexyl (meth) acrylate, N- (2- (meth) acryloxyethyl) tetrahydrophthalimide, and the like. .

  Examples of the filler include silica and alumina.

  The curable composition of the present invention can be an active energy ray curable composition and a thermosetting composition, and a polymerization initiator is selected and blended according to the purpose.

  As for the kind of the organic solvent, it is essential to dissolve the reactive polysiloxane used in the present invention, and it is preferable to dissolve other components. More specifically, alkyl alcohols, alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, aromatic compounds such as toluene and xylene, esters such as propylene glycol monomethyl ether acetate, ethyl acetate and butyl acetate, acetone, methyl ethyl ketone and methyl Examples include ketones such as isobutyl ketone, ethers such as dibutyl ether, and N-methylpyrrolidone.

  The composition of the present invention can be used as a coating material as it is or with an additive, but for applications such as coating on a plastic substrate such as polycarbonate or polyester, and overcoating on a non-crosslinked coating film, an organic solvent is used as a base. There is a risk of eroding the material. Preferred organic solvents are alkylene glycol monoalkyl ethers such as alkyl alcohol and propylene glycol monomethyl ether because there is no erosion of the base material.

  Moreover, if the organic solvent is not miscible with water at an arbitrary ratio, the washing water can be separated by a liquid separation operation after the washing in the fifth step, so that the sixth step becomes unnecessary, which is preferable.

  In the case where the organic solvent has an alcoholic hydroxyl group such as alkyl alcohol or propylene glycol monoalkyl ether, the effect of the alcohol solvent in the present invention itself is exhibited, so that it is not necessary to separately add an alcohol solvent. More preferable alcohol-based organic solvents are alkyl alcohols having 3 to 5 carbon atoms or propylene glycol monoalkyl ethers, which have good solubility for the reactive polysiloxane of the present invention. Among these, pentanol and propylene glycol monobutyl ether are more preferable because they are easily separated from water.

  As the organic solvent having no alcoholic hydroxyl group, the reactive polysiloxane of the present invention is well dissolved and mixed well with an alcohol solvent, and the solvent of the reactive polysiloxane composition remains as it is in the application of a curable composition or the like. Propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA), ethyl acetate, butyl acetate, methyl ethyl ketone, methyl amyl ketone (abbreviated as MAK), methyl isobutyl in terms of good wettability with the substrate even if it remains. Ketone (abbreviated as MIBK), N-methylpyrrolidone, and the like are preferable, and PGMEA is more preferable because it is excellent in separability from water. Only one organic solvent listed above may be used, or two or more organic solvents may be used in combination.

  The content of impurities in the organic solvent is preferably small, and the water content is preferably 1000 ppm or less, more preferably 500 ppm or less, more preferably 50 ppm or less, based on mass. In order to remove water in the organic solvent, a dehydrating agent such as molecular sieves can be used in combination, or a known method such as distillation can be used. The amount of water can be measured by the Karl Fischer method or the like.

  The alcohol solvent used in the present invention may be any compound having an alcoholic hydroxyl group, but preferably has one alcoholic hydroxyl group in the molecule, preferably an alkyl alcohol or alkylene glycol monoalkyl ether. Specifically, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 2, 2-dimethyl-1-propanol, 2-pentanol, 3-methyl-2-butanol, 3-pentanol, 2-methyl-2-butanol, cyclopentanol, propylene glycol monomethyl ether (hereinafter abbreviated as PGM), propylene glycol Roh (hereinafter abbreviated as PGE) ethyl ether, (hereinafter referred to as PGP) propylene glycol monopropyl ether, (hereinafter referred to PGB) propylene glycol monobutyl ether and the like are exemplified.

  Among these alcohols, alkyl alcohol having 1 to 5 carbon atoms or propylene glycol monoalkyl ether is preferable in the present invention, and more preferably propylene glycol monoalkyl having high effect of improving the storage stability of the composition of the present invention. Alkyl ethers, specifically PGM, PGE, PGP and PGB are preferred. Of these, a plurality of alcohols may be used in combination.

