WO2015198827A1 - オルガノポリシロキサン架橋物及びその製造方法、並びにミスト防止剤及び無溶剤型剥離紙用シリコーン組成物 - Google Patents
オルガノポリシロキサン架橋物及びその製造方法、並びにミスト防止剤及び無溶剤型剥離紙用シリコーン組成物 Download PDFInfo
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- 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
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- C08G77/08—Preparatory processes characterised by the catalysts used
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- 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
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- 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
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- 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
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- 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
- C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- 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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- 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
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2483/00—Presence of polysiloxane
- C09J2483/005—Presence of polysiloxane in the release coating
Definitions
- the present invention relates to a crosslinked organopolysiloxane and a method for producing the same.
- the present invention reduces the amount of mist generated in the coater head when a solvent-free release paper silicone composition is applied to a substrate such as paper or film using a high-speed rotating roll.
- the present invention relates to a mist preventing agent used by adding to the solvent, and a solvent-free silicone composition for release paper formed by blending this mist preventing agent.
- the gel-like organopolysiloxane cross-linked product is used for cosmetics, coating of electrical wiring connection sites, etc., but both are solid materials having no fluidity. For this reason, it does not dissolve in a solvent, and a long pulverization step is required for blending in cosmetics and resins.
- silicone oil dispersion of silicone gel is used.
- a solid silicone gel is prepared by an addition reaction and then dispersed in silicone oil while being pulverized. This manufacturing method is time-consuming, and solid silicone gel does not proceed any further even if there is an unreacted functional group in the vicinity of the site that has become solid due to the reaction. The crosslink density changed each time it was produced, and it was difficult to control the physical properties.
- silicone oil or silicone gum having a high polymerization degree is dispersed in a resin for the purpose of increasing fluidity at the time of molding, preventing dirt and imparting slipperiness.
- Silicone oil with a low degree of polymerization is excellent in the effect of increasing fluidity and slipperiness, but the silicone oil bleeds out to the surface, so that the surface becomes slimy.
- gum-like silicone having a high degree of polymerization is used, but it takes time and effort to form a master batch in advance for uniform dispersion.
- most of the added silicone is embedded in the resin, only a part of the surface is involved in the action, and the efficiency is poor.
- a solid silicone gel or resin there are many components that remain in the resin, and the compatibility with the resin is poor, so that the dispersion is poor and the mechanical strength often decreases. Also, the surface modification effect is poor.
- a cured film of an organopolysiloxane composition is formed on the base material surface to impart release characteristics.
- the peelable film formation method by addition reaction is excellent in curability and can respond to various peel characteristics requirements from low speed peel to high speed peel. It is widely used.
- the solventless type has no solvent to be removed by volatilization and has a high flash point. Therefore, in mass production, high-speed coating is performed to increase productivity. However, when solvent-free high-speed coating is performed, mist is generated. In order to solve this mist problem, various mist inhibitors shown below have been proposed.
- the mist inhibitor disclosed in JP-A-2006-290919 is a condensation reaction product of both ends silanol-blocked diorganopolysiloxane and organohydrogenpolysiloxane by a tin catalyst.
- a condensation reaction it is difficult to control the reaction, and the difference in the polymerization degree of the reaction product due to LOT is severe.
- the higher the degree of polymerization the higher the mist prevention effect, but a gel-like product can be formed and mixing with the release paper silicone is difficult.
- the tin catalyst is concerned about toxicity, and if used in a silicone composition for addition-type release paper, it becomes a catalyst poison of a platinum catalyst and inhibits curing.
- the mist prevention agent disclosed in JP-T-2006-506509 is a partially substituted hydride silicone obtained by partially reacting an organohydrogensilicon compound with a long-chain olefin and partially crosslinking an MQ resin containing a vinyl group.
- a compound. Patent Document 4 attempts to make siloxane containing Q units oily.
- MQ units are added to an organohydrogensilicon compound, gelation may occur due to LOT even with the same composition, and it is difficult to control the viscosity.
- the addition reaction rate of the MQ resin having a vinyl group is low, and after the completion of the reaction, the reaction may occur over time to increase the viscosity.
- the amount of platinum catalyst increases, and it can no longer be pre-mixed in the silicone composition for release paper as a mist preventing agent. Will get worse.
- JP-T-2006-506510 and JP-T-2006-508206 relate to a star-branched polymer as a mist inhibitor for coating, and the star-branched polymer is a silicon atom-bonded hydrogen atom.
- the mist inhibitor disclosed in Japanese Patent Application Laid-Open No. 2010-150537 includes branched organopolysiloxane oligomers and diorganosiloxane oligomers containing Q units (SiO 4/2 units) in a silicone composition for release paper. An equilibrium polymer is blended. Organopolysiloxane oligomers containing Q units are difficult to produce with controlled molecular weight, have large variations in molecular weight due to LOT, and are difficult to uniformly disperse by equilibration, so that a constant equilibrium compound can always be obtained. Have difficulty.
- JP 2010-502778 A has (a) an organosilicon compound having at least two unsaturated hydrocarbon functional groups per molecule and (b) at least two silylhydride functional groups per molecule.
- a branched polysiloxane component made from a copolymer with an organosilicon compound is blended with a silicone-based coating component (silicone composition for release paper) as a mist inhibitor.
- This reaction product often forms a gel, and the presence of the silicone gel causes unevenness or unevenness of the coating film.
- the platinum catalyst remains in the branched polysiloxane component, if a silylhydride functional group remains in the branched polysiloxane component, a dehydrogenation reaction occurs during storage, and the container may expand, and in severe cases, it may burst. Furthermore, when the amount of the control agent is small, an addition reaction may be caused to the silicone-based coating component during dispersion.
- JP 2006-290919 A Japanese Patent No. 5033293 Japanese Patent No. 5033294 JP 2006-506509 A JP 2006-506510 A Special table 2006-508206 gazette JP 2010-150537 A Special table 2010-502778
- the present invention has been made in view of the above circumstances, and an object thereof is to provide a crosslinked organopolysiloxane exhibiting intermediate properties between dimethylpolysiloxane oil and a gel-like crosslinked siloxane, and a method for producing the same.
- the present invention is a mist prevention agent that is an additive for reducing the mist generated when a solvent-free release paper silicone composition is applied to a roll of a coating machine and the roll is rotated at a high speed and transferred.
- Another object of the present invention is to provide a solvent-free release paper silicone composition to which an agent and this mist inhibitor are added.
- an organopolysiloxane having two or more alkenyl groups in one molecule and an organopolysiloxane having two or more silicon-bonded hydrogen atoms in one molecule A compound having a siloxane unit represented by the following formula (3) is added to a silicone gel obtained by hydrosilylation reaction with hydrogen polysiloxane in the presence of a platinum group metal catalyst, and an acid or alkali catalyst is added. It was found that an oil-like organopolysiloxane obtained by equilibration in the above can obtain a cross-linked organopolysiloxane having a fluidity stably exhibiting intermediate properties between oil and gel.
- the mist prevention effect is high, but due to the presence of the silicone gel, unevenness on the coating surface is likely to occur. I noticed that it was a problem that it caused unevenness and became a separator that had no value as a product. On the other hand, when the addition reaction product has few cross-linking sites and an oily product is used, it is confirmed that the effect of preventing mist is low. On the other hand, the organopolysiloxane cross-linked product is used as a silicone composition for solventless release paper. As a result, it was found that the mist prevention effect was excellent, and the present invention was made.
- R 1 2 SiO 2/2 (3) (Wherein R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which does not have the same or different aliphatic unsaturated bond, or — (CH 2 ) a —CH ⁇ CH 2 (a is 0 or (The integer of 1 to 6) is selected from alkenyl groups, and the average degree of polymerization of the siloxane represented by formula (3) is 3 to 2,000.)
- the present invention provides the following organopolysiloxane crosslinked product, a method for producing the same, a mist inhibitor, and a solvent-free silicone composition for release paper.
