WO2020196751A1 - シラノール基の脱水縮合反応抑制剤及び抑制方法、並びに、シラノール基含有ポリオルガノシロキサンの製造方法及びその組成物 - Google Patents

シラノール基の脱水縮合反応抑制剤及び抑制方法、並びに、シラノール基含有ポリオルガノシロキサンの製造方法及びその組成物 Download PDF

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WO2020196751A1
WO2020196751A1 PCT/JP2020/013658 JP2020013658W WO2020196751A1 WO 2020196751 A1 WO2020196751 A1 WO 2020196751A1 JP 2020013658 W JP2020013658 W JP 2020013658W WO 2020196751 A1 WO2020196751 A1 WO 2020196751A1
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compound
polyorganosiloxane
group
silanol group
dehydration condensation
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PCT/JP2020/013658
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English (en)
French (fr)
Japanese (ja)
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洋樹 深海
松尾　陽一
信二 鍵谷
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株式会社カネカ
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Priority to CN202080022585.0A priority Critical patent/CN113631637A/zh
Priority to JP2021509587A priority patent/JP7418411B2/ja
Publication of WO2020196751A1 publication Critical patent/WO2020196751A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups

Definitions

  • the present invention relates to a silanol group-containing dehydration condensation reaction inhibitor and method, a method for producing a silanol group-containing polyorganosiloxane, and a composition thereof.
  • the most common method for synthesizing polyorganosiloxane is to use organoalkoxysilane as a starting material and hydrolyze / dehydrate-condensate it in the presence of water from the viewpoint of cost and handleability.
  • polyorganosiloxane synthesized using organotrialkoxysilane as a main raw material is preferably used in consideration of compatibility with an organic resin and reactivity.
  • the polyorganosiloxane obtained by the above method retains a silanol group which is a functional group exhibiting condensability and also contains residual water, the condensation reaction of the silanol group easily proceeds with time, whereby the condensation reaction of the silanol group easily proceeds. Storage stability becomes a problem because the physical properties fluctuate.
  • the silanol group is converted into an alkoxy group by reacting the synthesized polyorganosiloxane with an organoalkoxysilane to improve the storage stability.
  • the technique is known (see, for example, Patent Document 1).
  • the present invention comprises a silanol group dehydration condensation reaction inhibitor used to suppress the progress of the silanol group dehydration condensation reaction without converting the silanol group to another functional group, and the inhibition thereof. It is an object of the present invention to provide a method for suppressing a dehydration condensation reaction of a silanol group using an agent, a method for producing a silanol group-containing polyorganosiloxane having improved storage stability, and a composition thereof.
  • the present invention relates to a silanol group dehydration condensation reaction inhibitor composed of a ⁇ -dicarbonyl compound and / or a sulfonyl isocyanate compound.
  • the present invention also relates to a method for suppressing the progress of the dehydration condensation reaction of the silanol group by adding a ⁇ -dicarbonyl compound and / or a sulfonyl isocyanate compound to a system containing a compound having a silanol group.
  • the present invention is a step of hydrolyzing and dehydrating and condensing a monoorganotrialkoxysilane and / or an alkoxysilane component containing a diorganodialkoxysilane in the presence of water to form a polyorganosiloxane having a silanol group. It also relates to a method for producing a polyorganosiloxane having a silanol group, which comprises a step of adding a ⁇ -dicarbonyl compound and / or a sulfonyl isocyanate compound as a silanol group dehydration condensation reaction inhibitor to the polyorganosiloxane.
  • the amount of the water added is 30 mol% or more and 60 mol% or less with respect to 100% of the total number of moles of the alkoxy groups directly bonded to the silicon atom contained in the alkoxysilane component.
  • the hydrolysis and dehydration condensation reaction is carried out in the presence of a basic compound and / or a neutral salt as a condensation catalyst, and the reaction inhibitor is a ⁇ -dicarbonyl compound.
  • the hydrolysis and dehydration condensation reaction is carried out in the absence of a condensation catalyst or in the presence of an acidic compound as a condensation catalyst, and the reaction inhibitor is a sulfonyl isocyanate compound.
  • the sulfonyl isocyanate compound is added after removing 80 mol% or more of the alcohol generated by the hydrolysis reaction.
  • the present invention is a hydrolysis condensate of an alkoxysilane component containing 70 mol% or more and 100 mol% or less of monoorganotrialkoxysilane and 0 mol% or more and 30 mol% or less of diorganodialkoxysilane.
  • the structural unit derived from the organotrialkoxysilane is the structural unit T1 that forms one siloxane bond, the structural unit T2 that forms two siloxane bonds, and the structural unit that forms three siloxane bonds.
  • the ratio of the number of moles of T3 to the total number of moles of T1, T2, and T3 measured by 29 Si-NMR is 10% or more and 70% or less, and polyorganosiloxane having a silanol group, and It also relates to a composition containing 0.1 part by weight or more and 10 parts by weight or less of ⁇ -dicarbonyl compound and / or sulfonylisocyanate compound with respect to 100 parts by weight of the polyorganosiloxane. Preferably, before and after holding the composition at 50 ° C.
