TW201529768A - Solventless release coating organopolysiloxane composition and sheet-form substrate having cured release coating - Google Patents

Abstract

This invention relates to solventless release coating organopolysiloxane composition and sheet-form substrate having cured release coating, providing a solventless release coating organopolysiloxane composition having a viscosity of 50 to 3,000 mPa,s, comprising (A) 100 parts of an organopolysiloxane fluid having a viscosity at 25 DEG C of 10 to 1,000 mPa,s and alkenyl content of 0.10 to 3.0 wt%; (B) 0.5 to 15 parts of a diorganopolysiloxane having a viscosity at 25 DEG C of 10,000 to 150,000 mPa,s, and 0.05 to 0.30% of alkenyl groups at the pendant position of its siloxane-chain and trialkylsiloxy-terminals; (C) a prescribed quantity of an organohydrogenpolysiloxane; and (D) a hydrosilylation reaction catalyst. Also, a cured release coating-bearing sheet-form substrate that has a cured coating from this solventless release coating organopolysiloxane composition is provided.

Description

Solvent-free release coating organic polyoxane composition and sheet substrate having cured release coating

This invention relates to a solventless composition for use in polyoxynitride release coating applications.

This invention relates to curable polyoxynitride release coating compositions. Polydecyloxy bottom release coatings can be used in applications where a relatively tack free surface is desired. The curable polyoxynitride release coating composition is applied to a substrate, also known as a "substrate", which may for example be a paper or polymer film, which is then cured. A single-sided substrate such as a backing paper for a pressure-sensitive adhesive label is used to temporarily hold the label without affecting the adhesion of the label. Double-sided substrates, such as release paper for double-sided and transfer tape, are used to ensure protection of the double-sided self-adhesive tape or mucosa and desired unwinding characteristics. The release coating is required to adhere well to the substrate, while at the same time having a relatively low viscosity to the adhesive such that the label can be removed from the substrate by a predetermined peel force.

The coating of the base substrate is performed by applying a polydecyloxy bottom release coating composition onto the substrate and subsequently curing the composition. A preferred curing mechanism is a thermally initiated hydrazine hydrogen addition reaction which can be adjusted to alter the adhesion between the release coating and the viscous label.

The hydrazine hydrogen addition reaction is an addition reaction in which a compound containing at least one unsaturated bond reacts with a compound containing at least one Si-H bond. An unsaturated bond contains a double or triple bond between two atoms. The two atoms of the bond may be carbon atoms or carbon-hybrids. child. For example, the unsaturated bond can be an alkenyl group.

The basic composition of the polydecyloxy bottom release coating composition which is cured by the hydroquinone addition reaction is classified into (A) an alkenyl group-containing polyorganosiloxane, and (B) an organic hydroquinone-containing alkyl group. A cross-linking agent (also known as a crosslinker) and a catalyst for the hydrazine hydrogen addition reaction between (A) and (B).

The backing substrate can be a paper or polymer substrate such as a polyester such as polyethylene terephthalate, film, polypropylene or polyethylene, particularly suitable for transparent-transparent labels.

Polysiloxane or polyoxane is a polymer based on Si units. It may comprise at least one of the following units: M unit (monofunctional), D unit (bifunctional), T unit (trifunctional), Q unit (tetrafunctional). The Si atom system of the M unit is bonded to one O atom. The Si atom system of the D unit is bonded to two O atoms. The Si atom system of the T unit is bonded to three O atoms. The Si atom of the Q unit is bonded to four O atoms.

The M unit usually has the formula R ^a SiO _1/2 . The D unit typically has the formula R ^b R ^c SiO _2/2 . The T unit has the formula R ^d SiO _3/2 . The Q unit usually has the formula SiO _4/2 .

R ^a , R ^b , R ^c and R ^{d are} each a substituent, preferably an organic substituent. Each substituent R ^a R ^b R ^c or R ^d may be selected, for example, from an alkyl group, an aryl group, an alkenyl group, an acrylate, a methacrylate, and others. For example, it may be an alkenyl group having 2 to 6 carbon atoms, such as a vinyl group (aka Vi or vi) or a hexenyl group.

Branched polyoxyalkylenes, sometimes referred to as resins, typically comprise at least one T unit and/or at least one Q unit. Linear polyoxyalkylenes typically comprise a D unit and an optional M unit. The MQ resin is an organopolyoxane containing at least one M unit and at least one Q unit. The Q-branched resin is a branched polyfluorene containing at least one Q unit.

The polyoxynitride release coating composition can be used to coat a layer on a film or paper substrate and cure under heat to form a coated substrate. The present invention is intended to provide a coated release coated substrate having a slippery surface and low release force for use in tape release or label release applications. In particular, the present invention relates to a solventless release coating organopolyoxane composition, a composition obtained by curing a solvent-free release coating organopolyoxane composition on a sheet-like substrate in a film form. a sheet-type substrate having a cured release coating, and a method for applying a solvent-free release coating organopolyoxane composition on at least one side of a sheet-like substrate using a multiple roll coater to produce a cured A method of producing a sheet-type substrate from which a coating is peeled off.