- Cross-linked organopolysiloxane is characterized by cross-linked organopolysiloxane.
- R 1 2 SiO 2/2 (3) (Wherein R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which does not have the same or different aliphatic unsaturated bond, or — (CH 2 ) a —CH ⁇ CH 2 (a is 0 or (The integer of 1 to 6) is selected from alkenyl groups, and the average degree of polymerization of the siloxane represented by formula (3) is 3 to 2,000.) [2] The crosslinked organopolysiloxane according to [1], wherein 1 ⁇ ⁇ + ⁇ + ⁇ + ⁇
- a compound having a siloxane unit represented by formula (3) is octamethyltetrasiloxane, decamethylpentasiloxane, formula M 2 D n (M represents an R 3 SiO 1/2 unit, and D represents R 2 SiO 2/2 And R represents an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, each independently having an aliphatic unsaturated bond, and n is an integer of 0 to 200).
- the linear siloxane shown, and the formula M 2 + m D n T m (M, D, n are as described above, T is RSiO 3/2 unit, R is as described above, m is 1 to 10
- the weight average molecular weight of the organopolysiloxane represented by the formula (1) is 260 to 74,186
- the weight average molecular weight of the organohydrogenpolysiloxane represented by the formula (2) is 208 to 14,934.
- a siloxane composition prepared by diluting the crosslinked organopolysiloxane according to any one of [1] to [5] with a low-viscosity organopolysiloxane having a viscosity of 1 to 400 mPa ⁇ s at 25 ° C.
- a mist inhibitor comprising the crosslinked organopolysiloxane according to any one of [1] to [5] or the siloxane composition according to [6].
- R 1 2 SiO 2/2 (3) (Wherein R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which does not have the same or different aliphatic unsaturated bond, or — (CH 2 ) a —CH ⁇ CH 2 (a is 0 or (The integer of 1 to 6) is selected from alkenyl groups, and the average degree of polymerization of the siloxane represented by formula (3) is 3 to 2,000.)
- the organopolysiloxane cross-linked product according to the present invention exhibits intermediate properties between dimethyl silicone oil and gel-like siloxane cross-linked product, and is suitably used for various applications such as cosmetic silicone gels. It is valid.
- the amount of mist generated can be greatly reduced when transferring by rotating the roll at high speed.
- the mist inhibitor of the present invention does not contain a solid gel and does not contain an active platinum group metal catalyst, it may be mixed with an organohydrogenpolysiloxane having silicon-bonded hydrogen atoms. Dehydrogenation does not occur, there is no action to promote the crosslinking reaction over time, and it has an excellent mist prevention effect.
- the crosslinked organopolysiloxane of the present invention comprises an organopolysiloxane (I) having a structure represented by the following formula (1), an organohydrogenpolysiloxane (II) having a structure represented by the following formula (2), and Per 1,000 mol of siloxane units obtained by adding and equilibrating compound (IV) having a siloxane unit represented by the following formula (3) to silicone gel (III) obtained by hydrosilylation reaction of It consists of organopolysiloxane (V) containing 0.1-50 mol of silethylene bonds.
- R 1 2 SiO 2/2 (3) (Wherein R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which does not have the same or different aliphatic unsaturated bond, or — (CH 2 ) a —CH ⁇ CH 2 (a is 0 or (The integer of 1 to 6) is selected from alkenyl groups, and the average degree of polymerization of the siloxane represented by formula (3) is 3 to 2,000.)
- organopolysiloxane (I) having a structure represented by the following formula (1) and the organohydrogenpolysiloxane (II) having a structure represented by the following formula (2) will be described.
- M, M Vi , D, D Vi , T, T Vi , M H , D H , T H , and Q are units shown below.
- Q SiO 4/2
- each R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, which does not have an aliphatic unsaturated bond.
- Examples include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group; a cycloalkyl group such as a cyclohexyl group; a phenyl group, a naphthyl group, and a tolyl group Or a group in which a part of hydrogen atoms bonded to carbon atoms of these groups are substituted with a halogen atom, a cyano group, a hydroxyl group, or the like.
- P is an alkenyl group represented by — (CH 2 ) a —CH ⁇ CH 2 (a is 0 or an integer of 1 to 6), and preferably —CH ⁇ CH 2 .
- ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , and ⁇ are each independently 0 or a positive number.
- ⁇ , ⁇ , and ⁇ are not simultaneously 0, ⁇ + ⁇ + ⁇ is 2 or more, preferably 2 to 10, more preferably 2 to 5, and ⁇ , ⁇ , and ⁇ are not simultaneously 0, ⁇ + ⁇ + ⁇ is 2 or more, preferably 2 to 10, more preferably 2 to 5.
- ⁇ + ⁇ + ⁇ + ⁇ is preferably 1 to 1,000, more preferably 10 to 500. More preferably, it is 50-400.
- ⁇ is particularly preferably 1 to 1,000, more preferably 10 to 500, and still more preferably 50 to 400.
- ⁇ is preferably 0 to 20, more preferably 0 to 10, and still more preferably 0 to 5.
- ⁇ is preferably from 0 to 50, particularly preferably from 0 to 10, and ⁇ is preferably from 0 to 5, particularly preferably from 0 to 1.
- ⁇ + ⁇ + ⁇ is preferably 1 to 200, more preferably 10 to 150, and still more preferably. 20 to 100.
- ⁇ is preferably 1 to 200, more preferably 10 to 150, and still more preferably 20 to 100.
- ⁇ is preferably 0 to 20, more preferably 0 to 10, and still more preferably 0 to 5.
- ⁇ is preferably 0 to 50, more preferably 0 to 10.
- the organopolysiloxane (I) represented by the formula (1) is an organopolysiloxane having 2 or more, preferably 2 to 10 silicon atom-bonded vinyl groups in one molecule.
- the weight average molecular weight of the organopolysiloxane is preferably 260 to 74,186, more preferably 408 to 7,586. If the weight average molecular weight is too small, the alkali equilibration reaction following the addition reaction may not proceed sufficiently. If it is too large, the gel may be soft and sticky and difficult to handle.
- a weight average molecular weight can be measured by the weight average molecular weight of polystyrene conversion by gel permeation chromatography (GPC) analysis (solvent: toluene) (hereinafter the same).
- organopolysiloxanes (I) include alkenyl group-containing siloxanes at both ends, alkenyl group-containing siloxanes at one end, alkenyl group-containing siloxanes at one end and side chains, alkenyl group-containing siloxanes at both ends, branched Mention may be made of terminal alkenyl group-containing siloxanes.
- the vinyl group content (mol / g) is preferably in the range of 0.00001 to 0.01 mol / g, and more preferably in the range of 0.0001 to 0.001 mol / g.
- the organohydrogenpolysiloxane (II) represented by the formula (2) is an organohydrogenpolysiloxane having 2 or more, preferably 2 to 100 silicon-bonded hydrogen atoms (SiH groups) in one molecule. is there.
- a silicone gel is formed by the addition reaction between the SiH group of the organohydrogenpolysiloxane (II) and the vinyl group of the organopolysiloxane (I).
- the weight average molecular weight of the organohydrogenpolysiloxane (II) is preferably 208 to 14,934, more preferably 874 to 5,000. If the weight average molecular weight is too small, the alkali equilibration reaction following the addition reaction may not proceed sufficiently. If the weight average molecular weight is too large, the gel may be soft and sticky and difficult to handle.
- organohydrogenpolysiloxane (II) specifically, both terminal hydrogen group-containing siloxane, side chain hydrogen group-containing siloxane, one terminal and side chain hydrogen group-containing siloxane, both terminals and side chain Examples include hydrogen group-containing siloxane, branched chain-containing both ends, and side chain hydrogen group-containing siloxane.
- the SiH group content is preferably in the range of 0.0001 to 0.1 mol / g, and more preferably in the range of 0.0001 to 0.01 mol / g.