  • the present invention may be a two-component composition composed of a liquid A containing the composition and a liquid B containing a condensation catalyst. Furthermore, the present invention comprises 0.5 parts by weight or more based on 100 parts by weight of the compound having a silanol group in a composition containing a compound having a silanol group and a ⁇ -dicarbonyl compound and / or a sulfonyl isocyanate compound. It also relates to a method of accelerating the dehydration condensation reaction of the silanol group by adding the condensation catalyst of the above.
  • a silanol group dehydration condensation reaction inhibitor used for suppressing the progress of the silanol group dehydration condensation reaction without converting the silanol group to another functional group, and the inhibitor are used. It is possible to provide a method for suppressing a dehydration condensation reaction of a silanol group, a method for producing a silanol group-containing polyorganosiloxane having improved storage stability, and a composition thereof.
  • the first invention relates to a silanol group dehydration condensation reaction inhibitor, which is composed of a ⁇ -dicarbonyl compound and / or a sulfonyl isocyanate compound.
  • the reaction inhibitor suppresses the progress of the dehydration condensation reaction in which water molecules are desorbed from two silanol groups to form a siloxane bond (Si—O—Si).
  • the reaction inhibitor according to the present invention does not convert the hydroxyl group in the silanol group into another functional group such as an alkoxy group, and can suppress the dehydration condensation reaction while maintaining the form of the silanol group. Therefore, there is an advantage that good storage stability can be achieved without changing the original physical properties of the compound having a silanol group.
  • the ⁇ -dicarbonyl compound is a compound having a structure in which two carbonyl groups are bonded with one carbon atom sandwiched between them.
  • Specific examples of the ⁇ -dicarbonyl compound are not particularly limited, and examples thereof include acetylacetone, dimedone, cyclohexane-1,3-dione, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate, diethyl malonate, and meldrum's acid. Be done.
  • the ⁇ -carbonyl compound has a high effect of suppressing the dehydration condensation reaction of the silanol group, particularly when the basic compound and / or the neutral salt is present in the system containing the silanol group-containing compound.
  • acetylacetone is preferable because it has a boiling point of around 140 ° C. and is easily volatilized after coating, and the dehydration condensation reaction proceeds due to the volatilization of the compound and the coating film is easily
  • Sulfonyl isocyanate compounds have the effect of suppressing the progress of dehydration condensation reaction of silanol groups by dehydration action, and in addition, sulfonylamide groups are generated by reaction with water. Therefore, in the case of ordinary isocyanate compounds, amino groups It is presumed that the effect of suppressing the progress of the dehydration condensation reaction is enhanced as compared with the case where the compound is generated and the basicity is enhanced.
  • the sulfonyl isocyanate compound is not particularly limited, and examples thereof include tosyl isocyanate, benzenesulfonyl isocyanate, and chlorosulfonyl isocyanate. Among them, a monofunctional sulfonyl isocyanate compound is preferable, and an aromatic monosulfonyl isocyanate is more preferable because of its high solubility.
  • the sulfonyl isocyanate compound is a silanol group-containing compound when an acidic compound is present in the system containing a silanol group-containing compound, or when none of the basic compound, the neutral salt, and the acidic compound is present. Highly effective in suppressing dehydration condensation reaction.
  • the dehydration condensation reaction suppression of the present invention can achieve the effect of suppressing the progress of the dehydration condensation reaction of silanol groups by adding it to a system containing a compound having a silanol group.
  • the compound having a silanol group is not particularly limited, and examples thereof include polyorganosiloxane having a silanol group, acrylic resin having a silanol group, and polyoxyalkylene having a silanol group.
  • the amount of the dehydration condensation reaction inhibitor added is not particularly limited and can be appropriately determined in consideration of the content of silanol groups in the system, the temperature of the system, etc., but as an example, 100 parts by weight of the compound having a silanol group On the other hand, it is preferably 0.1 parts by weight or more and 10 parts by weight or less, more preferably 0.2 parts by weight or more and 4 parts by weight or less, and further preferably 0.3 parts by weight or more and 3 parts by weight or less.
  • the system containing the compound having a silanol group may be composed of only the compound having a silanol group, or in addition to the compound having a silanol group, a solvent other than water and other components. May be included.
  • the solvent is not particularly limited, and an organic solvent described later can be used.
  • a ⁇ -dicarbonyl compound and / or a sulfonyl isocyanate compound is added to a system containing a compound having a silanol group, the progress of the dehydration condensation reaction of the silanol group can be suppressed, but thereafter, the silanol group
  • a catalyst for the dehydration condensation reaction of the above By adding the catalyst for the dehydration condensation reaction of the above, the suppression of the dehydration condensation reaction can be released and the dehydration condensation reaction can be promoted.
  • a condensation catalyst such as an acidic compound, a basic compound, or a neutral salt, which will be described later, can be appropriately used.
  • the amount of the condensation catalyst added to release the suppression of the dehydration condensation reaction is preferably 0.5 parts by weight or more with respect to 100 parts by weight of the compound having a silanol group. It is more preferably 1 part by weight or more, and further preferably 2 parts by weight or more.
  • the upper limit value can be appropriately set by those skilled in the art in consideration of the effect of the condensation catalyst, but for example, it is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less.