The composition for the release coating application may be in the form of an emulsion (water base), a solvent base or a solvent free (solvent free). The solvent-free polyfluorene stripping coating composition has some important advantages not found in solvent substrates and emulsion coating compositions:

. Less environmental, health, safety and regulatory considerations

. No solvent recovery equipment required

. Does not contain carriers that must be removed, so production speed can be increased

. Less likely to damage the film

Traditionally, solvent-free (SL) type polyoxynitride strip coatings cure quickly, but the base polymer in the coating bath must have a low viscosity to meet the requirements of a multi-roller coating process. This low viscosity limits the degree of polymerization of the polyorganosiloxane used as the base polymer. Mainly because of the tight crosslink density of the cured coating, it is difficult for the cured coating to provide a slippery surface and a low release force suitable for the adhesive. In order to overcome such technical questions The problem is that the prior art proposes several solutions.

For example, WO 2008084747 A2 (Patent Reference 1, incorporated herein by reference) discloses a solvent-free organic polyoxoxane composition for forming a cured release coating comprising: (A) 100 parts of organic poly a oxoxane fluid having a branched structure and comprising: (i) a _oxoxane unit represented by the formula SiO _4/2 , (ii) represented by the formula R ₂ SiO _2/2 a oxoxane unit, and (iii) ^a oxoxane unit represented by the formula R ^a R ₂ SiO _1/2 ; (B) 0.5 parts to 15 parts of a diorganopolyoxy siloxane, the diorganopolyoxy siloxane Having an average structural formula: R ^a R ^c ₂ SiO(R ^b R ^c SiO _2/2 ) _n1 (R ^c ₂ SiO _2/2 ) _n2 SiR ^c ₂ R ^a ; (C) the specified amount of organic hydrogen polyoxymethane (organohydrogenpolysiloxane); and (D) hydrosilylation reaction catalyst.

A sheet-like substrate having a cured coating is also provided, and the cured coating is formed from such a solvent-free organic polyoxoxane composition for forming a cured release coating.

The diorganopolyoxane (B) contains an alkenyl group. It is stated that [0029] the alkenyl content must be maintained to be very low, especially up to 0.1 mol% of the polyoxynium-bonded organic group being an alkenyl group (the term "mole" may actually mean "weight"). According to the embodiment, the component (B) of Patent Reference 1 has a vinyl content of 0.02% by weight.

Component (B) of Patent Reference 1 must have a viscosity of at least 100,000 mPa s at 25 C and preferably at least 1,000,000 mPa s (see [0030]).

Comparative Example 3 of WO 2008084747 A2 discloses the following composition: 100 parts of dimethylvinylsiloxy-end blocked dimethylpolysiloxane, as shown by the following average structural formula ( Viscosity = 400 mPa.s, calculated vi% (vinyl%) = 0.62% by weight); 1.0 part (B<1>) of a copolymer of dimethyl methoxyoxane and diphenyl decane which is blocked by dimethylvinyl methoxy and trimethyl methoxy The end of the molecular chain (content of diphenyloxane unit = 5 mol%, viscosity = 50,000 mPa.s); 2.0 parts of (C) methylhydrogen polyoxyalkylene, and the methyl hydrogen polyfluorene Both ends of the two molecular chains of the oxyalkylene block the two ends with a trimethyl methoxy group (viscosity = 20 mPa.s, hydrogen content bonded to ruthenium = 1.6% by weight); and 0.30 parts of (E) 1-ethynyl group 1-cyclohexanol, and the above ingredients are uniformly mixed; a sufficient amount of (D) chloroplatinic acid-1,3-divinyl-1,1,3,3-tetramethyldifluorene is mixed into the mixture. An oxane complex (platinum metal content = 0.60% by weight) to provide 100 ppm of platinum (also known as platinum) metal to form a solvent-free organic polyoxane composition for forming a cured release coating (viscosity = 400 mPa.s); the dynamic coefficient of friction and the peel resistance value of the obtained composition were measured; the results are shown in Table 4. WO 2008084747 A2 teaches that the technical purpose of this case is to "bleed-out" a slip additive having a high viscosity on the surface of the cured layer. The additive can establish a loose structure by forming a weak end-linked with the vulcanized network structure by the entanglement of the crosslinking agent or the long polymer chain.

For example, JP 61159480 A (Patent Reference 2, which is incorporated herein by reference) discloses a PCT PCT PCT PCT PCT PCT PCT PCT PCT PCT PCT PCT PCT PCT PCT PCT PCT PCT PCT PCT PCT PCT PCT PCT Patent No. Containing: 1) 100 parts by weight of an organic polyoxyalkylene having at least two or more vinyl groups in one molecule, at least one or more vinyl bonds at a side chain position And the vinyl content is between 0.5 mol% and 10.0 mol%, and the viscosity at 25 ° C is 50 to 10,000 mPa s; 2) 0.5 to 30.0 parts by weight of the organic polyfluorene having a lower vinyl content Oxyalkane, the vinyl content of the organopolyoxane is less than the vinyl content of the above organopolyoxane, and the viscosity at 25 ° C is at least 100,000 mPa s; 3) 0.5 to 60.0 parts by weight of the organic hydrogen polycondensation a oxoxane having at least two hydrogen bonded to the oxime in one molecule of the organohydrogenpolysiloxane; and 4) a catalytic amount of platinum or a platinum compound.

JP 61159480 A provides a release coating characterized in that no or only a low amount of reactive adhesive migrates (bleeds) onto the surface of the cured coating thereby providing good slip. JP 61159480A indicates that the purpose of the case is to obtain a polyfluorene oxide composition by mixing two kinds of organic polyoxyalkylene oxide, an organic hydrogen polyoxyalkylene oxide and a platinum catalyst, which can be brought to the material to be treated. Excellent slip.

