WO2019216141A1 - Procédé de production d'organopolysiloxane polymérisable par voie cationique, additif fortement antiadhésif, composition de silicone durcissable par rayonnement amovible, feuille anti-adhésive et procédé de production associé - Google Patents

Procédé de production d'organopolysiloxane polymérisable par voie cationique, additif fortement antiadhésif, composition de silicone durcissable par rayonnement amovible, feuille anti-adhésive et procédé de production associé Download PDF

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WO2019216141A1
WO2019216141A1 PCT/JP2019/016482 JP2019016482W WO2019216141A1 WO 2019216141 A1 WO2019216141 A1 WO 2019216141A1 JP 2019016482 W JP2019016482 W JP 2019016482W WO 2019216141 A1 WO2019216141 A1 WO 2019216141A1
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group
organopolysiloxane
component
mass
cationically polymerizable
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PCT/JP2019/016482
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English (en)
Japanese (ja)
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田中　賢治
青木　俊司
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信越化学工業株式会社
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Priority to JP2020518221A priority Critical patent/JP7060091B2/ja
Publication of WO2019216141A1 publication Critical patent/WO2019216141A1/fr

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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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • 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
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers

Definitions

  • the present invention relates to a method for producing a cationically polymerizable organopolysiloxane suitably used as a heavy release additive for a release sheet, and a releasability using the obtained cationic polymerizable organopolysiloxane as a heavy release additive for a release sheet.
  • the present invention relates to a radiation curable silicone composition, a release sheet using the composition, a production method thereof, and the like.
  • the organopolysiloxane composition is applied to the surface of various papers, laminated papers, synthetic films, transparent resins, metal foils, etc., and a cured film is formed by a cross-linking reaction. Release sheets such as release paper and release film having the property are manufactured.
  • Radiation curing methods include radical polymerization using (meth) acryl-modified polysiloxane, ene-thiol reaction using mercapto-modified organopolysiloxane and alkenyl-modified organopolysiloxane, and cation by ring opening of epoxy group of epoxy-modified polysiloxane. Examples thereof include curing using polymerization.
  • curing using cationic polymerization by ring opening of epoxy group of epoxy-modified polysiloxane is not hindered by oxygen and does not require heat for curing reaction. Since it can be applied to the tape and is excellent in convenience and operability, it is especially used as a coating agent for adhesive tape backing treatments, adhesive label release paper, and fixing fastener tapes using tape. The market is expected to expand in the future.
  • release sheets used for labels and production process papers are surface-treated with a silicone composition mainly composed of organopolysiloxane, and the release sheet silicone composition used for the release sheet includes: What has various peeling force is calculated
  • a release sheet having heavy release or variable release characteristics may be required.
  • the silicone release agent be a heavy release.
  • a light peelable silicone composition on one side and a heavy peelable silicone composition on the other side are coated and cured.
  • the attached laminate is required to have a peeling force that does not easily peel off on the heavy surface side. Furthermore, when the heavy peeling property is required, the peeling force does not change with time, and the properties such as the release sheet and the like do not change.
  • compositions containing organopolysiloxane resins are widely used.
  • organopolysiloxane resin is simply mixed, there is no sufficient heavy peeling effect, and even if it is added in a large amount, the desired peeling force may not be achieved. For this reason, it has been studied to produce a release sheet having a high heavy release effect by reacting and using an organosiloxane resin.
  • Patent Document 1 includes (SiO 4/2 ) units (Q units), (R 3 SiO 1/2 ) units (M units), epoxy functional M units as component (A). , (R 2 SiO) unit (D unit) or (RSiO 3/2 ) unit (T unit) and at least one of M unit and epoxy per 10 parts in total of Q unit, D unit and T unit 20 to 80% by mass of a cationically polymerizable organopolysiloxane having a total of at least 5 parts of functional M units and 80 to 80 of cationically polymerizable terminal organopolysiloxane containing an epoxy functional M unit as component (B)
  • An ultraviolet curable epoxy silicone composition containing 20% by mass and containing a cationically polymerizable organopolysiloxane having an epoxy equivalent of more than 1,000 and an onium-based photocatalyst has been proposed. .
  • Patent Document 2 an organohydrogensiloxane is used for an OH group of an OH group-containing organopolysiloxane having M units, Q units, and (HO) SiO 3/2 units as main constituent units.
  • a dehydrogenative condensation reaction is performed using an excess amount of SiH groups, and then an addition reaction is performed between the SiH groups remaining in the obtained reaction product and the alkenyl groups of a compound containing an epoxy group and an alkenyl group.
  • a method for producing a cationically polymerizable organopolysiloxane and a heavy release additive obtained therefrom are proposed.
  • Patent Document 3 polydiorganosiloxane having one or more hydroxyl groups or hydrolyzable groups in one molecule having an average degree of polymerization of 100 to 3,000, and M units and Q units are mainly used.