  • the dehydration condensation reaction inhibitor of the present invention can be used in a method for producing a polyorganosiloxane having a silanol group.
  • a silanol group dehydration condensation reaction inhibitor is added to the polyorganosiloxane.
  • a polyorganosiloxane having a silanol group is produced by hydrolyzing and dehydrating the condensation reaction of the alkoxysilane component with water in the presence of a condensation catalyst, if necessary.
  • a condensation catalyst if necessary.
  • some of the alkoxy groups contained in the alkoxysilane component remain unreacted, or after the alkoxy group undergoes a hydrolysis reaction, the dehydration condensation reaction does not proceed and remains as a silanol group.
  • the produced polyorganosiloxane can have an alkoxysilyl group and / or a silanol group.
  • the alkoxysilane component which is a raw material of polyorganosiloxane contains 70 mol% or more and 100 mol% or less of monoorganotrialkoxysilane and 0 mol% or more and 30 mol% or less of diorganodialkoxysilane.
  • the monoorganotrialkoxysilane refers to a silane compound having one organic group and three alkoxy groups as a substituent on the silicon atom, and the diorganodialkoxysilane is on the silicon atom.
  • a substituent it refers to a silane compound having two organic groups and two alkoxy groups.
  • the monoorganotrialkoxysilane is an essential component, but the diorganodialkoxysilane may or may not be used.
  • the proportion of diorganodialkoxysilane in the alkoxysilane component is 30 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less, further preferably 5 mol% or less, and 1 mol% or less. Even more preferable.
  • alkoxysilane The organic group that monoorganotrialkoxysilane and diorganodialkoxysilane (hereinafter collectively referred to as alkoxysilane) have as a substituent on the silicon atom refers to an organic group other than the alkoxy group. Specific examples thereof are not particularly limited, and examples thereof include an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms such as a phenyl group.
  • the alkyl group or aryl group may be an unsubstituted group, or may have an epoxy group as a substituent, such as a glycidyloxy group or an epoxycyclohexyl group.
  • the alkyl group having 1 to 6 carbon atoms is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group.
  • the alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably 1 to 3 carbon atoms, and even more preferably 1 to 2 carbon atoms.
  • As the organic group only one type may be used, or two or more types may be mixed.
  • the organic group contained in the alkoxysilane one selected from the group consisting of a methyl group, an ethyl group, a propyl group, and a phenyl group is preferable.
  • the ratio of the total of the ethyl group, the propyl group, and the phenyl group to the total organic group contained in the alkoxysilane is preferably 50% by weight or more, more preferably 70% by weight or more, and more preferably 80% by weight or more. More preferred.
  • the organic group contained in the alkoxysilane contains an ethyl group and / or a propyl group because the storage stability of the coating liquid becomes high when the produced polyorganosiloxane is used as a component of the coating liquid.
  • alkoxy group that the alkoxysilane has as a substituent on the silicon atom examples include an alkoxy group having 1 to 3 carbon atoms. Specifically, it is a methoxy group, an ethoxy group, or a propoxy group, preferably a methoxy group or an ethoxy group, and more preferably a methoxy group.
  • alkoxy group only one type may be used, or two or more types may be mixed.
  • monoorganotrialkoxysilane are not particularly limited, but for example, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, and propyl.
  • diorganodialkoxysilane are not particularly limited, but for example, dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and vinylmethyldimethoxysilane. , Vinylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane and the like.
  • the alkoxysilane may be either a monoorganotrialkoxysilane or a diorganodialkoxysilane.
  • alkoxysilanes include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 8-glycidyloxyoctyltrimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned.
  • an alkoxysilane having such an epoxy group the storage stability of the produced polyorganosiloxane is improved.
  • the alkoxysilane component may be composed only of an alkoxysilane having an epoxy group.
  • the alkoxysilane component contains both an alkoxysilane having an epoxy group and an alkoxysilane having no epoxy group.
  • the alkoxysilane component is preferably composed of 50 mol% or more and 100 mol% or less of an alkoxysilane having an epoxy group and 0 mol% or more and 50 mol% or less of an alkoxysilane having no epoxy group.
  • an alkoxysilane having an epoxy group and an alkoxysilane not having an epoxy group in combination at such a ratio it becomes easy to produce a polyorganosiloxane having a silanol group and improved storage stability. ..
  • the amount of alkoxysilane having an epoxy group is 60 mol% or more and 100 mol% or less, and the amount of alkoxysilane having no epoxy group is 0 mol% or more and 40 mol% or less, and even more preferably 70 mol of alkoxysilane having an epoxy group. % Or more and 100 mol% or less, and 0 mol% or more and 30 mol% or less of alkoxysilane having no epoxy group.
  • the alkoxysilane component may be composed of only monoorganotrialkoxysilane, or may be composed of only monoorganotrialkoxysilane and diorganodialkoxysilane.
  • other alkoxysilanes that do not belong to either monoorganotrialkoxysilane or diorganodialkoxysilane may be further contained.
  • examples of other alkoxysilanes include an alkoxysilane having a (meth) acryloyl group, an alkoxysilane having a vinyl group, a triorganomonoalkoxysilane, and a tetraalkoxysilane.
  • the amount used may be determined within a range that does not impair the effects of the present invention.