- the amount of the organohydrogenpolysiloxane (II) used is the molar ratio of the SiH group in the organohydrogenpolysiloxane and the alkenyl group in the organopolysiloxane represented by the above formula (1) (SiH group: alkenyl). Group) is preferably from 0.8: 5 to 2: 1, more preferably from 1: 1.5 to 1.5: 1.
- the silicone gel (III) which is a reaction product in the first stage, has an organopolysiloxane (I) having a structure represented by the above formula (1) and a structure represented by the above formula (2). It can be synthesized by hydrosilylation (addition) reaction of the organohydrogenpolysiloxane (II) having a platinum group metal catalyst. This is a reaction in which a SiH group in the organohydrogenpolysiloxane (II) is added to a vinyl group in the organopolysiloxane (I) by a platinum group metal catalyst.
- platinum group metal catalyst a known catalyst used as an addition reaction catalyst can be used.
- platinum group metal-based catalysts include platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts. Of these, platinum-based catalysts are particularly preferably used.
- platinum catalyst include chloroplatinic acid, alcohol solution or aldehyde solution of chloroplatinic acid, complexes of chloroplatinic acid with various olefins or vinyl siloxane, and the like.
- the amount of the platinum group metal catalyst added is a catalytic amount, but considering the economical point, the platinum group metal is added to the total amount of the organopolysiloxane (I) and the organohydrogenpolysiloxane (II).
- the mass is preferably in the range of 0.1 to 100 ppm, and more preferably in the range of 0.5 to 5 ppm.
- a solvent that is soluble in an organopolysiloxane such as toluene or no solvent may be used, but octamethyltetra compound (IV) described later is used.
- a low-viscosity cyclic siloxane such as siloxane or decamethylpentasiloxane or a linear diorganopolysiloxane before the alkali equilibration step and use it as a solvent. In this case, the amount of solvent used is.
- the reaction temperature is preferably 50 to 140 ° C., particularly 60 to 120 ° C.
- the reaction time is preferably 1 to 8 hours, particularly 2 to 5 hours.
- a compound (IV) having a siloxane unit represented by the following formula (3) is further added to the silicone gel (III) obtained by the hydrosilylation reaction and equilibrated with an acid or alkali catalyst.
- an oily organopolysiloxane (V) can be obtained.
- R 1 2 SiO 2/2 (3) wherein R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which does not have the same or different aliphatic unsaturated bond, or — (CH 2 ) a —CH ⁇ CH 2 (a is 0 or (The integer of 1 to 6) is selected from alkenyl groups, and the average degree of polymerization of the siloxane represented by formula (3) is 3 to 2,000.
- the monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms having no aliphatic unsaturated bond represented by R 1 is methyl group, ethyl Group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group and other alkyl groups; cyclohexyl group and other cycloalkyl groups; phenyl group, naphthyl group and tolyl group and other aryl groups; or these And those obtained by substituting a part of the hydrogen atoms bonded to the carbon atom of the group with a halogen atom, a cyano group, a hydroxyl group or the like.
- R 1 is preferably a methyl group.
- the average degree of polymerization of the compound (IV) having a siloxane unit represented by the formula (3) is 3 to 2,000, preferably 3 to 100. If the average degree of polymerization is less than 3, the mist prevention effect may be low, and if it is too large, the viscosity may be too high to be suitable for use.
- an average degree of polymerization can be calculated
- the compound (IV) includes (R 1 3 SiO 1/2 ) structural unit, (R 1 1 SiO 3/2 ) structural unit (in the formula, R is the same as described above.) And (SiO 4/2 ) structural units, the total amount of which is preferably 0 to 50% by mass, more preferably 0 to 10% by mass, based on the mass of all siloxane units. It may be included in the range.
- Examples of the compound (IV) having a siloxane unit represented by the formula (3) include low-viscosity cyclic siloxanes such as octamethyltetrasiloxane and decamethylpentasiloxane, M 2 D n (M and D are the same as above) N is a linear siloxane such as 0 to 200, preferably 1 to 50), M 2 + m D n T m (M, D and T are the same as above. N is 0 to 200, preferably Is an integer of 1 to 50, m is an integer of 1 to 10, and preferably an integer of 1 to 3).
- the amount of the compound (IV) having a siloxane unit represented by the above formula (3) is represented by the organopolysiloxane (I) having the structure represented by the above formula (1) and the above formula (2).
- An amount sufficient to make the silicone gel (III) produced by the addition reaction with the organohydrogenpolysiloxane (II) having a structure liquid is sufficient, but in particular, the formula (1) and the formula (2) It is preferably 2 to 100 times by mass, more preferably 3 to 50 times by mass, and still more preferably 3 to 25 times by mass with respect to the crosslinking reaction product.
- the compound (IV) having a siloxane unit represented by the above formula (3) may be blended before the addition reaction as described above, or may be blended after the addition reaction and subjected to alkali equilibration. Good.
- An acid or alkali is used as a catalyst in the equilibration reaction.
- an acid catalyst or an alkali catalyst By using an acid catalyst or an alkali catalyst, a highly ionic siloxane bond can be cleaved and recombined, whereby an equilibrated product can be obtained.
- the acid catalyst include sulfuric acid, hydrochloric acid, phosphoric acid, activated clay, iron chloride, boric acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and the like.
- the alkali catalyst include KOH, CsOH, NaOH, (CH 3 ) 4 NOH, (nC 4 H 9 ) 4 POH, and metal siliconates such as potassium and phosphorus.
- the silicone gel material (III) is a hard gel having a high crosslinking density
- These catalysts are used in an amount of 10 to 3,000 ppm, preferably 50 to 2,000 ppm.
- the reaction by the above equilibration is preferably performed at a reaction temperature of 10 to 160 ° C., particularly 120 to 160 ° C., and a reaction time of 1 to 20 hours, particularly 2 to 10 hours.
- the organopolysiloxane (V) (cross-linked organopolysiloxane) obtained above did not contain a gel and was oily, and was measured using a B-type rotational viscometer of the organopolysiloxane (V).
- the viscosity at 25 ° C. is preferably 50 to 100,000 mPa ⁇ s, more preferably 100 to 50,000 mPa ⁇ s.
- the organopolysiloxane (V) obtained above has a silethylene bond content per 1,000 mol of siloxane units calculated from 1 H-NMR of 0.1 to 50 mol, preferably 1 to 30 mol. . If the content of the silethylene bond is too small, the effect of preventing mist is not observed, and if it is too large, the viscosity becomes too high and mixing becomes difficult.
- the viscosity of the said organopolysiloxane (V) (organopolysiloxane crosslinked material)
- it can be set as the siloxane composition diluted with the low viscosity organopolysiloxane.
- the viscosity in this case can be 100 to 200,000 mPa ⁇ s, in particular 100 to 10,000 mPa ⁇ s.
- the viscosity is a value at 25 ° C. measured using a B-type rotational viscometer (hereinafter the same).
- the low-viscosity organopolysiloxane to be diluted is preferably a low-viscosity organopolysiloxane which may contain an unsaturated group and has a viscosity at 25 ° C. of 1 to 400 mPa ⁇ s, more preferably 10 to 200 mPa ⁇ s.
- Specific examples of such low-viscosity organopolysiloxanes include dimethylpolysiloxane having a viscosity of 1 to 400 mPa ⁇ s, dimethylpolysiloxane having dimethylvinylsiloxy groups at both ends of the molecular chain, and methyl having vinyl groups in the side chains. Examples thereof include vinyl polysiloxane, dimethylpolysiloxane having dimethylhydroxysilyl groups at both ends, and phenylmethylpolysiloxane having a phenyl group in the side chain.
- the mist inhibitor of the present invention is composed of the organopolysiloxane (V) obtained above (that is, a crosslinked product of organopolysiloxane) or the above siloxane composition.