  The amount of impurities in the alcohol solvent is preferably small, and the water content is preferably 5000 ppm or less, more preferably 1000 ppm or less, more preferably 300 ppm or less, based on mass. In order to remove the water in the alcohol solvent, a dehydrating agent such as molecular sieves can be used in combination, or a known method such as distillation can be used. The water content can be measured by the Karl Fischer method or the like.

  The concentration of the alcoholic solvent in the mixed solvent when used in combination with the organic solvent is not particularly defined, the alcoholic solvent is 100% and may not contain any organic solvent other than the alcoholic solvent, or the organic solvent itself is alcohol. When it is a system solvent, it is not necessary to add an alcohol solvent separately. However, the alcohol solvent is preferably 1% by mass or more and 100% by mass or less, more preferably 2% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 30% by mass or less of the total amount of the solvent.

  In the reactive polysiloxane composition of the present invention, the concentration of the reactive polysiloxane dissolved is not particularly limited, but the concentration of the polysiloxane in the entire composition is preferably between 0.1 and 80% by mass. More preferably, it is 1-70 mass%.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to this embodiment.
In addition, “Mn” in the description of Examples means a number average molecular weight, and is calculated using standard polystyrene by gel permeation chromatography (hereinafter abbreviated as “GPC”).
Further, ¹ H-NMR analysis of the obtained reactive polysiloxane was carried out by accurately weighing about 1 g of a measurement sample and about 100 mg of hexamethyldisiloxane (hereinafter referred to as “HMDSO”) as an internal standard substance. The mixture was mixed and analyzed based on the signal intensity of proton of HMDSO.

Production and Evaluation of Reactive Polysiloxane Composition <Synthesis Example 1 of Reactive Polysiloxane>
First, the monomer unit represented by the subscript “a” in the general formula (1) has four Si—O— bonds, and is also called “Q structure”. A monomer raw material that gives a Q structure after condensation is, for example, tetramethoxysilane (hereinafter referred to as “TMOS”), and a predetermined amount thereof is charged. A raw material giving another monomer unit structure of the formula (1) is selected and charged. In Synthesis Example 1, in order to exchange the methoxy group of TMOS with 1-propoxy group, after charging 150 g of 1-propanol and 36.53 g (0.24 mol) of tetramethoxysilane as a Q monomer, While stirring, 4.37 g of a 25 mass% tetramethylammonium hydroxide methanol solution (0.1 mol of methanol, 12 mmol of tetramethylammonium hydroxide) was gradually added. Then, it was made to react for 1 hour, stirring at an internal temperature of 60 degreeC at pH9. Here, when the reaction solution was subjected to gas chromatographic analysis (TCD detector), a compound in which the methoxy group of TMOS was substituted with an n-propoxy group (1 to 4 substitutes) and unreacted TMOS were detected. Only trace amounts of TMOS were detected. The ratio of the n-propoxy group-containing compound among these was approximately 100% by mass in total. Based on the peak area of the product in the gas chromatogram, the number of 1-propanol substitutions (average of the number of n-propoxy groups per molecule of n-propoxy group-containing compound) was determined to be 2.7.

  Next, 59.62 g (0.24 mol) of 3-methacryloxypropyltrimethoxysilane as a T monomer was added to the reaction solution, and 30.2 g of water was further added. Then, 7.88 g of a 25 mass% tetramethylammonium hydroxide methanol solution (0.18 mol of methanol, 21.6 mmol of tetramethylammonium hydroxide) was added, and the mixture was reacted at a temperature of 25 ° C. and a pH of 9 for 24 hours with stirring. It was. Thereafter, the mixture was neutralized by adding 22.2 g (35.3 mmol) of a 10% by mass nitric acid aqueous solution. Next, this neutralized solution was added to a mixed solution of 120 g of diisopropyl ether and 180 g of water for extraction. The diisopropyl ether layer is washed with water to remove salts and excess acid, and then N-nitrosophenylhydroxylami aluminum salt (trade name “Q-1301”, manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization inhibitor. 11.5 mg was added. From the obtained diisopropyl ether solution, the organic solvent was distilled off under reduced pressure to obtain a colorless transparent solid reactive polysiloxane (C1). The yield was 57.72g.