  • the ratio of the alkoxysilane component to the whole is 10 It is preferably mol% or less, more preferably 5 mol% or less, and even more preferably 1 mol% or less.
  • the amount of water used is preferably 30 mol% or more and 60 mol% or less, with the total number of moles of the alkoxy groups directly bonded to the silicon atoms contained in the alkoxysilane component being 100%. If the amount of water used is less than this, the reaction does not proceed sufficiently, and the product tends to contain a large amount of unreacted components or low molecular weight components.
  • the amount of water used is more preferably 30 mol% or more and 50 mol% or less, and further preferably 40 mol% or more and 50 mol% or less.
  • an organic solvent other than water may be used in addition to water.
  • a water-soluble organic solvent is preferable because it is used in combination with water.
  • an organic solvent having 4 or more carbon atoms is preferable.
  • preferred organic solvents include, for example, propylene glycol methyl ether acetate, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, and diethylene glycol monoisopropyl ether.
  • Ethylene glycol monobutyl ether diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol Monoethyl ether, propylene glycol monopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, methanol, Examples thereof include, but are not limited to, ethanol, 1-propanol, ethylene
  • an organic solvent having a boiling point of 150 ° C. or lower under atmospheric pressure is preferable.
  • ethylene glycol monoethyl ether and ethylene are used.
  • Glycol monoisopropyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monoethyl ether and propylene glycol dimethyl ether are particularly preferable.
  • the hydrolysis and dehydration condensation reaction can be carried out in the presence of a condensation catalyst to promote the reaction.
  • a condensation catalyst a known one can be used.
  • Condensation catalysts are roughly classified into basic catalysts and acidic catalysts.
  • the acidic catalyst has an action of accelerating hydrolysis compared to condensation, and as a result, the obtained polyorganosiloxane has a relatively large number of silanol groups. Since the silanol group is stabilized in the solvent, the storage stability of the obtained polyorganosiloxane is likely to be improved. Therefore, it is preferable to carry out the hydrolysis and dehydration condensation steps in the presence of an acidic catalyst as the condensation catalyst.
  • an organic acid is preferable, and a phosphoric acid ester or a carboxylic acid is more preferable, because of compatibility with an alkoxysilane component and an organic solvent.
  • organic acids include ethyl acid phosphate, butyl acid phosphate, dibutyl pyrophosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, isotridecyl acid phosphate, dibutyl phosphate, bis (2-ethylhexyl) phosphate, and formic acid. Examples thereof include acetic acid, butyric acid and isobutyric acid.
  • Examples of the basic catalyst include N-ethylmorpholine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, Nt-butyldiethanolamine, triethylamine, n-butylamine, hexylamine, and triethanolamine.
  • Examples thereof include amine compounds such as diazabicycloundecene and ammonia, and metal hydroxides such as sodium hydroxide and potassium hydroxide.
  • a neutral salt can also be used as the condensation catalyst. Even if a neutral salt is used, the same effect as when an acidic catalyst is used can be obtained.
  • the neutral salt is a normal salt composed of a strong acid and a strong base, and is, for example, a group consisting of a group 1 element ion, a group 2 element ion, a tetraalkylammonium ion, and a guanidium ion as cations. It is a salt composed of a combination of any one selected from the above and one selected from the group consisting of Group 17 element ions excluding fluoride ions, sulfate ions, nitrate ions, and perchlorate ions as anions.
  • the anion is preferably a group 17 element ion because it has high nucleophilicity
  • the cation is a group 1 element ion or a group 2 ion as a non-bulky ion so as not to inhibit the nucleophilic action.
  • Element ions are preferred.
  • the specific compound of the neutral salt is not particularly limited, but for example, preferred neutral salts include lithium chloride, sodium chloride, potassium chloride, ravidium chloride, cesium chloride, magnesium chloride, calcium chloride, strontium chloride, lithium bromide, and the like.
  • Examples include magnesium, calcium iodide, and strontium iodide.
  • the amount of the condensation catalyst added can be adjusted as appropriate, but may be, for example, about 50 ppm to 3% by weight with respect to the alkoxysilane component.
  • the smaller the amount of the condensation catalyst used the more suitable it is within the range in which the effect of shortening the reaction time by the condensation catalyst is achieved.
  • reaction temperature when carrying out the hydrolysis and dehydration condensation steps, but for example, it is preferable to heat the reaction solution in the range of 50 to 110 ° C.
  • the hydrolysis and dehydration condensation reaction is carried out at a temperature of 110 ° C. or lower, the polyorganosiloxane of the present invention can be easily produced.
  • the reaction time when carrying out the hydrolysis and dehydration condensation steps can be appropriately set by those skilled in the art, but may be, for example, about 10 minutes to 12 hours.
  • the alcohol removal step can be carried out by subjecting the reaction solution after the hydrolysis and dehydration condensation steps to vacuum distillation to distill off the alcohol.
  • the conditions for vacuum distillation can be appropriately set by those skilled in the art, but the temperature at this time is preferably 50 to 110 ° C. for the same reason as described above.
  • the ratio of the number of moles of T3 to the total number of moles of T1, T2, and T3 measured by 29 Si-NMR as described later in polyorganosiloxane is When 10% or more and 70% or less are satisfied, the progress of the hydrolysis and dehydration condensation reaction is stopped, and specifically, the alcohol removal step is stopped to synthesize a polyorganosiloxane having a silanol group. be able to.