- the silicone composition for solvent-free release paper which contains the mist inhibitor of the present invention, (A) Organopolysiloxane having 2 or more silicon-bonded alkenyl groups in one molecule: 100 parts by mass (B) Organohydrogenpolysiloxane containing 3 or more silicon-bonded hydrogen atoms (SiH groups) in one molecule: 0.1 to 30 parts by mass (C) Platinum group metal catalyst: catalyst amount, (D) The mist inhibitor: 0.01 to 20 parts by mass, It is preferable that it is an addition reaction curable type silicone composition containing a reaction control agent (E) as necessary.
- the organopolysiloxane having 2 or more, preferably 2 to 50 alkenyl groups in one molecule of the component (A) has an alkenyl group at the terminal and / or side chain represented by the following general formula (4).
- the linear organopolysiloxane is preferably contained.
- R 2 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms which does not have the same or different aliphatic unsaturated bond, or — (CH 2 ) q —CH ⁇
- the unsubstituted or substituted monovalent hydrocarbon group having 1 to 12, preferably 1 to 6 carbon atoms not having an aliphatic unsaturated bond of R 2 includes, for example, a methyl group Alkyl groups such as ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group and dodecyl group; cycloalkyl groups such as cyclohexyl group; aryl groups such as phenyl group, naphthyl group and tolyl group; Or what substituted some hydrogen atoms couple
- Alkyl groups such as ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group and dodecyl group
- At least 50 mol% of the total number of R 2 is a methyl group in order to reduce the peeling force. Further, at least 2, preferably 2 to 50, more preferably 2 to 10 in all R 2 are alkenyl groups. p is 1 to 1,000, and preferably 10 to 300.
- the organohydrogenpolysiloxane containing three or more silicon-bonded hydrogen atoms (SiH groups) in one molecule of the component (B) is preferably represented by the following general formula (5). (Wherein R 3 is an unsubstituted or substituted monovalent hydrocarbon group, r is 1 to 300, s is 0 to 150, and exists in a ratio of r> s.)
- R 3 is an unsubstituted or substituted monovalent hydrocarbon group, preferably having 1 to 12 carbon atoms, particularly 1 to 6 carbon atoms, having no aliphatic unsaturated bond.
- monovalent hydrocarbon groups include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, octyl groups, decyl groups, dodecyl groups and other alkyl groups, and cyclohexyl groups and other cycloalkyl groups.
- R is 1 to 300, preferably 10 to 100.
- s is 0 to 150, preferably 0 to 50.
- R and s exist at a ratio of r> s.
- the blending amount of the component (B) is preferably 0.1 to 30 parts by mass, particularly preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A).
- the organohydrogenpolysiloxane of the component (B) is an organohydrogenpolysiloxane (component (B)) with respect to the total number of moles of alkenyl groups in the linear organopolysiloxane having an alkenyl group (component (A)).
- the number of moles of silicon-bonded hydrogen atoms (SiH group / alkenyl group) is preferably an amount corresponding to 1.5 to 2.5 times mole, more preferably 1.6 to 2.2 times mole. The corresponding amount.
- SiH group / alkenyl group compounding ratio is less than 1.5 times mol, curing may be insufficient, and when it exceeds 2.5 times mol, the change in peel strength with time may increase.
- platinum group metal catalyst of component (C) a known catalyst used as an addition reaction catalyst can be used.
- platinum group metal-based catalysts include platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts. Of these, platinum-based catalysts are particularly preferably used.
- platinum catalyst include chloroplatinic acid, alcohol solution or aldehyde solution of chloroplatinic acid, complexes of chloroplatinic acid with various olefins or vinyl siloxane, and the like.
- the addition amount of the platinum group metal catalyst is a catalyst amount, but the platinum group metal mass contained is preferably 10 to 1,000 ppm, more preferably 10 to 200 ppm with respect to the total amount of the components (A) and (B).
- Component (D) is the mist inhibitor, and the amount of the mist inhibitor is 0.01 to 20 parts by weight, particularly 0.1 to 5 parts by weight, based on 100 parts by weight of component (A). It is preferable. If the blending amount of the mist preventing agent is too small, the mist preventing effect may not be observed. If the blending amount is too large, the viscosity of the entire composition may become too high, or the peeling force may deviate from the target value.
- the (E) component reaction control agent is a component that is blended as necessary, and controls the catalytic activity of the platinum group metal catalyst.
- Various organic nitrogen compounds, organophosphorus compounds, acetylene compounds, oxime compounds, An organic chloro compound etc. are mentioned.
- acetylene series such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-penten-3-ol, and phenylbutynol
- Acetylene compounds such as alcohol, 3-methyl-3-pentene-1-in, 3,5-dimethyl-1-hexyne-3-in, these acetylene compounds and alkoxysilane or siloxane or hydrogensilane or Examples thereof include reactants with siloxane, vinyl siloxanes such as tetramethylvinylsiloxane cyclics, organic nitrogen compounds such as benzotriazole, other organic phosphorus compounds, oxime compounds, and organic chromium compounds.
- the blending amount in the case of blending the reaction control agent (E) is only required to obtain good treatment bath stability, and is generally 0 to 3% by weight, particularly 0.01 to 3% by weight with respect to the total composition amount.
- the amount is preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of component (C).
- Anti-mist additive added solvent-free release paper silicone composition contains other optional ingredients such as antioxidants, pigments, stabilizers, antistatic agents, antifoaming agents, adhesion improvers, silica and other inorganic fillers. , And can be blended as long as the object of the present invention is not impaired.
- a mist inhibitor-added solventless release paper silicone composition can be prepared by uniformly mixing the above-mentioned components according to a conventional method.
- the silicone composition for release paper is used as it is or after diluting with a suitable organic solvent, and then roll coating, reverse coating or gravure. After applying 0.01-100 g / m 2 on a substrate such as paper or film using a coating method such as a coat, the coating is cured on the substrate by heating at 50 to 200 ° C. for 1 to 120 seconds.
- the base material include glassine paper, polyethylene laminated paper, kraft paper, clay coated paper, mirror coated paper, and plastic films such as polypropylene, polyethylene, polyethylene terephthalate, and polyvinyl chloride.
- the mist prevention agent of this invention does not give any change to the peeling force of the cured product of the silicone composition for solventless release paper.
- the reaction was stopped when gelation occurred at 50 to 60 ° C., 29.9 g of linear dimethylpolysiloxane having vinyl groups at both ends represented by M Vi 2 D 585.32 was added, and the mixture was sufficiently stirred. Thereafter, 1,200 ppm of KOH was added, and an equilibration reaction was performed at 150 ° C. for 6 hours. After the temperature was lowered to 80 ° C., 0.2 g of ethylene chlorohydrin was added and neutralized, followed by concentration under reduced pressure at 150 ° C. for 2 hours under 2 mmHg conditions. The obtained product had a viscosity of 1,550 mPa ⁇ s and was oily. The silethylene bond per 1,000 mol of siloxane units calculated from 1 H-NMR was 6.2 mol.
- the reaction was stopped when gelation occurred at 50 to 60 ° C., and further 870 g of linear dimethylpolysiloxane represented by M 2 D 24 was added thereto, followed by stirring while grinding the gel with a homomixer at 2,000 rpm for 3 hours.
- the viscosity of the obtained product was 280 mPa ⁇ s, but a fine gel remained.
- the silethylene bond per 1,000 mol of siloxane units in the crosslinked product calculated from 1 H-NMR was 11.3 mol.
- the viscosity of the obtained silicone oil was 2,400 mPa ⁇ s.
- generation of hydrogen gas was confirmed over time with this silicone oil.
- the silethylene bond per 1,000 mol of siloxane units calculated from 1 H-NMR was 74.4 mol.
- Examples 1 to 3 Comparative Examples 1 to 4
- Various mist inhibitors prepared in the above synthesis examples were blended into the basic composition shown below, and various organopolysiloxane compositions were prepared by the following method and cured.
- the mist generation amount, peeling force, and residual adhesion rate of the organopolysiloxane composition were measured by the following methods.