For example, WO 2005059039 A2 (Patent Reference 3, which is incorporated herein by reference) discloses a thermally-cured, non-solvent, polyoxy-oxygen stripping composition having a reduced coefficient of friction and enhanced slip properties. . The invention also relates to a method for producing a heat-curable solvent-free polyoxynene stripping composition on a substrate using an alpha-olefin and a reactive polyorganosiloxane, the method comprising the composition of the heat-curing solvent-free stripping of the invention The coating is applied to the substrate and the coating on the substrate is cured with heat. The invention further relates to A heated, curable, solvent-free, polyoxynated, epitaxially coated article having a reduced coefficient of friction and enhanced slip properties.

For example, US Pat. No. 2,010, 287, 267, issued to A. No.. The viscosity of s, the composition comprises: (A) 100 parts by weight of a diorganopolyoxyalkylene having an alkenyl functional group, and the diorganopolyoxyalkylene has a 25 to 1,000 mPa. a viscosity of s; (B) 0.5 to 15 parts by weight of a diorganopolyoxyalkylene oxide having a concentration of at least 10,000 mPa. a viscosity of s and containing not more than 0.1 mol% of unsaturated aliphatic group content; (C) 0.5 to 5 parts by weight of branched organopolyoxyalkylene, the branched organopolysiloxane having more than one a SiO _4/2 unit, and the branched organopolyoxane is a compound of the formula (1) (SiO _4/2 ) (R ^a R ^b ₂ SiO _1/2 ) _x (1) a polymer product formed by equilibrium polymerization between a branched organooxane oligomer and a diorganooxyalkylene oligomer; (D) a specific amount of an organohydrogenpolyoxyalkylene, the organic hydrogen polycondensation The siloxane has a temperature of 1 to 1,000 mPa. The viscosity of s; and (E) a catalytic amount of a hydrosilylation reaction catalyst.

For example, US Pat. No. 6,569,914, B2 (Patent Reference 5, which is incorporated herein by reference in its entirety in its entirety herein in the the the the the the the the the the the the the the the the the the the the the the the the A release coating having a variable coefficient of friction (COF) was prepared without reacting the organopolysiloxane. By supplying the COF additive in the form of a relatively low viscosity master batch, a coating coater can be used to achieve an adjustment of the coefficient of friction. Very low coefficient of friction (COF) can be obtained by a Wuxi solventless coating system, while these coatings have extremely low extractables.

For example, US 4,123,604 A (Patent Reference 6, incorporated herein by reference) A new and improved coating composition and an improved process for coating a substrate are disclosed. The compositions are substantially solvent free and provide a highly abrasion resistant coating, a non-blocking characteristic, a fast cure, and an overall aesthetic appearance when the composition is cured. An embodiment of the coated substrate is applied to a paper product such that the paper product can be detached from the adhesive.

For example, US 4,870,149 A (Patent Reference 7, incorporated herein by reference) discloses a solvent-free release polyoxyl composition for making the surface non-sticky, the composition providing a cured film having the desired Slip factor, toughness and high-speed peel characteristics without sacrificing the inherent advantages of the film, such as curability, uniformity of peel resistance, residual adhesive strength, the composition uses trivinyl A decyloxy group is a terminal group and a diorganovinyl polyoxyalkylene having a vinyl dimethyl fluorenyl group or a trimethyl fluorenyl group as the other terminal group.

For example, US Pat. No. 543, 2006, filed on Jun The composition comprises: (a) a first polydiorganotoxioxane, and the end of the first polydiorganotoxioxane is a mercapto group having a reactive group; (b) a second polydiorganotoxioxane, And the terminal of the second polydiorganotoxioxane is a mercapto group having a reactive group, and the reactive group of (a) and the reactive group of (b) may be the same reactive group or different reactive groups, the above (a) The reactive groups with (b) may be reacted with each other to form a covalent bond; (c) a polydiorganotoxioxane having three or more reactive groups capable of reacting with the reactive group of (a) Or reacting one or both of the reactive groups of (b) to form a covalent bond; and (d) reacting the reactive groups of (a), (b) and (c) to form a covalent bond Key catalyst. When the composition is coated on a substrate and cured, the composition can provide a release substrate for a pressure sensitive tape and a pressure sensitive transfer tape.

However, the above patent references 1-8 do not properly solve the above technical problems. In particular, both Patent Reference 1 and Patent Reference 2 disclose the use of an organopolyoxane having a viscosity higher than 100,000 mPa s. Furthermore, in these patent references, a viscosity of less than 100,000 mPa s may result in poor slip of the resulting cured coating due to insufficient bleeding effect, and many adhesives may remain on the cured coating. From the practical point of view of these inventions, the viscosity of 100,000 mPa s does not seem to be sufficient. The preferred embodiment should be a polyoxyalkylene having a viscosity of 1,000,000 mPa s or higher. For example, the above two patent references disclose the use of ultrahigh molecular weight (gelatinous) organopolyoxane having a viscosity of at least 1,000,000 mPa s in all practical embodiments. Therefore, both Patent Reference 1 and Patent Reference 2 require the use of a polymer having a higher viscosity to achieve a special technical effect. For example, referring to paragraph [0006] and paragraphs [0026] to [0030] of Patent Reference 1, component (B) is a polyoxyalkylene having a viscosity of at least 100,000 mPa s, and the effect of the component (B) is to enhance the curing. The peelability of the coating to the viscous material and the component (B) can also provide slip for the cured coating. That is, although there is a light linkage between the component (B) and the cured network structure, the component (B) should have a free polymer chain oozing out on the surface of the cured coating and on the surface of the cured coating. Provides good slip on the top. Further, in the case where there is no vinyl group in the overhang position within the defined range, if the terminal group reaction does not proceed well, the colloidal organopolysiloxane is easily extracted from the solidified body. However, it is apparent that none of Patent Reference 1, Patent Reference 2 or Patent Reference 5 can easily provide a limited release coating composition that maintains a suitable low viscosity for a multi-roller coater while having superior properties.