  • a radiation curable silicone composition using a heavy release additive composed of a condensation reaction product obtained by dehydration-condensation reaction has been proposed.
  • the present invention has been made in view of the above circumstances, and is capable of suppressing increase in viscosity and gelation, and is obtained by this method for producing a cationically polymerizable organopolysiloxane that is suitably used as a heavy release additive for a release sheet.
  • An object of the present invention is to provide a releasable radiation-curable silicone composition using the obtained cationic polymerizable organopolysiloxane as a heavy release additive for a release sheet, a release sheet using the composition, a production method thereof, and the like. To do.
  • a cationically polymerizable organopolysiloxane containing an epoxy group is usually obtained by an addition reaction of an organohydrogenpolysiloxane and an alkenyl group-containing epoxy compound, but the addition reaction may cause a polymerization reaction of the epoxy group as a side reaction. In some cases, the viscosity of the product was remarkably increased or gelled.
  • an addition reaction between an organohydrogenpolysiloxane containing a hydroxyl group-containing organopolysiloxane resin and an alkenyl group-containing epoxy compound is caused by an increase in viscosity due to side reactions during the addition reaction due to the influence of the hydroxyl group-containing organopolysiloxane resin. The tendency of gelation was remarkable.
  • the present inventors have conducted a cyano group-containing organic compound in an addition reaction between an organohydrogenpolysiloxane containing a hydroxyl group-containing organopolysiloxane resin and an alkenyl group-containing epoxy compound.
  • (SiO 4/2 ) unit and (R 1 3 SiO 1/2 ) unit (wherein R 1 is the same or different, 1 to 12 carbon atoms having no hydroxyl group or aliphatic unsaturated bond.
  • the main component is a valence hydrocarbon group), and the ratio of (R 1 3 SiO 1/2 ) units to (SiO 4/2 ) units is 0.6 to 1.2 in terms of molar ratio.
  • An organopolysiloxane resin having a total content of bonded hydroxyl groups of 0% by mass or more and 1.2% by mass or less and an organohydrogen (poly) siloxane are dehydrogenated in the presence or absence of a cyano group-containing organic compound.
  • an alkenyl group-containing epoxy compound is blended with the condensation product subjected to the condensation reaction or a mixture of the organopolysiloxane resin and organohydrogen (poly) siloxane, and the condensate and / or Or Cationic polymerizable organopolysiloxane obtained by addition reaction of SiH group in ganohydrogen (poly) siloxane and alkenyl group in alkenyl group-containing epoxy compound is more effective than conventional cationic polymerizable organopolysiloxane.
  • the release sheet obtained using the release radiation curable silicone composition containing the cationic polymerizable organopolysiloxane as a heavy release additive has a strong release effect and a stable release force over time.
  • the present invention provides the following method for producing a cationically polymerizable organopolysiloxane, a releasable radiation-curable silicone composition, a release sheet, a method for producing the same, and the like. 1.
  • the following (a1) component and (a2) component are subjected to a dehydrocondensation reaction in the presence or absence of the following (a3) component, or a mixture of the following (a1) component and (a2) component:
  • the following component (a4) is blended, and the SiH group remaining in the condensate of the component (a1) and component (a2) and / or the SiH group in component (a2):
  • a method for producing a cationically polymerizable organopolysiloxane which comprises subjecting an alkenyl group in the component to an addition reaction.
  • (A1) (SiO 4/2 ) unit and (R 1 3 SiO 1/2 ) unit (wherein R 1 is the same or different and has 1 to 12 carbon atoms having no hydroxyl group or aliphatic unsaturated bond) Is a monovalent hydrocarbon group), and the ratio of (R 1 3 SiO 1/2 ) units to (SiO 4/2 ) units is 0.6 to 1.2 in terms of molar ratio.
  • R 3 is the same or different, A monovalent hydrocarbon group having 1 to 10 carbon atoms, a ⁇ 2, b ⁇ 0, c ⁇ 0, d ⁇ 0, 2 ⁇ a + b + c + d ⁇ 3,000, and e ⁇ 1, f ⁇ 0, e + f ⁇ 3.)
  • A3 a cyano group-containing organic compound represented by the following general formula (3): R 4 -CN (3) (In the formula, R 4 is a monovalent hydrocarbon group having 1 to 15 carbon atoms which does not have an aliphatic unsaturated bond.)
  • (A1) The method for producing a cationically polymerizable organopolysiloxane according to 1, wherein the total content of hydroxyl groups in the component organopolysiloxane resin is 0% by mass or more and 0.6% by mass or less. 5).
  • (A3) The method for producing a cationically polymerizable organopolysiloxane according to 1, wherein the cyano group-containing organic compound as a component has a boiling point of 300 ° C. or lower under normal pressure. 6).
  • a releasable radiation-curable silicone composition comprising the cationically polymerizable organopolysiloxane obtained by the production method according to any one of 1 to 5 as a heavy release additive. 8).