- the viscosity of the final composition was measured by the above method. All the organopolysiloxane compositions were in a state of no problem with curability.
- the organopolysiloxane composition is applied to a polyethylene laminated paper base so as to be 0.9 to 1.1 g / m 2 and heated in a hot air dryer at 140 ° C. for 30 seconds. This was used as a separator for the following measurements.
- a silicone separator obtained by the above curing method was stored at 25 ° C. for 20 hours, and then a TESA-7475 tape bonded together was stored in a dryer at 70 ° C. with a load of 20 g / m 2 and stored for 20 hours.
- the sample TESA-7475 tape was peeled off at a 180 ° angle at 0.3 m / min using a tensile tester, and the force required for peeling was measured to obtain a peeling force (N / 25 mm). .
- the results are shown in Table 1.
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Abstract
Description
縮合反応は、反応コントロールが難しく、LOTによる反応物の重合度の差が激しい。重合度が高い程ミスト防止効果が高くなるが、ゲル状物ができるようになり、剥離紙用シリコーンへの混合が困難である。逆に重合度が低ければ、剥離紙用シリコーンへの混合は容易となるが、ミスト防止効果は低く、未反応物の移行が起こり、剥離力が軽くなる場合がある。また錫触媒は、毒性が懸念される上、付加型剥離紙用シリコーン組成物に用いると白金触媒の触媒毒となり、硬化を阻害するため使用は好ましくない。
しかし、ミスト防止剤中に残存する白金触媒により、SiH基/アルケニル基が4.6以上の場合は経時で脱水素が起こる危険性が高く、またキュアーに影響を与える場合や部位により架橋密度にムラができる場合がある。逆にアルケニル基/SiH基が4.6以上の場合は剥離紙用シリコーンのSiH基/アルケニル基の比率が低くなり、架橋密度が変わるため剥離力が変わってしまう。
特許文献4は、Q単位を含有するシロキサンをオイル状にしようとしたものである。MQ単位を有機水素ケイ素化合物に付加する場合、同じ配合でもLOTによりゲル化が起こる場合があり、粘度をコントロールすることが難しい。またビニル基を有するMQレジンの付加反応率は低く、反応終了後、経時で反応し、高粘度化する場合もある。ビニル基を有するMQレジンの付加反応率を高くしようとすると白金触媒量が多くなり、ミスト防止剤として剥離紙用シリコーン組成物中に予め配合することはできなくなり、使用時に添加する場合でもポットライフが悪化してしまう。
これらは反応物にゲルができやすく、粘着性及びオレフィン鎖の効果により、剥離力が高くなる場合がある。
Q単位を含有するオルガノポリシロキサンオリゴマーは、分子量をコントロールして製造することが難しく、LOTによる分子量のバラツキが大きい上、平衡化により均一分散させることが難しく、常に一定の平衡化合物を得ることが困難である。
この反応物はゲルが生成する場合が多く、シリコーンゲルの存在は塗膜の凹凸や不均一化を引き起こす。また分岐ポリシロキサン成分には白金触媒が残っているため、分岐ポリシロキサン成分中にシリルヒドリド官能基が残ると保管時に脱水素反応が起こり、容器が膨張、ひどいケースでは破裂する場合がある。更に制御剤量が少ない配合においては分散時にシリコーン系コーティング成分に付加反応を引き起こす場合がある。
また、本発明は、無溶剤型剥離紙用シリコーン組成物を塗工機のロールに塗布して高速でロールを回転し、転写する際に発生するミストを低減するための添加剤であるミスト防止剤、及びこのミスト防止剤を添加してなる無溶剤型剥離紙用シリコーン組成物を提供することを他の目的とする。
また、上記平衡化前のシリコーンゲル状物を無溶剤型剥離紙用シリコーン組成物に配合した場合、ミスト防止効果は高いが、シリコーンゲルの存在により、塗膜表面に凹凸ができやすく、塗工ムラを引き起こし、商品として価値の無いセパレーターとなってしまうことが問題であることに気が付いた。一方、上記付加反応物において、架橋部位が少なく、オイル状のものを用いた場合は、ミスト防止効果が低いことを確認する一方、上記オルガノポリシロキサン架橋物を無溶剤型剥離紙用シリコーン組成物に添加したところ、ミスト防止効果に優れることを見出し、本発明をなすに至った。
R1 2SiO2/2 (3)
(式中、R1は同一又は異種の脂肪族不飽和結合を有さない炭素原子数1~20の一価炭化水素基、又は-(CH2)a-CH=CH2(aは0又は1~6の整数)で表されるアルケニル基から選択される基である。式(3)で表されるシロキサンの平均重合度は3~2,000である。)
〔1〕
下記式(1)で表される構造を有するオルガノポリシロキサンと下記式(2)で表される構造を有するオルガノハイドロジェンポリシロキサンとをヒドロシリル化反応して得られるシリコーンゲル状物に、下記式(3)で表されるシロキサン単位を有する化合物を加えて平衡化することにより得られる、シロキサン単位1,000molあたりシルエチレン結合を0.1~50mol含有するオルガノポリシロキサンからなることを特徴とするオルガノポリシロキサン架橋物。
MαMVi βDγDVi δTεTVi ζQη (1)
MθMH ιDκDH λTμTH ν (2)
(式中、MはR3SiO1/2、MViはR2PSiO1/2、DはR2SiO2/2、DViはRPSiO2/2、TはRSiO3/2、TViはPSiO3/2、MHはR2HSiO1/2、DHはRHSiO2/2、THはHSiO3/2、QはSiO4/2であり、Rはそれぞれ独立に脂肪族不飽和結合を有さない炭素原子数1~12の非置換又は置換の一価炭化水素基であり、Pは-(CH2)a-CH=CH2(aは0又は1~6の整数)で表されるアルケニル基である。α、β、γ、δ、ε、ζ、η、θ、ι、κ、λ、μ、νはそれぞれ独立に0又は正の数であり、β、δ、ζが同時に0になることはなく、β+δ+ζ≧2で、ι、λ、νも同時に0になることはなく、ι+λ+ν≧2である。)
R1 2SiO2/2 (3)
(式中、R1は同一又は異種の脂肪族不飽和結合を有さない炭素原子数1~20の一価炭化水素基、又は-(CH2)a-CH=CH2(aは0又は1~6の整数)で表されるアルケニル基から選択される基である。式(3)で表されるシロキサンの平均重合度は3~2,000である。)
〔2〕
式(1)において、1≦α+γ+ε+η≦1,000であり、式(2)において、1≦θ+κ+μ≦200である〔1〕記載のオルガノポリシロキサン架橋物。
〔3〕
式(1)において、1≦γ≦1,000であり、式(2)において、1≦κ≦200である〔2〕記載のオルガノポリシロキサン架橋物。
〔4〕
式(3)で示されるシロキサン単位を有する化合物が、オクタメチルテトラシロキサン、デカメチルペンタシロキサン、式M2Dn(MはR3SiO1/2単位を示し、DはR2SiO2/2単位を示し、Rはそれぞれ独立に脂肪族不飽和結合を有さない炭素原子数1~12の非置換又は置換の一価炭化水素基であり、nは0~200の整数である。)で示される直鎖シロキサン、及び式M2+mDnTm(M、D、nは上記の通り、TはRSiO3/2単位を示し、Rは上記の通りである。mは1~10の整数である。)で示される分岐鎖シロキサンから選ばれるオルガノシロキサンである〔1〕~〔3〕のいずれかに記載のオルガノポリシロキサン架橋物。