Therefore, there is still a need in the art to obtain a release coating composition that maintains a suitable low viscosity and superior properties for use in a multi-roller coater, which includes rapid curing using a low amount of catalyst, Low migration cured layer, coating surface It is slippery and has a good smooth feel, can be well fixed to the substrate and has a low peeling force for the adhesive.

The present invention seeks to solve the above problems and an object of the present invention is to introduce a solventless composition useful for polyoxynitride release coating applications. The release coating composition is for coating a layer on a film substrate or a paper substrate and curing under heat to form a substrate having a coating. Another object of the present invention is to provide a coated release coated substrate having a slippery surface and a low release force, which is applied to tape release or label release.

In order to overcome the above-mentioned existing drawbacks, the present invention discloses a cured release coating composition comprising: (A) a reactive organopolyoxane fluid, and the organopolyaluminane fluid has a 10 mPa at 25 ° C . s to 1,000mPa. The viscosity of s and the alkenyl content of 0.10% by weight to 3.0% by weight of the organopolyoxyalkylene (A) (according to Vi); and (B) the polyether having a specific long chain in the hydrogen addition reaction curing system Alkane additive. The component (B) has a high viscosity in a limited range (10,000 mPa s to 150,000 mPa s), and the component (B) has a range (0.05% by weight to 0.30% by weight relative to the weight of (A)) Within the reactive ethylene functional group, the reactive ethylene functional group is at the side chain position and the non-reactive end. This structural feature of component (B) readily forms a covalent bond with the SiH functional crosslinking agent by a hydroquinone addition reaction.

The viscous system was measured at 25 C unless otherwise indicated.

Ingredient (B) has some pendant ethylene functional groups (alkenyl groups) which form a covalent bond with the curing system by hydrosilylation. And the two trialkyl decyloxy ends do not undergo a curing reaction with the system, thus helping to freely transfer a part of the molecular chains. To the surface of the cured release coating. This property provides a slippery feel and low peel force to the cured release coating. The oxime with moderate viscosity (10,000 mPa.s to 150,000 mPa.s at 25 ° C) provides the final release coating bath with a suitable viscosity for operation with a multi-roller coater and is undergoing a vulcanization reaction. It also has appropriate reactivity.

Furthermore, the concept of the present invention differs from the above-mentioned "bleed-out" effect in that the pendant alkenyl group in the siloxane is used as a "fixing point" for anchoring the component (B) in the curing system. Point)". And has 10,000 mPa at 25 ° C. s to 150,000mPa. The enthalpy of the viscosity of s has an entanglement effect with the curing system, and this entanglement effect may also reduce the silicone migration.

On the substrate, by crosslinking or sulfurization reaction (addition curing in the presence of a platinum (Pt) catalyst), component (B) is in the above-mentioned reactive organopolyoxane fluid and SiH functional crosslinking agent (ie, component A portion of the cured network structure is formed between (C)). This imparts a slippery feel to the dried coating and this also provides a lower peel force for the viscous adhesive. The viscosity of the coating bath is maintained at a reasonable basic viscosity suitable for use with a multi-roller coater. These performance attributes of the coated substrate can reduce noise during the coating stage, and these performance attributes can protect the operator's fingers or arms from scratches when repeatedly peeling off the substrate. Furthermore, the present invention can reduce the risk of clogging problems in the manufacturing process of in-situ double-sided coatings.

The above-mentioned Patent Reference 1 (closest prior art) does not disclose a Q-branched or linear reactive organopolyoxane in a hydrazine hydrogen addition curing composition as defined in the present invention and a low reaction a di-organopolyoxane having a viscosity of from 10,000 mPa·s to 150,000 mPa·s at 25 ° C and having a pendant of 0.05 to 0.30% of its oxirane chain The combination of the extended position and the alkenyl group at the terminal of the trialkyl decyloxy group, that is, undisclosed A combination between the component (A) and the component (B). In particular, the component (B) preferred in Patent Reference 1 is substantially different from the component (B) in the present invention (i.e., a polymer having a trimethyl methoxy group and having a vinyl group at an overhang position) Dimethyl decane (PDMS)). The above-mentioned Patent Reference 2 does not disclose or teach the use of a branched polymer at all, and in particular, it is not taught to use a Q-branched polymer. The other alkenyl content of the reactive polymer is higher than the alkenyl content of the component (A) in the present invention. For the above-mentioned Patent Reference 1 and Patent Reference 2, which are intended to exude the polymeric chains of such colloidal organopolyoxyalkylenes on the surface of the cured body, Document 1 and Document 2 have never taught the use of a certain amount of bits in the polyorganic The vinyl group in the overhang position of the siloxane is used to easily form a bond by a hydrazine hydrogen addition reaction with the Si-H polymer.