  • a method for producing a release sheet wherein the release radiation curable silicone composition according to 7 is applied on a substrate and cured by irradiation with radiation.
  • a release sheet formed by forming a cured film of the peelable radiation-curable silicone composition according to 7 on a substrate.
  • the cationic polymerizable organopolysiloxane obtained by the production method of the present invention can suppress an increase in viscosity and gelation, and the cationic polymerizable organopolysiloxane can be used as a heavy release additive for a release sheet.
  • the release sheet obtained using the heavy release additive is more release than the release sheet obtained using the conventional heavy release additive, and the release force with time is more stable.
  • the method for producing a cationically polymerizable organopolysiloxane of the present invention uses the components (a1) to (a4) described later, and the SiOH group in the component (a1) in the presence or absence of the component (a3). And (a2) component (a4) in the presence of component (a3) in a condensate obtained by dehydrogenative condensation reaction of SiH group in component (a2) or a mixture of component (a1) and component (a2) below.
  • the SiH group remaining in the condensate and / or the SiH group in the component (a2) and the alkenyl group in the component (a4) are subjected to an addition reaction.
  • the cationic polymerizable organopolysiloxane is not limited to the organopolysiloxane obtained by addition-reacting the component (a4) to the condensate of the component (a1) and the component (a2), and the component (a2) includes the component (a4). It is defined to include a mixture of an organopolysiloxane obtained by addition reaction of components and the component (a1).
  • the component (a1) has (SiO 4/2 ) units (Q units) and (R 1 3 SiO 1/2 ) units (M units) as main components, and (R 1 3 SiO relative to (SiO 4/2 ) units.
  • the ratio of 1/2 ) units (M units / Q units) is 0.6 to 1.2 as a molar ratio, and the total content of hydroxyl groups bonded to silicon atoms is 0% by mass to 1.2% by mass.
  • An organopolysiloxane resin is an organopolysiloxane resin.
  • R 1 is the same or different monovalent hydrocarbon group having 1 to 12 carbon atoms which does not have a hydroxyl group or an aliphatic unsaturated bond, and specifically, a hydroxyl group, a methyl group, an ethyl group, a propyl group.
  • a methoxy substituted with a halogen-substituted alkyl group such as a 3,3,3-trifluoropropyl group, a perfluorobutylethyl group or a perfluorooctylethyl group substituted with a halogen atom such as fluorine or chlorine, or an alkoxy group.
  • R 1 is preferably a hydroxyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or an isobutyl group.
  • the ratio of M unit to Q unit is 0.6 to 1.2, preferably 0.65 to 1.1, and more preferably, as a molar ratio. 0.7 to 1.0.
  • the ratio of the M unit to the Q unit is less than 0.6, the viscosity of the reaction product becomes too high and the synthesis becomes difficult. If it exceeds 1.2, the degree of polymerization cannot be increased, so that the heavy peeling effect is also lowered.
  • the organopolysiloxane resin may contain R 1 2 SiO 2/2 units (D units) and R 1 SiO 3/2 units (T units) (R 1 is the same as above) as necessary.
  • D units R 1 2 SiO 2/2 units
  • T units R 1 SiO 3/2 units
  • the blending of these D units and T units is preferably 20 mol% or less, particularly preferably 10 mol% or less.
  • the total content of hydroxyl groups bonded to silicon atoms is 0% by mass to 1.2% by mass, preferably 0% by mass to 1.0% by mass, more preferably 0%.
  • the content is not less than mass% and not more than 0.8 mass%, more preferably not less than 0 mass% and not more than 0.6 mass%.
  • the hydroxyl group is derived from the raw material for producing the organopolysiloxane resin, and the contamination is usually unavoidable.
  • the organohydrogen (poly) siloxane as component (a2) is represented by the following average composition formula (1) and / or (2).
  • R 2 is the same or different hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and at least one of R 2 contains a hydrogen atom.
  • R 3 is the same or different, A monovalent hydrocarbon group having 1 to 10 carbon atoms, a ⁇ 2, b ⁇ 0, c ⁇ 0, d ⁇ 0, 2 ⁇ a + b + c + d ⁇ 3,000, and e ⁇ 1, f ⁇ 0, e + f ⁇ 3.
  • R 2 is the same or different hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms
  • R 3 is the same or different and has 1 to 10 carbon atoms. It is a monovalent hydrocarbon group.
  • these monovalent hydrocarbon groups having 1 to 10 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group, cycloalkyl groups such as cyclohexyl group, phenyl Groups, aryl groups such as tolyl groups, and 3,3,3-trifluoropropyl in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms such as fluorine and chlorine
  • halogen atoms such as fluorine and chlorine
  • An unsubstituted or substituted carbon group such as a group, a halogen-substituted alkyl group such as a perfluorobutylethyl group or a perfluorooctylethyl group, an alkoxy-substituted alkyl group such as a methoxypropyl group or an e
  • R 2 is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or an isobutyl group
  • R 3 is preferably a methyl group, an ethyl group, a propyl group or an isopropyl group.