〔5〕
式(1)で表されるオルガノポリシロキサンの重量平均分子量が260~74,186であり、また式(2)で表されるオルガノハイドロジェンポリシロキサンの重量平均分子量が208~14,934であることを特徴とする〔1〕~〔4〕のいずれかに記載のオルガノポリシロキサン架橋物。
〔6〕
〔1〕~〔5〕のいずれかに記載のオルガノポリシロキサン架橋物を、25℃における粘度が1~400mPa・sの低粘度オルガノポリシロキサンで希釈してなるシロキサン組成物。
〔7〕
〔1〕~〔5〕のいずれかに記載のオルガノポリシロキサン架橋物又は〔6〕記載のシロキサン組成物からなるミスト防止剤。
〔8〕
(A)1分子中に2個以上のケイ素原子結合アルケニル基を有するオルガノポリシロキサン:100質量部、
(B)1分子中に3個以上のケイ素原子結合水素原子を有するオルガノハイドロジェンポリシロキサン:0.1~30質量部、
(C)白金族金属系触媒:触媒量、
(D)〔7〕に記載のミスト防止剤:0.01~20質量部
を含有する無溶剤型剥離紙用シリコーン組成物。
〔9〕
下記式(1)で表される構造を有するオルガノポリシロキサンと下記式(2)で表される構造を有するオルガノハイドロジェンポリシロキサンとをヒドロシリル化反応してシリコーンゲル状物を製造した後、このシリコーンゲル状物を下記式(3)で表されるシロキサン単位を有する化合物を加えて平衡化することにより、シロキサン単位1,000molあたりシルエチレン結合を0.1~50mol含有するオルガノポリシロキサンを得ることを特徴とするオルガノポリシロキサン架橋物の製造方法。
MαMVi βDγDVi δTεTVi ζQη (1)
MθMH ιDκDH λTμTH ν (2)
(式中、MはR3SiO1/2、MViはR2PSiO1/2、DはR2SiO2/2、DViはRPSiO2/2、TはRSiO3/2、TViはPSiO3/2、MHはR2HSiO1/2、DHはRHSiO2/2、THはHSiO3/2、QはSiO4/2であり、Rはそれぞれ独立に脂肪族不飽和結合を有さない炭素原子数1~12の非置換又は置換の一価炭化水素基であり、Pは-(CH2)a-CH=CH2(aは0又は1~6の整数)で表されるアルケニル基である。α、β、γ、δ、ε、ζ、η、θ、ι、κ、λ、μ、νはそれぞれ独立に0又は正の数であり、β、δ、ζが同時に0になることはなく、β+δ+ζ≧2で、ι、λ、νも同時に0になることはなく、ι+λ+ν≧2である。)
R1 2SiO2/2 (3)
(式中、R1は同一又は異種の脂肪族不飽和結合を有さない炭素原子数1~20の一価炭化水素基、又は-(CH2)a-CH=CH2(aは0又は1~6の整数)で表されるアルケニル基から選択される基である。式(3)で表されるシロキサンの平均重合度は3~2,000である。)
本発明のミスト防止剤は、無溶剤型剥離紙用シリコーン組成物に少量添加することにより、高速でロールを回して転写を行う際、発生するミスト量を大幅に低減することができる。
更に、本発明のミスト防止剤は、固体状のゲルを含まず、また活性な白金族金属系触媒を含有しないため、ケイ素原子結合水素原子を有するオルガノハイドロジェンポリシロキサンと混合しておいても脱水素が起こらず、経時で架橋反応を促す作用がない上、優れたミスト防止効果を有するものである。
MθMH ιDκDH λTμTH ν (2)
(式中、MはR3SiO1/2、MViはR2PSiO1/2、DはR2SiO2/2、DViはRPSiO2/2、TはRSiO3/2、TViはPSiO3/2、MHはR2HSiO1/2、DHはRHSiO2/2、THはHSiO3/2、QはSiO4/2であり、Rはそれぞれ独立に脂肪族不飽和結合を有さない炭素原子数1~12の非置換又は置換の一価炭化水素基であり、Pは-(CH2)a-CH=CH2(aは0又は1~6の整数)で表されるアルケニル基である。α、β、γ、δ、ε、ζ、η、θ、ι、κ、λ、μ、νはそれぞれ独立に0又は正の数であり、β、δ、ζが同時に0になることはなく、β+δ+ζ≧2で、ι、λ、νも同時に0になることはなく、ι+λ+ν≧2である。)
R1 2SiO2/2 (3)
(式中、R1は同一又は異種の脂肪族不飽和結合を有さない炭素原子数1~20の一価炭化水素基、又は-(CH2)a-CH=CH2(aは0又は1~6の整数)で表されるアルケニル基から選択される基である。式(3)で表されるシロキサンの平均重合度は3~2,000である。)
MαMVi βDγDVi δTεTVi ζQη (1)
MθMH ιDκDH λTμTH ν (2)
M:R3SiO1/2、
MVi:R2PSiO1/2、
D:R2SiO2/2、
DVi:RPSiO2/2、
T:RSiO3/2、
TVi:PSiO3/2、
MH:R2HSiO1/2、
DH:RHSiO2/2、
TH:HSiO3/2、
Q:SiO4/2
また、Pは-(CH2)a-CH=CH2(aは0又は1~6の整数)で表されるアルケニル基であり、-CH=CH2であることが好ましい。
構造式で表すと、MVi 2Dγ、M2DγDVi δ、MVi 3DγT1、MVi 4DγT2、MVi 2DγDVi δ、MVi 2DγQ1、MαDγDVi δTVi ζ(但し、γは1~1,000、特に10~500、とりわけ50~400、δは2~20、特に2~10、とりわけ2~5、ζは1~20、特に1~10、とりわけ1~6)等を挙げることができる。更に具体的な構造例としては、MVi 2D10、MVi 2D100、M2D27DVi 3、M2D97DVi 3、M2D26DVi 4、M2D25DVi 5、M2D24DVi 6、M2D96DVi 4、M2D95DVi 5、MVi 3D100T1、MVi 4D100T2、MVi 2D97DVi 1、MVi 2D95DVi 3、M3D93DVi 3TVi 1等を挙げることができる。
また構造式で表すと、M2DH λ、M2DκDH λ、MH 2DκDH λ、MH 3DκT1、MθDκDH λTH ν(但し、κは1~200、特に10~150、とりわけ20~100、λは1~20、特に1~10、とりわけ1~5、θは3~22、特に3~12、とりわけ3~7、νは1~20、特に1~10、とりわけ1~5)等を挙げることができる。更に具体的な構造例としては、MH 2D10、MH 2D100、M2D27DH 3、M2D97DH 3、M2D26DH 4、M2D25DH 5、M2D24DH 6、M2D96DH 4、M2D95DH 5、MH 3D100T1、MH 4D100T2、MH 2D97DH 1、MH 2D95DH 3、M3D93DH 3TH 1等を挙げることができる。
R1 2SiO2/2 (3)
(式中、R1は同一又は異種の脂肪族不飽和結合を有さない炭素原子数1~20の一価炭化水素基、又は-(CH2)a-CH=CH2(aは0又は1~6の整数)で表されるアルケニル基から選択される基である。式(3)で表されるシロキサンの平均重合度は3~2,000である。)
酸触媒としては、硫酸、塩酸、リン酸、活性白土、塩化鉄、ホウ酸、トリフルオロ酢酸、メタンスルホン酸、トリフルオロメタンスルホン酸等が挙げられる。
アルカリ触媒としては、KOH、CsOH、NaOH、(CH3)4NOH、(n-C4H9)4POH及びカリウムやリン等の金属シリコネートが挙げられる。
このような低粘度のオルガノポリシロキサンとして、具体的には、粘度1~400mPa・sのジメチルポリシロキサン、ジメチルビニルシロキシ基を分子鎖両末端に有するジメチルポリシロキサン、側鎖にビニル基を有するメチルビニルポリシロキサン、ジメチルヒドロキシシリル基を両末端に有するジメチルポリシロキサン、側鎖にフェニル基を有するフェニルメチルポリシロキサン等が挙げられる。
(A)1分子中に2個以上のケイ素原子結合アルケニル基を有するオルガノポリシロキサン:100質量部、
(B)1分子中に3個以上のケイ素原子結合水素原子(SiH基)を含有するオルガノハイドロジェンポリシロキサン:0.1~30質量部、
(C)白金族金属系触媒:触媒量、
(D)上記ミスト防止剤:0.01~20質量部、
必要により
(E)反応制御剤
を含有してなる付加反応硬化型のシリコーン組成物であることが好ましい。
また、全R2中の少なくとも2個、好ましくは2~50個、より好ましくは2~10個はアルケニル基である。
pは1~1,000であり、好ましくは10~300である。