The above objectives can be achieved by the following scheme:

{1} One has a range of 50 to 3,000 mPa. The solventless release coating organic polyoxane composition of s viscosity comprises: (A) 100 parts by weight of an organopolyaluminane fluid having a concentration of 10 mPa at 25 ° C. s to 1,000mPa. a viscosity of s and an alkenyl content of from 0.10% by weight to 3.0% by weight; (B) from 0.5 part by weight to 15 parts by weight of the mono-diorganopolysiloxane, the diorganopoly group represented by the following average structural formula (1) Oxyalkane, and the diorganopolyoxyalkylene has a 10,000 mPa at 25 ° C. s to 150,000mPa. a viscosity of s and an alkenyl content of 0.05% by weight to 0.30% by weight: R ^c ₃ SiO(R ^b R ^c SiO _2/2 ) _n1 (R ^c ₂ SiO _2/2 ) _n2 SiR ^c ₃ (1)

Wherein R ^b is an alkenyl group having 2 to 8 carbon atoms; R ^c is an alkyl group having 1 to 8 carbon atoms or a phenyl group; n 1 is a number providing an alkenyl content of 0.05% by weight to 0.30% by weight (according to Vi); n2 is a number with a value of at least 1; and n1+n2 is provided to provide 10,000 mPa at 25 °C. s to 150,000mPa. The number of s viscosity; (C) an organohydrogen polyoxyalkylene having an organic hydrogen polyoxyalkylene of 1 mPa at 25 ° C. s to 1,000mPa. a viscosity of s, and the organic hydrogen polyoxyalkylene has at least two hydrogen atoms bonded to the oxime in each molecule, wherein the organic group bonded to the oxime has 1 to 8 carbon atoms An alkyl group or a phenyl group, and the amount of the organic group bonded to the hydrazine is sufficient to cause a hydrogen atom bonded to the hydrazine in the organohydrogen polyoxyalkylene: the alkenyl group in the component (A) and the component (B) The molar ratio is from 0.8:1 to 5:1; and (D) a catalytic amount of a hydrogen addition reaction catalyst.

[2] The solventless release coating organopolyoxane composition according to [1], wherein the component (B) has an alkenyl group content of from 0.05% by weight to 0.20% by weight.

[3] The solventless release coating organopolyoxane composition according to [1], wherein the component (A) is 100 parts by weight of at least one organopolyoxane fluid, the at least one organopolyoxane The fluid is selected from the group consisting of a linear organopolyoxane, a branched organopolyoxane, and an organopolyoxane having a different alkenyl content of from 0.10% to 3.0% by weight. a mixture, and a mixture of a linear organopolyoxane and a branched organopolyoxane.

[4] The solventless release coating organopolyoxane composition according to [1], wherein the component (A) is a polydimethyl methoxyoxane having an alkenyl group only at the molecular terminal (A-1) And (A-2) a mixture of polydimethylsiloxane having an alkenyl group at a molecular terminal and a side chain position.

[5] The solventless release coating organopolyoxane composition according to [1], wherein the component (A) comprises at least one organopolyoxane fluid, the at least one organopolyoxane fluid having one point The dendritic structure and 10mPa at 25 ° C. s to 1,000mPa. a viscosity of s, the at least one organopolyoxane fluid comprising a oxoxane unit (i) to a oxoxane unit (iii), and the at least one organopolyoxane fluid has a plurality of decane oxides a straight chain portion of unit (ii) and a branching point comprising a oxoxane unit (i), wherein the end of the linear portion is blocked by the oxirane unit (iii): (i) silicon _4/2 siloxane units represented by: 1 or more; (ii) to silicon siloxane units of formula R ₂ SiO _2/2 represented by: 15 to 995; (iii) the formula R ^a R ₂ SiO ₁ a oxoxane unit represented by _/2 , wherein R ^a is a group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and having 2 to 8 carbon atoms. An alkenyl group, a phenyl group, an alkoxy group having 1 to 8 carbon atoms, and a hydroxyl group; and R is a group selected from the group consisting of alkyl groups having 1 to 8 carbon atoms, having An alkenyl group of 2 to 8 carbon atoms, and a phenyl group, wherein at least 0.10% by weight to 3.0% by weight of R ^a and R in the molecule are alkenyl groups having 2 to 8 carbon atoms, and in the molecule at least 50% of the total number of R ^a and R having from 1 to 8 Alkyl group carbon atoms.

[6] The solventless release coating organopolyoxane composition according to [5], wherein the component (A) comprises at least one organopolyoxane fluid having a branched structure and has an average enthalpy as described below. The oxane unit formula (2) represents the at least one organopolyoxane fluid: (R ^a R ₂ SiO _1/2 ) ₄ (R ₂ SiO _2/2 ) _m (SiO _4/2 ) (2)

Wherein R ^a is a group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a phenyl group, having 1 to 8 carbon atoms And a hydroxy group; R is a group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and a phenyl group; At least 3.0% by weight of R ^a and R in the molecule are alkenyl groups having 2 to 8 carbon atoms; at least 50% of the total number of R ^a and R in the molecule are alkyl groups having 1 to 8 carbon atoms; And m = 15 to 995.