The reactive polysiloxane (C1) was analyzed by ¹ H-NMR, and the presence of a methacryloyl group was confirmed.
Further, the content of the T structure and the content of the remaining alkoxy group were determined by this ¹ H NMR analysis, and the content of the Q structure was calculated based on this. As a result, it was confirmed that the obtained reactive polysiloxane was a copolycondensate obtained by reacting each monomer raw material stoichiometrically.

The content ratio of the remaining alkoxy groups (n-propoxy groups bonded to silicon atoms) calculated from the ¹ H-NMR chart of the reactive polysiloxane (C1) is 2 with respect to the total alkoxy groups contained in the raw materials. The amount corresponds to 5%. Moreover, Mn was 9,600.

<Synthesis Example 2 of Reactive Polysiloxane>
Instead of 59.62 g (0.24 mol) of 3-methacryloxypropyltrimethoxysilane as the T monomer in Synthesis Example 1, 3-ethyl-3-((3- (trimethoxysilyl) propoxy) methyl) Reactive polysiloxane (C2) was obtained in the same manner as in Synthesis Example 1 except that 36.19 g (0.13 mol) of oxetane was used and 24.3 g of water was used. The residual alkoxy amount was 1.0% and Mn was 4,400.

<Preparation of reactive polysiloxane composition>
<Examples> Reactive polysiloxanes (C1, C2) were dissolved in various solvents shown in the examples of Table 1 so that the solid content was 50% by mass to obtain compositions.
<Comparative example> Reactive polysiloxane (C1, C2) was melt | dissolved in the various solvent shown by the comparative example of Table 1 so that solid content might be 50 mass%, and it was set as the composition. Moreover, it was set as the comparative example as reactive polysiloxane which does not melt | dissolve in a solvent but remains solid.

<Storage stability evaluation test>
Stability evaluation of the above reactive polysiloxane composition was carried out by sealing 20 g of various solutions of the reactive polysiloxanes of Synthesis Examples (C1) and (C2) into a 100 ml flask and storing them in an air constant temperature bath at 60 ° C. The test was conducted by shaking the flask every 24 hours. If the liquid flows vigorously when the flask is turned upside down, it is judged that gelation has not occurred. Was recorded as the number of storage days. This evaluation is performed every day for 10 days, and if the gelation does not occur after 10 days, the storage stability evaluation test is completed, and for the composition without the gelation, the viscosity after 10 days is measured and compared with before the start of the evaluation. did. The viscosity of the composition was measured at 25 ° C. with an E-type viscometer. (Unit: mPa · s)

  For Comparative Examples 5 and 6 in which the storage stability test was performed in a solid state without using the reactive polysiloxane as a solution, 20 g of the reactive polysiloxane was stored in a weighing bottle with a lid and stored in a 60 ° C air constant temperature bath. A small amount of solid was taken every day, PGMEA was added and stirred for 1 hour to conduct a dissolution test, and the day when it did not dissolve was determined as the day of gelation.

  In Table 1, the number of parts of the solvent represents parts by mass. Except for Comparative Examples 5 and 6 in which no solvent was used, a storage test was carried out using a solution in which 100 parts by mass of the solid content was dissolved to 100 parts by mass with respect to a total of 100 parts of the solvent.

  Comparative Examples 1 to 4 in which the reactive polysiloxane was dissolved in an organic solvent not containing an alcohol-based solvent were all gelled by the sixth day of the storage stability evaluation test, and Comparative Example 5 in which no solvent was used. , 6 became insoluble in the solvent 2 days after the storage stability evaluation test, but Examples 1 to 6 dissolved in an alcohol solvent and Examples 7 to 12 dissolved in an organic solvent containing an alcohol solvent were used. Since gelation did not occur after 10 days of testing, Examples 1 to 12 using an alcohol solvent were superior.