  • R 2 at least 1, preferably 2 to 50 contain hydrogen atoms.
  • A, b, c, d in the average composition formula (1) are a ⁇ 2, b ⁇ 0, c ⁇ 0, d ⁇ 0, 2 ⁇ a + b + c + d ⁇ 3,000, preferably 2 ⁇ a ⁇ 4. 0 ⁇ b ⁇ 1,000, 0 ⁇ c ⁇ 1, 0 ⁇ d ⁇ 1, 2 ⁇ a + b + c + d ⁇ 1,002. Further, e and f in the average composition formula (2) are e ⁇ 1, f ⁇ 0, e + f ⁇ 3, preferably 1 ⁇ e ⁇ 15, 0 ⁇ f ⁇ 10, 3 ⁇ e + f ⁇ 25. .
  • A, b, c, d, e, and f in the average composition formula (1) and / or the average composition formula (2) are preferably such that the viscosity of the organohydrogen (poly) siloxane at 25 ° C. is 1 to 20,000 mPa ⁇ S, more preferably a number with a viscosity of 5 to 10,000 mPa ⁇ s.
  • the viscosity is a value measured with a BM type rotational viscometer.
  • the silicon atoms substituted with hydrogen atoms in the total siloxane units are preferably 2 to 100 mol%, preferably 2 to 70 mol% in the total silicon atoms.
  • the hydrogen atom bonded to the silicon atom is bonded to both of the molecular chain end and the molecular chain (side chain). Also good.
  • the SiOH group in the hydroxyl group-containing organopolysiloxane resin (a1) and the SiH group in the organohydrogen (poly) siloxane (a2) are subjected to a dehydrogenative condensation reaction.
  • the component (a1) does not contain SiOH groups (that is, when the total content of SiOH groups is 0% by mass)
  • the dehydration condensation reaction is not necessary, so the components (a1) and (a2) are mixed. Just do it.
  • the proportion of the organopolysiloxane resin (a1) and the organohydrogen (poly) siloxane (a2) used is the mass ratio (a1) of the organopolysiloxane resin (a1) and the organohydrogen (poly) siloxane (a2).
  • / (A2) is preferably from 1/99 to 95/5, more preferably from 2/98 to 90/10, still more preferably from 5/95 to 80/20. If the ratio of the organopolysiloxane resin (a1) is less than 1/99, the heavy release ability may be insufficient when the cationically polymerizable organopolysiloxane of the present invention is used as a heavy release additive. If it is more, the curability and the residual adhesion rate may decrease.
  • the molar ratio of the hydroxyl group of the organopolysiloxane resin (a1) containing the hydroxyl group to the SiH group of the organohydrogen (poly) siloxane (a2) ((a2) SiH group) / (A1) OH group) is preferably 2 or more and 10,000 or less, more preferably 4 or more and 8,000 or less, and still more preferably 5 or more and 6,000 or less.
  • the molar ratio is less than 2, a large amount of SiH groups are consumed by the condensation reaction, so that the amount of epoxy groups in the cationically polymerizable organopolysiloxane obtained by the addition reaction after the condensation reaction is reduced, and the cationic polymerizability is lowered. May end up.
  • the dehydrogenation condensation reaction of the component (a1) and the component (a2) uses a dehydrogenation condensation catalyst.
  • the catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and alcohol, a reaction product of chloroplatinic acid and an olefin compound, a reaction product of chloroplatinic acid and a vinyl group-containing siloxane, and the like.
  • platinum-based catalysts platinum-based catalysts.
  • the amount of the catalyst added is not particularly limited, but is preferably 0.01 to 5% by mass based on the total mass of the hydroxyl group-containing organopolysiloxane resin (a1) and the organohydrogen (poly) siloxane (a2). More preferably, the content is 0.02 to 4% by mass, and still more preferably 0.05 to 3% by mass.
  • Solvents include aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane and octane, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and isobutyl acetate, or a mixture thereof. Solvents can be used.
  • the dehydrogenative condensation reaction of the above components (a1) and (a2) is usually carried out at 20 to 300 ° C., but the reaction proceeds faster when heated to 40 ° C. or higher.
  • the reaction time is not particularly limited, but is preferably 0.1 to 10 hours.
  • the reaction atmosphere may be either air or inert gas.
  • the alkenyl group-containing epoxy compound (a4) is blended, The SiH group remaining in the condensate and / or the SiH group in the component (a2) is added to the alkenyl group in the alkenyl group-containing epoxy compound (a4).
  • the component (a3) does not participate in the condensation reaction, it may be added before the components (a1) and (a2) are condensed or added after the condensation reaction of the components (a1) and (a2). However, it is preferable to add the component (a3) after the condensation reaction of the component (a1) and the component (a2).
  • the (a3) component cyano group-containing organic compound is represented by the following general formula (3).