[7] The solvent-free release coating organopolyoxane composition according to [5], wherein the component (A) is an organopolyoxane having a branched structure and the following average decane The unit formula (3) represents the organopolyoxane: [(R ^b R ^c ₂ SiO _1/2 ) _n (R ^d R ^c ₂ SiO _1/2 ) _1-n ] ₄ (R ^b R ^c SiO _{2/ 2} ) _m1 (R ^c ₂ SiO _2/2 ) _m2 (SiO _4/2 ) (3)

Wherein R ^b is an alkenyl group having 2 to 8 carbon atoms; R ^c is an alkyl group having 1 to 8 carbon atoms or a phenyl group; and R ^d is a group selected from the group consisting of: having An alkyl group of 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a hydroxyl group; having at least three R ^b in the molecule; at least a total of R ^b , R ^c and R ^d in the molecule 50% is an alkyl group having 1 to 8 carbon atoms; n is 0 or 1; m1 is a number having a value of at least 1, m2 is a number having a value of at least 0; and m1 + m2 = 15 to 995.

The solvent-free release coating organopolyoxane composition according to any one of {1} to (7), wherein the composition additionally comprises: (E) 0.001 to 5 parts by weight of a bismuth A hydrogen addition reaction inhibitor, and the composition does not cure at ambient temperature and the composition cures under heat.

{9} A curing of a solventless release coating organopolyoxane composition according to any one of {1} to {8} in a film form on a sheet substrate A coated sheet substrate is peeled off.

[10] The sheet-type substrate having a cured release coating according to [9], wherein the sheet-type substrate is cellophane, clay coated paper, polyolefin laminated paper, thermoplastic resin film or metal foil.

{11} A method for producing a sheet-type substrate having a cured release coating, which is a solventless release coating according to any one of {1} to {8} using a multi-roller coater. organic The polyoxyalkylene composition is coated on at least one side of the sheet-type substrate.

In the hydroquinone addition curing system, the reactive organic polyoxane fluid having a specific viscosity (10 mPa.s to 1,000 mPa.s) and an alkenyl content of 0.1 to 3.0% by weight (A) B) 10,000 mPa at 25 ° C. s to 150,000mPa. a viscosity of s and containing from 0.05% by weight to 0.30% by weight of an alkenyl group at the pendant position of the oxirane chain of the diorganopolyoxyalkylene and at a trialkyldecyloxy group The combination of diorganopolyoxyalkylenes at the end allows the resulting release coating composition to maintain the proper viscosity for use in a multi-roller coater and achieves the following performance: i) using a low amount of catalyst High speed curing; ii) a cured layer with low migration; iii) a smooth and smooth touch on the surface of the coating; iv) good adhesion to the substrate; and v) for viscous adhesives Has a low peel force.

The following application uses are obtained: i) noise reduction in the coating stage; ii) protection of the operator from scratches when the substrate is peeled off repeatedly; and iii) clogging problems in the process of manufacturing the in-situ double-sided coating The risk is down.

Preferred embodiment of the invention

The solventless release coating organic polyoxane composition of the invention has a composition of 50 mPa. s to 3,000mPa. The viscosity of s is characterized by: (A) 100 parts by weight of an organopolyoxane fluid having a concentration of 10 mPa at 25 ° C. s to 1,000mPa. a viscosity of s and an alkenyl content of from 0.10% by weight to 3.0% by weight; (B) from 0.5 part by weight to 15 parts by weight of the mono-diorganopolysiloxane, the diorganopoly group represented by the following average structural formula (1) Oxyalkane, and the diorganopolyoxyalkylene has a 10,000 mPa at 25 ° C. s to 150,000mPa. a viscosity of s and an alkenyl content of 0.05% by weight to 0.30% by weight: R ^c ₃ SiO(R ^b R ^c SiO _2/2 ) _n1 (R ^c ₂ SiO _2/2 ) _n2 SiR ^c ₃ (1)

Wherein R ^b is an alkenyl group having 2 to 8 carbon atoms; R ^c is an alkyl group having 1 to 8 carbon atoms or a phenyl group; n 1 is a number providing an alkenyl content of 0.05% by weight to 0.30% by weight; n2 Is a number with a value of at least 1; and n1+n2 is provided to provide 10,000 mPa at 25 °C. s to 150,000mPa. The number of s viscosity; (C) an organohydrogen polyoxyalkylene having an organic hydrogen polyoxyalkylene of 1 mPa at 25 ° C. s to 1,000mPa. a viscosity of s, and the organic hydrogen polyoxyalkylene has at least two hydrogen atoms bonded to the oxime in each molecule, wherein the organic group bonded to the oxime has 1 to 8 carbon atoms An alkyl group or a phenyl group, and the amount of the organic group bonded to the hydrazine is sufficient to cause a hydrogen atom bonded to the hydrazine in the organohydrogen polyoxyalkylene: the alkenyl group in the component (A) and the component (B) The molar ratio is from 0.8:1 to 5:1; and (D) a catalytic amount of a hydrogen addition reaction catalyst.

Ingredient (A) is 100 parts by weight of at least one organopolyoxane fluid selected from the group consisting of linear organopolyoxane, branched organopolyfluorene An oxane, a mixture of organopolyoxane having a different alkenyl content of from 0.10% by weight to 3.0% by weight, and a mixture of a linear organopolyoxane and a branched organopolyoxane.

Ingredient (A) is a polydimethyl methoxyoxane having an alkenyl group only at the molecular end of (A-1) And (A-2) a mixture of polydimethylsiloxane having an alkenyl group at a molecular terminal and a side chain position.