  • ⁇ -dicarbonyl compound and / or sulfonyl isocyanate compound which are the above-mentioned dehydration condensation reaction inhibitors
  • storage stability is achieved while having a silanol group.
  • An improved polyorganosiloxane can be produced.
  • the amount of the dehydration condensation reaction inhibitor added can be based on the above-mentioned numerical values.
  • ⁇ -dicarbonyl when the hydrolysis and dehydration condensation reaction is carried out in the presence of a basic compound and / or a neutral salt as a condensation catalyst, ⁇ -dicarbonyl as a dehydration condensation reaction inhibitor. It is preferable to use a compound. This is because the ⁇ -dicarbonyl compound has a high effect of suppressing the dehydration condensation reaction of the silanol group in the presence of the basic compound or the neutral salt.
  • dehydration condensation when the hydrolysis and dehydration condensation reaction is carried out without the addition of a condensation catalyst, or when it is carried out in the presence of an acidic compound as a condensation catalyst, dehydration condensation It is preferable to use a sulfonyl isocyanate compound as a reaction inhibitor. This is because the sulfonyl isocyanate compound has a high effect of suppressing the dehydration condensation reaction of the silanol group in the absence of a condensation catalyst or in the presence of an acidic compound.
  • the sulfonyl isocyanate compound has high reactivity with alcohol, it is desirable to add it after removing most of the alcohol from the system in order to exert the effect of the sulfonyl isocyanate compound. Therefore, when a sulfonyl isocyanate compound is used as a dehydration condensation reaction inhibitor, a step of removing the alcohol as described above from the reaction solution is carried out to remove 80 mol% or more of the total alcohol generated in the hydrolysis reaction. After that, it is preferable to add the sulfonyl isocyanate compound to the reaction system. More preferably, 85 mol% or more of the total alcohol generated in the hydrolysis reaction is removed, and more preferably 90 mol% or more is removed, and then the sulfonyl isocyanate compound is added.
  • the polyorganosiloxane produced in the present invention has a silanol group, but may have an alkoxysilyl group in addition to the silanol group (both groups are also collectively referred to as a reactive silicon group).
  • the silanol group contained in the polyorganosiloxane of the present invention is one in which the alkoxy group contained in the alkoxysilane component undergoes a hydrolysis reaction and then the dehydration condensation reaction does not proceed and remains.
  • the alkoxysilyl group that the polyorganosiloxane of the present invention may have is a part of the alkoxy group contained in the alkoxysilane component that remains unreacted without undergoing a hydrolysis reaction. ..
  • the presence of such a silanol group and / or an alkoxysilyl group enables the polyorganosiloxane to exhibit curability by a hydrolysis / dehydration condensation reaction.
  • the ratio of the number of moles of the structural unit T3 forming three siloxane bonds (hereinafter, also referred to as the molar ratio of T3) among the monoorganotrialkoxysilanes is less than 100%. It is necessary.
  • the molar ratio of T3 is based on the total number of moles of the structural units T1, T2, and T3 forming one, two, or three siloxane bonds among the monoorganotrialkoxysilanes contained in the raw material of the polyorganosiloxane.
  • the molar ratio of T3 is the structural unit derived from monoorganotrialkoxysilane, the structural unit T1 forming one siloxane bond, the structural unit T2 forming two siloxane bonds, and the siloxane bond. Based on the peak areas of the peaks derived from T1, T2, and T3, which are classified into the three constituent units T3 and measured by 29 Si-NMR, the peaks derived from T3 with respect to the total peak area of these. Calculated as an area ratio (%).
  • the polyorganosiloxane produced by the present invention preferably has a molar ratio of T3 of 10% or more and 70% or less. More preferably, it is 10% or more and 66% or less, and further preferably 10% or more and 60% or less.
  • the molar ratio of T3 can be adjusted by adjusting the amount of water used during the hydrolysis / dehydration condensation reaction for forming polyorganosiloxane, the type / amount of catalyst, the reaction temperature, etc., or using epoxy-containing alkoxysilane. It can be adjusted by using it.
  • the weight average molecular weight (MW) of the polyorganosiloxane produced by the present invention is not particularly limited, but is 500 or more and 20000 from the viewpoints of storage stability, compatibility with the organic resin, and the effect of improving the physical properties of the organic resin. It is preferably less than or equal to, more preferably 1000 or more and 10000 or less, and further preferably 3000 or more and 10000 or less.
  • the weight average molecular weight of the polyorganosiloxane can be determined by the method described in the section of Examples.
  • the polyorganosiloxane of the present invention does not refer to a composite resin in which organopolysiloxane and acrylic silicon are composited, as disclosed in, for example, International Publication No. 2017/1649459, and is not bonded to an organic resin. It refers to polyorganosiloxane.
  • the polyorganosiloxane produced according to the present invention may be in the form of a solution containing an organic solvent.
  • an organic solvent those described above can be used.
  • the composition containing a polyorganosiloxane having a silanol group and a dehydration condensation reaction inhibitor according to the present invention exhibits excellent storage stability.