  • R 4 -CN (3) (In the formula, R 4 is a monovalent hydrocarbon group having 1 to 15 carbon atoms which does not have an aliphatic unsaturated bond.)
  • R 4 is a monovalent hydrocarbon group having 1 to 15 carbon atoms that does not have an aliphatic unsaturated bond.
  • An alkyl group such as a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, a tolyl group, and a naphthyl group, or a part or all of hydrogen atoms bonded to carbon atoms of these groups may be An unsubstituted or substituted carbon number of 1 to 15 having no aliphatic unsaturated bond, such as a cyanoethyl group, a 3-chloropropyl group, or a 3,3,3-trifluoropropyl group, substituted with a group or a halogen atom;
  • the cationically polymerizable organopolysiloxane obtained after the addition reaction described later can be made solvent-free, in which case it is necessary to remove the cyano group-containing organic compound from the reaction mixture.
  • the method of distilling together with the used solvent or low-boiling substances under heating and reduced pressure can be used. Therefore, if the cyano group-containing organic compound has a boiling point under normal pressure, preferably 300 ° C. or lower, and more preferably 250 ° C. or lower, distillation after the addition reaction is facilitated.
  • the amount of the cyano group-containing organic compound used is 10 mass ppm or more, preferably 100 mass ppm or more, more preferably 200 mass ppm or more of the alkenyl group-containing epoxy compound (a4) described later.
  • the upper limit is not particularly limited, but is usually preferably 10% by mass or less.
  • alkenyl group-containing epoxy compound as component (a4) examples include compounds represented by the following formulas (a4-1) to (a4-7), but preferably the following formulas (a4-1) and (a4): -2), a compound represented by (a4-4), (a4-6) or (a4-7), more preferably the following formula (a4-1), (a4-6) or (a4-7) It is a compound shown by these.
  • the use ratio of the containing epoxy compound (a4) is such that the number of alkenyl groups in the alkenyl group-containing epoxy compound is larger than the total number of SiH groups remaining in the condensate and / or SiH groups in the component (a2).
  • the molar ratio of the alkenyl group / SiH group is 1.0 or more and 2.0 or less, preferably 1.05 or more and 1.8 or less, and more preferably 1.1 or more and 1.5 or less. It is desirable. If the molar ratio is too small, the addition reaction may not be able to proceed completely. If the molar ratio is too large, the addition reaction rate may not be improved.
  • the addition reaction is carried out using a catalytic amount of an addition reaction catalyst.
  • a platinum-based catalyst as a dehydrogenation condensation catalyst is present, it is not necessary to add a new addition reaction catalyst. It is advantageous because the following addition reaction can be carried out by adding the cyano group-containing organic compound (a3) and the alkenyl group-containing epoxy compound (a4) to the performed reaction vessel.
  • the addition reaction catalyst include the above platinum-based catalysts.
  • the amount of the catalyst used for this addition reaction may be an effective amount, but platinum is used relative to the total mass of the condensate obtained above and / or the component (a2) and the component (a4). It is preferably 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, still more preferably 0.5 to 20 ppm in terms of the mass of the group metal.
  • the addition reaction is carried out in the solvent used in the dehydrogenative condensation reaction as necessary. This addition reaction is usually carried out at 20 to 300 ° C., but the reaction proceeds faster when heated to 40 ° C. or higher.
  • the reaction time is not particularly limited, but is preferably 10 minutes to 24 hours.
  • the reaction atmosphere may be either air or inert gas.
  • the viscosity of the cationically polymerizable organopolysiloxane thus obtained at 25 ° C. is preferably 50 to 20,000 mPa ⁇ s, particularly preferably 100 to 15,000 mPa ⁇ s.
  • the amount of epoxy groups in the cationically polymerizable organopolysiloxane obtained in the present invention is such that the proportion of silicon atoms bonded with epoxy group-containing organic groups is 1 to 40 mol%, preferably 3 to 30 mol%, based on the total silicon atoms. Preferably, it is 5 to 25 mol%. If it is less than 1 mol%, the curability and the residual adhesion rate may decrease. When it exceeds 40 mol%, it will be heavy peeling more than necessary, and peeling from an adhesive substance may become impossible.
  • the amount of epoxy groups is shown by the ratio of the silicon atom which the epoxy group containing organic group couple
  • a Hiranuma automatic titration device COM-1750S manufactured by Hiranuma Sangyo Co., Ltd. is effective for measuring the epoxy equivalent.
  • the epoxy equivalent of the resulting cationically polymerizable organopolysiloxane is preferably 500 to 3,000 g / mol.
  • the cationic polymerizable organopolysiloxane obtained by the production method of the present invention can be suitably used as a heavy release additive for a release sheet, and the cationic polymerizable organopolysiloxane of the present invention alone or with this
  • different kinds of cationically polymerizable organopolysiloxanes can be mixed, and a photoacid generator can be further added to obtain a releasable radiation curable silicone composition.