The component (A) comprises at least one organopolyoxane fluid having a branched structure and 10 mPa at 25 ° C. s to 1,000mPa. a viscosity of s, the at least one organopolyoxane fluid comprising a oxoxane unit (i) to a oxoxane unit (iii), and the at least one organopolyoxane fluid has a plurality of decane oxides a straight chain portion of unit (ii) and a branching point comprising a oxoxane unit (i), wherein the end of the linear portion is blocked by the oxirane unit (iii): (i) silicon _4/2 siloxane units represented by: 1 or more; (ii) to silicon siloxane units of formula R ₂ SiO _2/2 represented by: 15 to 995; (iii) the formula R ^a R ₂ SiO ₁ a oxoxane unit represented by _/2 , wherein R ^a is a group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and having 2 to 8 carbon atoms. An alkenyl group, a phenyl group, an alkoxy group having 1 to 8 carbon atoms, and a hydroxyl group; and R is a group selected from the group consisting of alkyl groups having 1 to 8 carbon atoms, having An alkenyl group of 2 to 8 carbon atoms, and a phenyl group, wherein at least 0.10% by weight to 3.0% by weight of R ^a and R in the molecule are alkenyl groups having 2 to 8 carbon atoms, and in the molecule at least 50% of the total number of R ^a and R having from 1 to 8 Alkyl group carbon atoms.

The component (A) comprises at least one organopolyoxane fluid having a branched structure, and the at least one organopolyoxane fluid is represented by the following average oxirane unit formula (2): (R ^a R ₂ SiO _{1 /2} ) ₄ (R ₂ SiO _2/2 ) _m (SiO _4/2 ) (2)

Wherein R ^a is a group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a phenyl group, having 1 to 8 carbon atoms And a hydroxy group; R is a group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and a phenyl group; At least 3.0% by weight of R ^a and R in the molecule are alkenyl groups having 2 to 8 carbon atoms; at least 50% of the total number of R ^a and R in the molecule are alkyl groups having 1 to 8 carbon atoms; And m = 15 to 995.

The component (A) is an organic polyoxyalkylene having a branched structure, and the organopolyoxyalkylene is represented by the following average oxirane unit formula (3): [(R ^b R ^c ₂ SiO _1/2 ) _n ( R ^d R ^c ₂ SiO _1/2 ) _1-n ] ₄ (R ^d R ^c SiO _2/2 ) _m1 (R ^c ₂ SiO _2/2 ) _m2 (SiO _4/2 ) (3)

Wherein R ^b is an alkenyl group having 2 to 8 carbon atoms; R ^c is an alkyl group having 1 to 8 carbon atoms or a phenyl group; and R ^d is a group selected from the group consisting of: having An alkyl group of 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a hydroxyl group; having at least three R ^b in the molecule; at least a total of R ^b , R ^c and R ^d in the molecule 50% is an alkyl group having 1 to 8 carbon atoms; n is 0 or 1; m1 is a number having a value of at least 1, m2 is a number having a value of at least 0; and m1 + m2 = 15 to 995.

In the preferred component (A), R ^b is a vinyl group or a hexenyl group, m1 ranges from 0 to 20, and the total number of siloxane units (= m1 + m2 + 4) ranges from 50 to 400. The preferred viscosity of the component (A) is in the range of 50 mPa. s to 1,000mPa. s. The vinyl content is in the range of from 0.10% by weight to 3.0% by weight.

Typical examples of the alkyl group having 1 to 8 carbon atoms are a methyl group, an ethyl group, a propyl group, and the like, with a methyl group being preferred. Typical examples of alkenyl groups having 2 to 8 carbon atoms are vinyl, allyl, hexenyl, and the like, with vinyl being preferred. The alkoxy group having 1 to 8 carbon atoms may be a methoxy group, an ethoxy group, or the like.

Examples of the R ^a R ₂ SiO _1/2 unit may be Vi(Me ₂ )SiO _1/2 unit, He(Me) ₂ SiO _1/2 unit, (Me) ₃ SiO _1/2 unit, ViMePhSiO _1/2 Unit, and (HO)(Me) ₂ SiO _1/2 unit (where Vi represents a vinyl group, He represents a hexenyl group, Me represents a methyl group, and Ph represents a phenyl group; such abbreviations may also be applied to the following) There may be a combination of such units in the same molecule (for example, Vi(Me ₂ )SiO _1/2 units and (Me) ₃ SiO _1/2 units).

Examples of the R ₂ SiO _2/2 unit may be a (Me) ₂ SiO _2/2 unit, an iMeSiO _2/2 unit, and a MePhSiO _2/2 unit. There may be combinations of such units in the same molecule (for example, (Me) ₂ SiO _2/2 units and ViMeSiO _2/2 units).

In order to achieve good adhesion to the substrate, the R ^a R ₂ SiO _1/2 unit preferably contains an alkenyl group having 2 to 8 carbon atoms, such as Vi(Me) ₂ SiO _1/2 unit, He(Me) ₂ SiO. _1/2 unit and ViMePhSiO _1/2 unit.

The hydrazone-bonded alkenyl group in the component (A) is crosslinked by a hydrazine hydrogen addition reaction with a hydrazine-bonded hydrogen atom in the component (C). Thus, at least two alkenyl groups are required to be present in each molecule; at least 3 alkenyl groups are required in each molecule to establish excellent adhesion to the sheet-type substrate.

The component (A) is a base component of the solventless release coating organopolyoxane composition of the present invention. Preferably, component (A) may have a low degree of polymerization. The component (B) preferably has a linear structure and has a high viscosity, and thus has a high degree of polymerization. Ingredient (B) has an overhanging ethylene functional group which can form a covalent bond with the curing system by a hydroquinone addition reaction. Moreover, the trimethylphosphonium end does not cure with the system, but helps to migrate part of the molecular chain to the surface of the cured release coating. This property provides a slippery feel and low peel force to the cured release coating. The oxime with moderate viscosity (10,000 mPa.s to 150,000 mPa.s at 25 ° C) provides the final release coating bath with a suitable viscosity for operation with a multi-roller coater and is undergoing a vulcanization reaction. It also has appropriate reactivity.