  • the above-mentioned increase rate of the molar ratio of T3 before and after storing the composition containing the polyorganosiloxane at 50 ° C. for 2 weeks is used, and the increase rate is used. It is preferably 15% or less. The smaller the value of this increase rate, the more difficult it is for the structural unit T3 forming three siloxane bonds during storage to increase, and the better the storage stability.
  • the rate of increase is more preferably 12% or less, still more preferably 10% or less.
  • composition for paint The composition according to the present invention can constitute a composition for paints. By using the composition according to the present invention, it is possible to provide a composition for a coating material having improved storage stability.
  • the coating composition only the polyorganosiloxane may be a component that functions as a curable resin, or a curable organic resin may be further blended in addition to the polyorganosiloxane.
  • the weather resistance and scratch resistance of the cured coating film can be enhanced by the polyorganosiloxane.
  • the polyorganosiloxane produced by the present invention has a silanol group, it has high compatibility with an organic resin, and according to a preferred embodiment, it is simply added to the organic resin and stirred at room temperature. A uniform resin mixture can be obtained.
  • the curable organic resin is not particularly limited, but at least one selected from the group consisting of acrylic resin, polyester, and polyether is preferable.
  • the organic resin may be only one kind, or two or more kinds may be used in combination. Acrylic resin is particularly preferable.
  • the organic resin is preferably a resin having a functional group capable of reacting with the reactive silicon group of the polyorganosiloxane of the present invention.
  • a functional group include a hydroxyl group and a reactive silicon group.
  • the acrylic resin having a hydroxyl group for example, a resin obtained by radical polymerization of an acrylic monomer and a monomer having a hydroxyl group can be used.
  • the acrylic monomer is not particularly limited, but for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2 -Alkyl (meth) acrylate having 1 to 20 carbon atoms such as ethylhexyl (meth) acrylate; Cycloalkyl having 4 to 20 carbon atoms such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate.
  • Examples thereof include aralkyl (meth) acrylate having 3 to 20 carbon atoms such as (meth) acrylate; allyl (meth) acrylate; dicyclopentenyl (meth) acrylate; and benzyl (meth) acrylate.
  • the monomer having a hydroxyl group is not particularly limited, but for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate. , 4-Hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, 4-hydroxystyrene vinyl toluene, etc.
  • Modified lactone or polyester having a polymerizable carbon-carbon double bond at the end such as PlaccelFA-1, PlaccelFA-4, PlaccelFM-1, PlaccelFM-4 (all manufactured by Daicel Chemical Co., Ltd.); Blemmer PP series, Blemmer PE series, Blemmer PEP series (manufactured by Nichiyu Co., Ltd.), MA-30, MA-50, MA-100, MA-150, RA-1120, RA-2614, RMA-564, RMA- Examples thereof include polyoxyalkylenes having a polymerizable carbon-carbon double bond at the end, such as 568, RMA-1114, and MPG130-MA (all manufactured by Nippon Emulsifier Co., Ltd.).
  • a compound having two or more isocyanate groups as a cross-linking agent together with an acrylic resin having a hydroxyl group.
  • Specific examples of compounds having two or more isocyanate groups include hexamethylene diisocyanate, dicyclohexylmethane 4,4'-isocyanate, 2,2,4-trimethyl-1,6-diisocyanate, and isophorondi.
  • Aliphatic polyisocyanates such as isocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylene diisocyanate, polymethylene-polyphenylel-polyisocyanate
  • aromatic polyisocyanates such as nat.
  • the structure of the compound having two or more isocyanate groups includes a monomer, a burette type, an adduct type, and an isocyanurate type. These compounds can be used for room temperature curing. In addition, those in which these isocyanate groups are masked with a blocking agent can also be used.
  • the organic resin and the polyorganosiloxane are crosslinked with a structure represented by CO-Si, so that the polyorganosiloxane can be added to the organic resin. It is preferable because the effect of the compounding can be easily obtained.
  • the acrylic resin having a reactive silicon group for example, a resin obtained by radical copolymerizing an acrylic monomer and a monomer having a reactive silicon group can be used.
  • the acrylic monomer the above-mentioned acrylic monomer can be used.
  • the monomer having a reactive silicon group is not particularly limited, and for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (n-propoxy) silane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltris ( ⁇ ).
  • -Methoxyethoxy) silane allyltriethoxysilane, trimethoxysilylpropylallylamine, ⁇ - (meth) acryloxypropyltrimethoxysilane, ⁇ - (meth) acryloxipropyltriethoxysilane, ⁇ - (meth) acryloxipropyltri Isopropoxysilane, ⁇ - (meth) acryloxipropyltris ( ⁇ -methoxyethoxy) silane, ⁇ - (meth) acryloxipropylmethyldimethoxysilane, ⁇ - (meth) acryloxipropylmethyldiethoxysilane, ⁇ - (meth) ) Acryloxypropyl dimethylmethoxysilane, ⁇ - (meth) acryloxipropyl dimethylethoxysilane, N-vinylbenzyl- ⁇ -aminopropyltrimethoxysilane, 2-styrylethyltrime
  • paint compositions of the present invention include pigments, plasticizers, dispersants, antisettling agents, anti-skinning agents, desiccants, anti-dripping agents, matting agents, antistatic agents, conductive agents, flame retardants and the like. Additives for paint can be appropriately blended.