また、rは1~300であり、好ましくは10~100である。sは0~150であり、好ましくは0~50である。また、r、sはr>sの比率で存在する。
ここで、基材としては、グラシン紙、ポリエチレンラミネート紙、クラフト紙、クレーコート紙、ミラーコート紙等の紙、ポリプロピレン、ポリエチレン、ポリエチレンテレフタレート、ポリ塩化ビニル等のプラスチックフィルムなどが挙げられる。
なお、本発明のミスト防止剤は、無溶剤型剥離紙用シリコーン組成物の硬化物の剥離力に何も変化を与えない。
M:(CH3)3SiO1/2
MH:(CH3)2HSiO1/2
MVi:(CH2=CH)(CH3)2SiO1/2
D:(CH3)2SiO2/2
DH:(CH3)HSiO2/2
DVi:(CH2=CH)(CH3)SiO2/2
TVi:(CH2=CH)SiO3/2
Q:SiO4/2
MH 2D29で表される直鎖状メチルハイドロジェンポリシロキサン10gとM2DVi 1.4D147TVi 1で表される分岐を含有する直鎖状ビニルメチルポリシロキサン48g(SiH基:ビニル基=1モル:1.17モル)をデカメチルペンタシロキサン(D5)280g中で混合後、ビニルメチルポリシロキサンを配位した白金触媒を白金質量として2ppm添加し、昇温した。50~60℃にてゲル化したところで反応を止め、KOHを200ppm投入し、150℃で6時間平衡化反応を行った。温度を80℃に下げた後、エチレンクロルヒドリン0.2gを投入し、中和した。得られたものの粘度は126,500mPa・sで、高粘度のオイル状であった。また1H-NMRより計算されるシロキサン単位1,000molあたりのシルエチレン結合は1.9molであった。
MH 2D59で表される直鎖状メチルハイドロジェンポリシロキサン4.1gとM0.74MVi 0.08Q1で表されるシリコーン樹脂12.24g(SiH基:ビニル基=1モル:4.2モル)を、M2D79で表される直鎖状ジメチルポリシロキサン33.5g及びデカメチルペンタシロキサン(D5)25.2gを混合した後、ビニルメチルポリシロキサンを配位した白金触媒を白金質量として2ppm添加し、昇温した。50~60℃にてゲル化したところで反応を止め、MVi 2D585.32で表される両末端にビニル基を有する直鎖状ジメチルポリシロキサンを29.9g添加し、十分に攪拌を行った。その後、KOHを1,200ppm投入し、150℃で6時間平衡化反応を行った。温度を80℃に下げた後、エチレンクロルヒドリンを0.2g投入し、中和した後、減圧濃縮を150℃で2時間、2mmHg条件下で行った。得られたものの粘度は1,550mPa・sで、オイル状であった。1H-NMRより計算されるシロキサン単位1,000molあたりのシルエチレン結合は6.2molであった。
MH 2D31.97で表される直鎖状ジメチルハイドロジェンポリシロキサン11gとM2DVi 2.4D150.4で表される直鎖状ビニルメチルポリシロキサン49.3g(SiH基:ビニル基=1モル:1.17モル)を、M2D24で表される直鎖状ジメチルポリシロキサン422g中で混合後、直鎖状ビニルポリシロキサンを配位した白金触媒を白金質量として2ppm添加し、昇温した。50~60℃でゲル化したところで反応を止め、そこへM2D24で表される直鎖状ジメチルポリシロキサンを更に870g加え、ホモミキサーで2,000rpm、3時間ゲルをすり潰しながら攪拌した。得られたものの粘度は280mPa・sであったが、微細なゲルは残存していた。1H-NMRより計算される架橋物のシロキサン単位1,000molあたりのシルエチレン結合は11.3molであった。
合成例3で合成したゲル含有シリコーンオイルをろ紙ろ過を行った。得られたオイルの収率は、合成例3のオイルの約20質量%で、粘度は41mPa・sであり、目視でゲルは確認できなかった。
M2D31.97DH 5で表される直鎖状ジメチルハイドロジェンポリシロキサン51gとM2DVi 4D148.56で表される直鎖状ビニルメチルポリシロキサン49g(SiH基:ビニル基=1モル:0.19モル)を混合後、ビニルポリシロキサンを配位した白金触媒を白金質量として2ppm添加し、昇温した。90℃で3時間反応を行った時点でSiH基量は0.085mol/100gであり、ビニル基は全量反応していた。この後、120℃で3時間2mmHgの条件にて揮発成分を減圧濃縮した。得られたシリコーンオイルの粘度は2,400mPa・sであった。
また、本シリコーンオイルは経時で水素ガスの発生が確認された。1H-NMRより計算されるシロキサン単位1,000molあたりのシルエチレン結合は74.4molであった。
下記に示す基本組成に上記合成例で調製した各種ミスト防止剤を配合し、各種オルガノポリシロキサン組成物を下記方法により調製し、硬化させた。
なお、オルガノポリシロキサン組成物のミスト発生量、剥離力、残留接着率は下記の方法により測定した。最終組成物の粘度は上記方法により測定した。いずれのオルガノポリシロキサン組成物も硬化性は問題ない状態であった。
下記式(6)
東洋精機製作所製 Misting Testerに試験サンプル1.6gを最上部のローラー上に塗布し、1,400rpmで3つのローラーを回転させ、発生するミスト量をIncorporated社製 Dust Trak Aerosol Monitor Model 8520 TSIにて測定した。ミストは最上部のローラーから真上15cmのところに内径7mmのビニールチューブ口を設置し、ビニールチューブのもう一方の口はDust Trakの吸気部位に連結させた。測定は180秒行い、最高値を記録した。Dust Trakの検出限界最高値は150mg/m3である。結果を表1に示す。
オルガノポリシロキサン組成物を調製後、ポリエチレンラミネート紙基材にオルガノポリシロキサン組成物を0.9~1.1g/m2となるように塗布し、140℃の熱風式乾燥機中で30秒間加熱し、これをセパレーターとして以下の測定に使用した。
上記方法にてオルガノポリシロキサン組成物を硬化させたシリコーンセパレーターの表面を目視で観察し、問題なく塗工されているものを○で表記し、凹凸や異物のあるものを×で表記した。結果を表1に示す。
前記の硬化方法により得られたシリコーンセパレーターを25℃で20時間保存した後、TESA-7475テープを貼り合わせたものを70℃の乾燥機中20g/m2の荷重を加え20時間保存したものを試料とし、試料のTESA-7475テープを、引張試験機を用いて180°の角度で0.3m/分で剥がし、剥離するのに要した力を測定して剥離力(N/25mm)とした。結果を表1に示す。
上記剥離試験後のTESA-7475テープをステンレンス板に貼り合わせ、2kgのテープローラーで1往復圧着後、引張試験機を用いて180°の角度で0.3m/分で剥がし、再剥離するのに要した力を測定し、下記の計算方法で残留接着率を求めた。結果を表1に示す。
残留接着率(%)=再剥離力÷剥離力×100
Claims (9)
- 下記式(1)で表される構造を有するオルガノポリシロキサンと下記式(2)で表される構造を有するオルガノハイドロジェンポリシロキサンとをヒドロシリル化反応して得られるシリコーンゲル状物に、下記式(3)で表されるシロキサン単位を有する化合物を加えて平衡化することにより得られる、シロキサン単位1,000molあたりシルエチレン結合を0.1~50mol含有するオルガノポリシロキサンからなることを特徴とするオルガノポリシロキサン架橋物。
MαMVi βDγDVi δTεTVi ζQη (1)
MθMH ιDκDH λTμTH ν (2)
(式中、MはR3SiO1/2、MViはR2PSiO1/2、DはR2SiO2/2、DViはRPSiO2/2、TはRSiO3/2、TViはPSiO3/2、MHはR2HSiO1/2、DHはRHSiO2/2、THはHSiO3/2、QはSiO4/2であり、Rはそれぞれ独立に脂肪族不飽和結合を有さない炭素原子数1~12の非置換又は置換の一価炭化水素基であり、Pは-(CH2)a-CH=CH2(aは0又は1~6の整数)で表されるアルケニル基である。α、β、γ、δ、ε、ζ、η、θ、ι、κ、λ、μ、νはそれぞれ独立に0又は正の数であり、β、δ、ζが同時に0になることはなく、β+δ+ζ≧2で、ι、λ、νも同時に0になることはなく、ι+λ+ν≧2である。)
R1 2SiO2/2 (3)