  • the different kind of cationically polymerizable organopolysiloxane may be any cationically polymerizable organopolysiloxane that does not contain a resin component, but is preferably a known one described in Japanese Patent No. 3384268 and Japanese Patent Application Laid-Open No. 2015-168721. Cationic polymerizable organopolysiloxane and the like can be used.
  • the amount of the different kind of cationically polymerizable organopolysiloxane used is not particularly limited. For example, it is 0 to 99 parts by weight, particularly 5 to 95 parts by weight, based on 100 parts by weight of the cationically polymerizable organopolysiloxane of the present invention. preferable.
  • a known onium salt photoacid generator described in Japanese Patent No. 6195413 can be used.
  • the amount of the photoacid generator used is not particularly limited.
  • the photoacid generator is used in an amount of 0.1 to 100 parts by mass with respect to a total of 100 parts by mass of the cationically polymerizable organopolysiloxane of the present invention or a different type of cationically polymerizable organopolysiloxane.
  • the amount is preferably 10 parts by mass, particularly 0.2 to 8 parts by mass.
  • the peelable radiation curable silicone composition includes, as optional components, an epoxy-based diluent, a vinyl ether-based diluent, an adhesion improver for a substrate, other types of organopolysiloxane, a leveling agent, a filler, and an antistatic agent.
  • Agents, flame retardants, antifoaming agents, pigments, flow regulators, light stabilizers, non-reactive resins, etc. may be added, or they may be diluted with an organic solvent.
  • the amount of the optional component added can be a normal amount as long as the effects of the present invention are not hindered.
  • the reason why the heavy release effect is stronger than that of a conventional heavy release additive is usually as follows. Siloxane undergoes cationic polymerization due to ring-opening polymerization of epoxy groups, and the formed film is given release, but organopolysiloxane resin becomes a heavy release component, and the amount of organopolysiloxane resin present on the cured film The greater the amount, the more the cured film will be peeled off.
  • the ring-opening polymerization of epoxy groups can also participate in the reaction of compounds having active hydrogen, but if a large amount of SiOH groups in the organopolysiloxane resin are contained, these will participate in the ring-opening polymerization of epoxy groups and cure. Since the organopolysiloxane resin is taken into the film, the organopolysiloxane resin cannot be deposited on the film surface, and the heavy peeling effect is reduced.
  • the amount of SiOH in the organopolysiloxane resin used in the production method of the present invention is as small as 0 to 1.2% by mass, the organopolysiloxane resin is incorporated into the film formed from the ring-opening polymerization of the epoxy group. Since it is difficult, it becomes heavy peeling compared with the conventional heavy release additive of cationically polymerizable organopolysiloxane.
  • Cationic polymerizable organopolysiloxanes that have undergone a polymerization reaction due to ring opening of epoxy groups due to side reactions that occur during the addition reaction of organohydrogen (poly) siloxanes and alkenyl group-containing epoxy compounds are increased in viscosity and gelled.
  • a release sheet prepared by curing a release radiation curable silicone composition containing a cationically polymerizable organopolysiloxane containing these byproducts has a migration amount because the ring-opened epoxy group cannot participate in cationic polymerization. It rises and light peeling occurs.
  • the presence of a cyano group-containing organic compound at the time of the addition reaction can suppress the polymerization reaction due to the opening of the epoxy group during the addition reaction described above. There is no increase in the migration amount due to the epoxy group and the effect of light peeling. Therefore, the cationically polymerizable organopolysiloxane produced using the production method of the present invention is considered to have a stronger heavy release effect than conventional heavy release additives when used as a heavy release additive for release sheets.
  • the peelable radiation curable silicone composition is applied onto various substrates and cured by irradiation to form a cured film having a peelability to obtain a release sheet having the peelability imparted to the substrate.
  • the substrate is not particularly limited, and various commonly used substrates can be used.
  • glassine paper, clay coated paper, fine paper, polyethylene laminated paper, polyester film, polystyrene film, polyethylene film examples thereof include plastic films such as polypropylene films, transparent resins such as polycarbonate, and metal foils such as aluminum foil.
  • the coating method of the peelable radiation curable silicone composition can be used as the coating method of the peelable radiation curable silicone composition.
  • the coating amount of the releasable radiation-curable silicone composition is usually about 0.05 to 3 g / m 2 .
  • the radiation energy ray is preferably a high-pressure or ultra-high pressure mercury lamp, metal halide lamp, xenon lamp, carbon arc lamp, fluorescent lamp, semiconductor solid laser, argon Energy rays in the ultraviolet to visible light region (about 100 to about 800 nm) obtained from a laser, He—Cd laser, KrF excimer laser, ArF excimer laser, F 2 laser, or the like are used.
  • a radiation light source having a strong light intensity of 200 to 400 nm is preferable.
  • radiation having high energy such as electron beam and X-ray can be used.