  In Examples 1 to 12 other than the gelled samples, the viscosities of the compositions before the storage stability evaluation test and after the 10-day test were measured, and the change rate of the viscosity was examined and shown in Table 1. The smaller the change in viscosity compared to before the test, the better the storage stability. However, when the reactive polysiloxane is C1, the result is that the alcohol solvent is used as the organic solvent, and 5 to 20% of the total solvent. The included Examples 7 to 9 were superior to Examples 1 to 3 in which the composition was 100% alcohol solvent, and the same tendency was observed when the reactive polysiloxane was C2.

<Preparation of curable composition>
In Example 9, curable compositions were prepared using the reactive polysiloxane compositions before the storage stability test and after the 10-day test, respectively. A curable composition was prepared by dissolving 3 parts by mass of 2-hydroxy-2-methyl-1-phenyl-propan-1-one, which is a radical polymerization initiator, in 200 parts by mass of the reactive polysiloxane composition. The curable composition using the reactive polysiloxane composition (Example 9) before the storage stability test (S1) and the curable composition using the reactive polysiloxane composition (Example 9) after the 10-day test. The composition was named (S2), applied to a glass plate using a bar coater, and heated at about 50 ° C. for 5 minutes to volatilize the solvent to form a film having a thickness of about 10 μm. Then, when it was cured by irradiation with ultraviolet rays under the following conditions in the atmosphere, both (S1) and (S2) were free of surface tack with a single irradiation and exhibited good curability.
[UV irradiation conditions]
Lamp: 80 W / cm high-pressure mercury lamp Lamp height: 10 cm
Conveyor speed: 10m / min

  Since the reactive polysiloxane of the present invention has a reactive group, it can be used as at least a part of a curable composition, and provides a curable composition having excellent curability. In addition, since it can be stored for a long time in the form of a solution, it is easy to store, transport and use, and is suitable as an industrial material.

Claims (5)

A reactive polysiloxane composition excellent in storage stability, comprising a reactive polysiloxane represented by the general formula (1) and an organic solvent containing an alcohol solvent of 1% by mass or more of the total solvent amount.

In [Equation (1), R ⁰ is an organic group containing at least one selected methacryloyl group, an acryloyl group, from the oxetanyl group, R ⁰ may be the same or different, R ¹ is It is an organic group containing at least one selected from 1 to 10 carbon atoms, and R ² and R ³ are each an alkyl group having 1 to 10 carbon atoms or a carbon number 2 to 10 having a carbon-carbon unsaturated group. R ⁴ is an alkyl group having 1 to 10 carbon atoms, R ⁵ is an alkyl group having 1 to 6 carbon atoms, w and z are positive numbers, and a, x and y are 0 or a positive number. Further, 0 ≦ a / w ≦ 3, 0 ≦ x / (a + w) ≦ 2, 0 ≦ y / (a + w) ≦ 2, and 0.01 ≦ z / (a + w + x + y) ≦ 1. ]
The reactive polysiloxane composition according to claim 1, wherein R ⁰ in the general formula (1) according to claim 1 is an organic group selected from the following general formula (2) or (3).

[In General Formula (2), R ⁶ is a hydrogen atom or a methyl group, R ⁶ may be the same or different, R ⁷ is an alkylene group having 1 to 6 carbon atoms, and R ⁷ is the same. Or different. ]

[In General Formula (3), R ⁸ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁸ may be the same or different, and R ⁹ is an alkylene group having 1 to 6 carbon atoms. Yes, R ⁹ may be the same or different. ]
The reactive polysiloxane composition of Claim 1 or 2 whose alcohol solvent is 2-50 mass% of the total amount of solvents.
The reactive polysiloxane composition according to any one of claims 1 to 3, wherein the organic solvent contains a water-insoluble solvent that is immiscible with water at an arbitrary ratio and is separable from water by a liquid separation operation. object.
  The reactive polysiloxane composition according to any one of claims 1 to 4, wherein the organic solvent comprises propylene glycol monomethyl ether acetate (PGMEA) and an alcohol solvent having a total solvent amount of 2 to 50% by mass.