  • the coating composition of the present invention can be used as any coating liquid, but since it has excellent weather resistance and high transparency, it is a pigment-free coating liquid for clear coating films or a coating liquid for clear coating films. It can also be suitably used as a colored coating liquid containing a pigment or dye.
  • the coating composition of the present invention contains a curing agent or a curing agent because the curing reaction of the coating film is promoted in the presence of the curing agent and the working time at the time of forming the coating film can be shortened.
  • a curing agent or a curing agent because the curing reaction of the coating film is promoted in the presence of the curing agent and the working time at the time of forming the coating film can be shortened.
  • a curing agent known as a curing agent used for a curable resin composition utilizing a hydrolysis reaction and a dehydration condensation reaction of a reactive silicon group can be appropriately used.
  • the above-mentioned condensation catalyst can be used as the curing agent.
  • the amount of the condensation catalyst added is preferably 0.5 parts by weight or more with respect to 100 parts by weight of the polyorganosiloxane having a silanol group. It is more preferably 1 part by weight or more, and further preferably 2 parts by weight or more.
  • the upper limit value can be appropriately set by those skilled in the art in consideration of the effect of the condensation catalyst, but for example, it is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less.
  • an organic tin compound a titanium chelate compound, an aluminum chelate compound, an organic amine compound and the like can also be used.
  • organic tin compounds include dioctyl tin bis (2-ethylhexyl malate), dioctyl tin oxide or a condensate of dibutyl tin oxide and silicate, dibutyl tin dioctate, dibutyl tin dilaurate, dibutyl tin distearate, and dibutyl tin diacetyl.
  • Acetonate, dibutyltin bis (ethylmalate), dibutyltin bis (butylmalate), dibutyltin bis (2-ethylhexylmalate), dibutyltin bis (oleylmalate), stanas octoate, tin stearate, di-n- Examples include butyltin laurate oxide.
  • Specific examples of the organotin compound having an S atom in the molecule include dibutyltin bisisononyl-3-mercaptopropionate, dioctyltin bisisononyl-3-mercaptopropionate, and octylbutyltin bisisononyl-3-mercaptopropio.
  • titanium chelate compound examples include titanium acetylacetonate, titaniumtetraacetylacetonate, titanium ethylacetate, titanium phosphate compound, titanium octylene glycolate, titanium ethylacetate acetate and the like.
  • the aluminum chelate compound examples include ethyl acetoacetate aluminum diisopropylate, aluminum tris (acetylacetone), aluminum tris (ethylacetate acetate), aluminum monoacetylacetate bis (ethylacetate acetate), and alkylacetylacetate aluminum diisopropi. The rate etc. can be mentioned.
  • organic amine compound examples include triethylamine, triethylenediamine, trimethylamine, tetramethylenediamine, N-methylmorpholine, N-ethylmorpholine, N, N'-diethyl-2-methylpiperazine, laurylamine, dimethyllaurylamine and the like. Can be mentioned.
  • the amount of the curing agent used can be appropriately adjusted according to the curing temperature and the curing time. For example, it is preferably about 0.01 part by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the polyorganosiloxane, and is 0.1. It is more preferably about 10 parts by weight or more by weight.
  • the composition of the present invention when configured as a one-component curable composition, the composition of the present invention preferably contains a photocation generator. Since the photocation initiator generates cations by irradiating with light, the initiation of curing can be controlled by irradiating with light.
  • the photocation initiator is not particularly limited, and examples thereof include aromatic diazonium salts, aromatic sulfonium salts, and aromatic iodonium salts. More specifically, for example, diphenyliodonium-hexafluorophosphate, bis (p-alkylphenyl) iodonium-hexafluorophosphate, bis (p-alkylphenyl) iodonium-hexafluoroantimonate, triphenylsulfonium-hexafluoro.
  • Phosphate tris (p-alkylphenyl) sulfonium-hexafluorophosphate, tris (p-alkylphenyl) sulfonium-hexafluoroantimonate and the like can be mentioned.
  • the amount of the photocation generator added is preferably 0.25 parts by weight or more and 4 parts by weight or less with respect to 100 parts by weight of the polyorganosiloxane. It is preferably 5 parts by weight or more and 3 parts by weight or less.
  • the coating composition of the present invention can be applied to a base material and cured to form a coating film.
  • the conditions for coating and curing are not particularly limited, but it is preferable to use a heat source to promote the evaporation of the solvent during curing.
  • the thickness of the coating film formed is not particularly limited, but in the present invention, the thickness after drying is preferably 5 ⁇ m or more and 100 ⁇ m or less. If the thickness is thinner than 5 ⁇ m, the water resistance and moisture resistance of the coating film may be insufficient. If the thickness exceeds 100 ⁇ m, cracks may occur due to curing shrinkage during formation of the coating film. It is more preferably 5 ⁇ m or more and 50 ⁇ m or less, and further preferably 10 ⁇ m or more and 40 ⁇ m or less.
  • the base material to which the composition for coating of the present invention can be applied is not particularly limited, and for example, an organic base material such as polycarbonate (PC), acrylic, ABS, ABS / PC, polyethylene terephthalate (PET), glass, aluminum, etc.