(式中、R1は同一又は異種の脂肪族不飽和結合を有さない炭素原子数1~20の一価炭化水素基、又は-(CH2)a-CH=CH2(aは0又は1~6の整数)で表されるアルケニル基から選択される基である。式(3)で表されるシロキサンの平均重合度は3~2,000である。) - 式(1)において、1≦α+γ+ε+η≦1,000であり、式(2)において、1≦θ+κ+μ≦200である請求項1記載のオルガノポリシロキサン架橋物。
- 式(1)において、1≦γ≦1,000であり、式(2)において、1≦κ≦200である請求項2記載のオルガノポリシロキサン架橋物。
- 式(3)で示されるシロキサン単位を有する化合物が、オクタメチルテトラシロキサン、デカメチルペンタシロキサン、式M2Dn(MはR3SiO1/2単位を示し、DはR2SiO2/2単位を示し、Rはそれぞれ独立に脂肪族不飽和結合を有さない炭素原子数1~12の非置換又は置換の一価炭化水素基であり、nは0~200の整数である。)で示される直鎖シロキサン、及び式M2+mDnTm(M、D、nは上記の通り、TはRSiO3/2単位を示し、Rは上記の通りである。mは1~10の整数である。)で示される分岐鎖シロキサンから選ばれるオルガノシロキサンである請求項1~3のいずれか1項に記載のオルガノポリシロキサン架橋物。
- 式(1)で表されるオルガノポリシロキサンの重量平均分子量が260~74,186であり、また式(2)で表されるオルガノハイドロジェンポリシロキサンの重量平均分子量が208~14,934であることを特徴とする請求項1~4のいずれか1項に記載のオルガノポリシロキサン架橋物。
- 請求項1~5のいずれか1項に記載のオルガノポリシロキサン架橋物を、25℃における粘度が1~400mPa・sの低粘度オルガノポリシロキサンで希釈してなるシロキサン組成物。
- 請求項1~5のいずれか1項に記載のオルガノポリシロキサン架橋物又は請求項6記載のシロキサン組成物からなるミスト防止剤。
- (A)1分子中に2個以上のケイ素原子結合アルケニル基を有するオルガノポリシロキサン:100質量部、
(B)1分子中に3個以上のケイ素原子結合水素原子を有するオルガノハイドロジェンポリシロキサン:0.1~30質量部、
(C)白金族金属系触媒:触媒量、
(D)請求項7に記載のミスト防止剤:0.01~20質量部
を含有する無溶剤型剥離紙用シリコーン組成物。 - 下記式(1)で表される構造を有するオルガノポリシロキサンと下記式(2)で表される構造を有するオルガノハイドロジェンポリシロキサンとをヒドロシリル化反応してシリコーンゲル状物を製造した後、このシリコーンゲル状物を下記式(3)で表されるシロキサン単位を有する化合物を加えて平衡化することにより、シロキサン単位1,000molあたりシルエチレン結合を0.1~50mol含有するオルガノポリシロキサンを得ることを特徴とするオルガノポリシロキサン架橋物の製造方法。
MαMVi βDγDVi δTεTVi ζQη (1)
MθMH ιDκDH λTμTH ν (2)
(式中、MはR3SiO1/2、MViはR2PSiO1/2、DはR2SiO2/2、DViはRPSiO2/2、TはRSiO3/2、TViはPSiO3/2、MHはR2HSiO1/2、DHはRHSiO2/2、THはHSiO3/2、QはSiO4/2であり、Rはそれぞれ独立に脂肪族不飽和結合を有さない炭素原子数1~12の非置換又は置換の一価炭化水素基であり、Pは-(CH2)a-CH=CH2(aは0又は1~6の整数)で表されるアルケニル基である。α、β、γ、δ、ε、ζ、η、θ、ι、κ、λ、μ、νはそれぞれ独立に0又は正の数であり、β、δ、ζが同時に0になることはなく、β+δ+ζ≧2で、ι、λ、νも同時に0になることはなく、ι+λ+ν≧2である。)
R1 2SiO2/2 (3)
(式中、R1は同一又は異種の脂肪族不飽和結合を有さない炭素原子数1~20の一価炭化水素基、又は-(CH2)a-CH=CH2(aは0又は1~6の整数)で表されるアルケニル基から選択される基である。式(3)で表されるシロキサンの平均重合度は3~2,000である。)
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JP2016529232A JP6222359B2 (ja) | 2014-06-23 | 2015-06-04 | オルガノポリシロキサン架橋物及びその製造方法、並びにミスト防止剤及び無溶剤型剥離紙用シリコーン組成物 |
CN201580033973.8A CN106459416B (zh) | 2014-06-23 | 2015-06-04 | 有机聚硅氧烷交联物及其制造方法、以及防雾剂和无溶剂型剥离纸用有机硅组合物 |
KR1020177000834A KR102156536B1 (ko) | 2014-06-23 | 2015-06-04 | 오가노폴리실록세인 가교물 및 그 제조 방법, 및 미스트 방지제 및 무용제형 박리지용 실리콘 조성물 |
US15/994,587 US10676642B2 (en) | 2014-06-23 | 2018-05-31 | Crosslinked organopolysiloxane and method for producing same, mist suppressant, and solvent-free silicone composition for release paper |
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US15/994,587 Division US10676642B2 (en) | 2014-06-23 | 2018-05-31 | Crosslinked organopolysiloxane and method for producing same, mist suppressant, and solvent-free silicone composition for release paper |
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JP2022527667A (ja) * | 2019-12-02 | 2022-06-02 | ダウ シリコーンズ コーポレーション | 剥離コーティングを調製するための組成物 |
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EP3635461A4 (en) * | 2017-06-06 | 2021-03-10 | Commscope Technologies LLC | FIBER ALIGNMENT DEVICE WITH SELF-HEALING REFRACTIVE INDEX ADJUSTMENT GEL |
CN115397890B (zh) * | 2020-04-16 | 2024-04-19 | 信越化学工业株式会社 | 含有烯基的有机聚硅氧烷的制造方法 |
CN115867613A (zh) * | 2020-07-02 | 2023-03-28 | 富士高分子工业株式会社 | 有机硅凝胶组合物及有机硅凝胶片材 |
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CN106459416A (zh) | 2017-02-22 |
JP6222359B2 (ja) | 2017-11-01 |
TW201615698A (zh) | 2016-05-01 |
CN106459416B (zh) | 2020-05-12 |
TW201906899A (zh) | 2019-02-16 |
US10676642B2 (en) | 2020-06-09 |
TWI669326B (zh) | 2019-08-21 |
KR20170021284A (ko) | 2017-02-27 |
JPWO2015198827A1 (ja) | 2017-04-20 |
TWI660984B (zh) | 2019-06-01 |
US20170218133A1 (en) | 2017-08-03 |
US10113036B2 (en) | 2018-10-30 |
US20180273692A1 (en) | 2018-09-27 |
KR102156536B1 (ko) | 2020-09-16 |
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