  • the irradiation time of radiation energy is usually about 0.1 to 10 seconds at room temperature (25 ° C.).
  • the film thickness of the releasable radiation curable silicone composition is low when the energy ray permeability is low. If it is thick, it may be preferable to spend more time. If necessary, after the irradiation with energy rays, after-curing by heating at room temperature (25 ° C.) to 150 ° C. for several seconds to several hours is also possible.
  • the physical properties in the table are measured by the following test methods.
  • the viscosity is a value at 25 ° C. measured with a BM type rotational viscometer
  • the epoxy equivalent is a value measured with a Hiranuma automatic titration device COM-1750S manufactured by Hiranuma Sangyo Co., Ltd.
  • Me in a structural formula shows a methyl group and Ep shows the following epoxy functional group.
  • reaction solution was distilled under reduced pressure at 100 ° C., 20 mmHg for 3 hours to obtain a cationically polymerizable organopolysiloxane (A1-1) having an average epoxy equivalent of 900 g / mol and a viscosity at 25 ° C. of 390 mPa ⁇ s. .
  • Table 1 shows the results of Synthesis Examples 1 to 7 and Comparative Synthesis Examples 1 to 4.
  • the cationically polymerizable organopolysiloxanes of Synthesis Examples 1 to 7 obtained by the production method of the present invention had a low viscosity without gelation.
  • the cationically polymerizable organopolysiloxanes of Comparative Synthesis Examples 1 to 4 are cases where no cyano group-containing organic compound is added during the addition reaction, but have a higher viscosity than the cationically polymerizable organopolysiloxanes of the above Synthesis Examples. .
  • peelable radiation curable silicone composition After preparing a peelable radiation curable silicone composition containing a heavy release additive, it was applied to PE laminated paper at a coating amount of about 0.8 g / m 2 by roll coating to obtain a coating film. The obtained coating film was irradiated with ultraviolet rays with an irradiation amount of 75 mJ / cm 2 using two 80 W / cm high-pressure mercury lamps to form a cured film. A 25 mm wide polyester adhesive tape TESA-7475 (manufactured by tesa, acrylic adhesive) was applied to the surface of the cured film, and a 2 kg roller was reciprocated once to make a pressure-sensitive adhesive sample. The sample was aged at 25 ° C.
  • the sample was aged at 25 ° C. for 20 to 24 hours while applying a load of 70 g / cm 2 . Thereafter, the bonded polyester pressure-sensitive adhesive tape was peeled off at an angle of 180 ° using a tensile tester at a peeling speed of 0.3 m / min, and the polyester pressure-sensitive adhesive tape was attached to a SUS plate. A 2 kg roller was reciprocated once for pressure bonding, and the force (Y) required to peel the polyester adhesive tape after standing at 25 ° C. for 30 minutes was measured. Measure the force (Z) required to peel the sample polyester adhesive tape from the SUS plate without applying the polyester adhesive tape to the cured film and apply the same treatment to the SUS plate. The value obtained by dividing by (Z) is the residual adhesion rate, and the results are shown in Table 2.
  • Example 1 50 parts by mass of the cationically polymerizable organopolysiloxane (A1-1) synthesized in Synthesis Example 1 and a mixture of compounds represented by the following average composition formulas (aa) and (ab) as a release modifier: 50 parts by mass of a cationically polymerizable organopolysiloxane (Y-1) having an average epoxy equivalent of 1,100 g / mol and a viscosity at 25 ° C.
  • silicone composition 1 150 mPa ⁇ s, a photoacid generator, and 50 parts by mass in isopropyl alcohol % Of dissolved bis- [4-nalkyl (C10 to C13) phenyl] iodonium hexafluoroantimonate solution (Z-1) (2.0 parts by mass) was uniformly mixed to obtain silicone composition 1.
  • the silicone composition 1 was cured by the method described above, and the peel force and the residual adhesion rate were measured.
  • Example 2 A silicone composition 2 was obtained by performing the same procedure as in Example 1 except that 50 parts by mass of the cationically polymerizable organopolysiloxane (A1-2) synthesized in Synthesis Example 2 was used. This silicone composition 2 was cured by the method described above, and the peel strength and the residual adhesion rate were measured.
  • Example 3 A silicone composition 3 was obtained by performing the same procedure as in Example 1 except that 50 parts by mass of the cationically polymerizable organopolysiloxane (A1-3) synthesized in Synthesis Example 3 was used. The silicone composition 3 was cured by the above-described method, and the peel strength and the residual adhesion rate were measured.
  • Example 4 A silicone composition 4 was obtained by performing the same procedure as in Example 1 except that 50 parts by mass of the cationically polymerizable organopolysiloxane (A1-4) synthesized in Synthesis Example 4 was used. The silicone composition 4 was cured by the above-described method, and the peel force and the residual adhesion rate were measured.