  • organic base material such as polycarbonate (PC), acrylic, ABS, ABS / PC, polyethylene terephthalate (PET), glass, aluminum, etc.
  • Inorganic substrates such as SUS, copper, iron and stone can be used.
  • Condensation catalyst DBP (manufactured by Johoku Chemical Industry Co., Ltd., dibutyl phosphate, molecular weight 210.2).
  • LiCl (manufactured by Tokyo Kasei Co., Ltd., lithium chloride, molecular weight 42.4).
  • MgCl 2 (manufactured by Tokyo Kasei Co., Ltd., magnesium chloride hexahydrate, molecular weight 203.3).
  • TEA manufactured by Tokyo Kasei Co., Ltd., triethylamine, molecular weight 101.2
  • Reaction inhibitor AcAc (manufactured by Tokyo Kasei Co., Ltd., acetylacetone, molecular weight 100.1)
  • TI manufactured by Tokyo Kasei Co., Ltd., tosyl isocyanate, molecular weight 197.2
  • Solvent PMA (manufactured by Tokyo Kasei Co., Ltd., propylene glycol methyl ether acetate, molecular weight 132.2)
  • the resin solution obtained by reacting for 4 hours is composed of polyorganosiloxane, alcohol generated in the reaction process, and a small amount of residual water.
  • the resin solution is heated in an oil bath heated to 105 ° C. and volatilized at about 450 Torr for about 2 hours.
  • the amounts of methanol and water listed in each table were removed to obtain the amounts of polyorganosiloxane listed in each table.
  • reaction inhibitor After cooling the distilled polyorganosiloxane to about 50 ° C., the reaction inhibitors listed in each table were added to the polyorganosiloxane.
  • the amount of the reaction inhibitor added was 100 parts by weight of the calculated resin obtained assuming that the hydrolysis / dehydration condensation reaction of all the organoalkoxylans used had theoretically completely proceeded. The amount was set so as to be 3 parts by weight. The amount was set to 2 parts by weight in Example 12 and 1 part by weight in Example 13. In each comparative example, no reaction inhibitor was added.
  • the calculated resin amount was calculated according to the following formula.
  • the calculated resin amount is the sum of the values obtained for each organoalkoxysilane according to the following formula.
  • Weight of organoalkoxysilane x molecular weight of the organoalkoxysilane-69
  • NV of polyorganosiloxane 0.2 g of the obtained polyorganosiloxane and 2 g of acetone were placed in an aluminum cup to prepare a uniform polyorganosiloxane solution, and then the cup was placed in a hot air dryer heated to 105 ° C. for 1 hour, and after cooling. The weight was measured.
  • the non-volatile content (NV) of the polyorganosiloxane was measured from the value obtained by subtracting the weight of the aluminum cup from the weight and the weight of the polyorganosiloxane before drying.
  • Example 1 Synthesis of polyorganosiloxane 20.3 g of methyltrimethoxysilane, 127.1 g of 3-glycidyloxypropyltrimethoxysilane, 0.020 g of dibutyl phosphate and 18.5 g of pure water are placed in a 300 ml 4-neck flask at 90 ° C. It was heated in an oil bath set in 1 and reacted for 4 hours. Then, using an evaporator and an oil bath set at 105 ° C., the generated methanol and residual water were removed, and then 3.0 g of tosyl isocyanate was added as a reaction inhibitor, and the mixture was stirred until uniform and silanol.
  • a polyorganosiloxane solution having a group was obtained.
  • the NV of the obtained polyorganosiloxane was measured and found to be 88%, a weight average molecular weight of 3200, and a condensation rate of 50%.
  • Example 2 to 13 and Comparative Examples 1 to 8 A polyorganosiloxane solution was obtained in the same manner as in Example 1 except that the amount of the raw material used and the reaction conditions were as described in each table. In each table, the unit of the blending amount of each component is gram (g).
  • Weight average molecular weight The weight average molecular weight of polyorganosiloxane was measured by GPC. GPC was carried out using HLC-8320GPC manufactured by Tosoh Corporation as a liquid feeding system, TSK-GEL H type manufactured by Tosoh Corporation as a column, and THF as a solvent, and the weight average molecular weight was calculated in terms of polystyrene. did.
  • the structural units derived from the monoorganotrialkoxysilane are the structural unit T1 forming one siloxane bond, the structural unit T2 forming two siloxane bonds, and the structural unit T2 forming three siloxane bonds. It is classified into the unit T3.
  • AVANCE III HD500 manufactured by BRUKER 29 Si-NMR of polyorganosiloxane was measured using deuterated chloroform as a solvent, and the ratio of each peak area to the total peak area of the peaks derived from T1, T2, and T3 was calculated. , The molar ratio (%) of T1, T2, and T3 contained in polyorganosiloxane.

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JPH09279046A (ja) * 1995-12-23 1997-10-28 Ara Werk Kraemer Gmbh 水分の存在下で架橋可能なシリコーン系組成物
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JPH09279046A (ja) * 1995-12-23 1997-10-28 Ara Werk Kraemer Gmbh 水分の存在下で架橋可能なシリコーン系組成物
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