  • Example 5 A silicone composition 5 was obtained by performing the same procedure as in Example 1 except that 50 parts by mass of the cationically polymerizable organopolysiloxane (A1-5) synthesized in Synthesis Example 5 was used. This silicone composition 5 was cured by the method described above, and the peel strength and the residual adhesion rate were measured.
  • Example 6 A silicone composition 6 was obtained by performing the same procedure as in Example 1 except that 50 parts by mass of the cationically polymerizable organopolysiloxane (A1-6) synthesized in Synthesis Example 6 was used. The silicone composition 6 was cured by the above-described method, and the peel strength and the residual adhesion rate were measured.
  • A1-6 cationically polymerizable organopolysiloxane
  • Example 7 A silicone composition 7 was obtained by performing the same procedure as in Example 1 except that 50 parts by mass of the cationically polymerizable organopolysiloxane (A1-7) synthesized in Synthesis Example 7 was used. The silicone composition 7 was cured by the above-described method, and the peel strength and the residual adhesion rate were measured.
  • Example 8 A procedure similar to that in Example 1 was performed except that 75 parts by mass of the cation polymerizable organopolysiloxane (A1-1) of Example 1 and 25 parts by mass of the cation polymerizable organopolysiloxane (Y-1) were used. A silicone composition 8 was obtained. This silicone composition 8 was cured by the method described above, and the peel strength and the residual adhesion rate were measured.
  • Example 9 A procedure similar to that in Example 7 was performed except that 75 parts by mass of the cation polymerizable organopolysiloxane (A1-7) and 25 parts by mass of the cation polymerizable organopolysiloxane (Y-1) were used. A silicone composition 9 was obtained. The silicone composition 9 was cured by the above-described method, and the peel strength and the residual adhesion rate were measured.
  • Example 1 A silicone composition 10 was obtained by performing the same procedure as in Example 1 except that 50 parts by mass of the cationically polymerizable organopolysiloxane (X1-1) synthesized in Comparative Synthesis Example 1 was used. The silicone composition 10 was cured by the method described above, and the peel strength and the residual adhesion rate were measured.
  • Example 2 A silicone composition 11 was obtained by performing the same procedure as in Example 1 except that 50 parts by mass of the cationically polymerizable organopolysiloxane (X1-2) synthesized in Comparative Synthesis Example 2 was used. This silicone composition 11 was cured by the above-described method, and the peel force and the residual adhesion rate were measured.
  • a silicone composition 12 was obtained by performing the same procedure as in Example 1 except that 50 parts by mass of the cationically polymerizable organopolysiloxane (X1-3) synthesized in Comparative Synthesis Example 3 was used.
  • the silicone composition 12 was cured by the above-described method, and the peel force and the residual adhesion rate were measured.
  • a silicone composition 13 was obtained by performing the same procedure as in Example 1 except that 50 parts by mass of the cationically polymerizable organopolysiloxane (X1-4) synthesized in Comparative Synthesis Example 4 was used. This silicone composition 13 was cured by the method described above, and the peel strength and the residual adhesion rate were measured.
  • Comparative Example 5 A procedure similar to that in Comparative Example 1 was performed except that 75 parts by mass of the cationic polymerizable organopolysiloxane (X1-1) of Comparative Example 1 and 25 parts by mass of the cationic polymerizable organopolysiloxane (Y-1) were used. A silicone composition 14 was obtained. This silicone composition 14 was cured by the method described above, and the peel force and the residual adhesion rate were measured.

Abstract

L'invention concerne un organopolysiloxane polymérisable par voie cationique obtenu par : incorporation d'un composé époxy alcénylé (a4) en présence d'un composé organique contenant un groupe cyano (a3) soit dans un condensat obtenu en soumettant à la fois une résine d'organopolysiloxane (a1) comprenant Q unités et M unités en tant que composants principaux, ayant un rapport molaire M/Q de 0,6 à 1,2, et ayant une teneur en groupes SiOH de 0 à 1,2 % en masse et un organohydrogène (poly)siloxane (a2) à une condensation avec déshydrogénation en présence ou en l'absence du composé (a3) ou dans un mélange des ingrédients (a1) et (a2) ; et le fait d'amener les groupes SiH dans le condensat et/ou l'ingrédient (a2) à subir une réaction d'addition avec les groupes alcényle contenus dans l'ingrédient (a4). Cet organopolysiloxane polymérisable par voie cationique a un effet fortement antiadhésif plus élevé que les organopolysiloxanes polymérisables par voie cationique classiques, peut être empêché de présenter une augmentation de la viscosité ou de la gélification, et est par conséquent approprié pour une utilisation en tant qu'additif fortement antiadhésif pour des feuilles anti-adhésives.
PCT/JP2019/016482 2018-05-09 2019-04-17 Procédé de production d'organopolysiloxane polymérisable par voie cationique, additif fortement antiadhésif, composition de silicone durcissable par rayonnement amovible, feuille anti-adhésive et procédé de production associé WO2019216141A1 (fr)

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