Accordingly, the addition of only a small amount of ingredient (B) provides excellent slip for the cured coating.

In the present invention, the component (A) is not limited to the Q-branched polymer, and includes "linear organopolysiloxane, Q-branched organopolyoxyalkylene, and different linear organopolypolymers. a mixture of oxoxane and a mixture of a linear organopolyoxane and a Q-branched organopolyoxane. The most preferred ingredient (A) is a mixture of Q-branched organopolyoxane and the Q-branched organopolyoxane.

The component (B) is a diorganopolyoxynonane represented by the following average structural formula (1), and the diorganopolyoxyalkylene has a 10,000 mPa at 25 ° C. s to 150,000mPa. The viscosity of s and the alkenyl content of 0.05% by weight to 0.30% by weight: R ^c ₃ SiO(R ^b R ^c SiO _2/2 ) _n1 (R ^c ₂ SiO _2/2 ) _n2 SiR ^c ₃ (1)

(wherein R ^b is an alkenyl group having 2 to 8 carbon atoms; R ^c is an alkyl group having 1 to 8 carbon atoms or a phenyl group; in the same molecule, each R ^b may be the same or different, and each R ^c may be the same or different; n1 is a number providing an alkenyl content of 0.05% to 0.30% by weight; n2 is a number having a value of at least 1; and n1+n2 is a number by which the composition is provided at 25 ° C The viscosity is 10,000 mPa.s to 150,000 mPa.s. The function of component (B) is to improve the peelability of the cured coating relative to the viscous material and the component (B) can also provide the smoothness of the cured coating. . When the coating is formed by curing by the hydrogen-addition reaction between the component (A) and the component (C), the component (B) gradually rises to the formed coating, thereby imparting a surface to the cured coating. Good slip. Ingredient (B) has an overhanging ethylene functional group (alkenyl group) which forms a covalent bond with the curing system by a hydroquinone addition reaction. And the trialkyl decyl end does not cure with the system, but helps to migrate part of the molecular chain to the surface of the cured release coating. This property provides a slippery feel and low peel force to the cured release coating. The oxime with moderate viscosity (10,000 mPa.s to 150,000 mPa.s at 25 ° C) provides the final release coating bath with a suitable viscosity for operation with a multi-roller coater and is undergoing a vulcanization reaction. It also has appropriate reactivity.

Furthermore, the concept of the present invention differs from the above-mentioned "bleed-out" effect in that the pendant alkenyl group in the siloxane is used as a "fixing point" for anchoring the component (B) in the curing system. Point)". And has 10,000 mPa at 25 ° C. s to 150,000mPa. The enthalpy of the viscosity of s has an entanglement effect with the curing system, and this entanglement effect may also reduce the silicone migration.

Here, typical examples of the alkyl group having 1 to 8 carbon atoms are a methyl group, an ethyl group, a propyl group, and the like, and a methyl group is preferred. Typical examples of alkenyl groups having 2 to 8 carbon atoms are vinyl, allyl and hexenyl, and vinyl is preferred.

An embodiment of the R ^b R ^c SiO _2/2 unit can be a ViMeSiO _2/2 unit.

Examples of R ^c ₂ SiO _2/2 units may be (Me) ₂ SiO _2/2 units and MePhSiO _2/2 units.

There may be a combination of such units in the same molecule.

The component (B) includes a component having an alkenyl group bonded to the oxime in the molecule, and thus the component (B) can undergo a hydroquinone addition reaction with the component (C). From the viewpoint of residual tackiness associated with the cured coating layer, it is preferred to use the component (B) having an alkenyl group in the molecule, whereby the component (B) can undergo a hydroquinone addition reaction with the component (C).

For the component (B) having a fluorene-bonded alkenyl group in the molecule and capable of undergoing a hydroquinone addition reaction with the component (C), an excessively high alkenyl content may cause impaired peeling properties of the cured coating layer. And the slip is reduced. If the alkenyl content of component (B) is too low, it will result in inability to bond or migrate more. Therefore, the alkenyl group content in the component (B) is preferably from 0.05% by weight to 0.30% by weight of the organic group bonded to the oxime in the molecule. The oxime-bonded alkenyl group is present at the side chain position, non-terminal position.

Ingredient (B) has a 10,000 mPa at 25 °C. s to 150,000mPa. The viscosity of s, and, from the viewpoint of residual viscosity, the viscosity of component (B) is preferably 20,000 mPa. s to 130,000mPa. s.

In some embodiments, component (B) has a viscosity of less than 100,000 mPa s, preferably less than 99,000 mPa s. In other embodiments, component (B) has a viscosity of between 100,000 and 150,000 mPa s, more preferably between 100,000 and 130,000 mPa s.

In each of the examples, 0.5 parts by weight to 15 parts by weight of the component (B) is added per 100 parts by weight of the above component (A). When the added component (B) is less than the above lower limit, the surface of the cured coating layer has insufficient slip. When the above upper limit value is exceeded, the organopolyoxane composition may have an extremely high viscosity, causing disturbance in the thin film coating on the sheet-like substrate.

Preferably, component (B) has from 0.011 to 03% of an alkenyl group (related to the total weight of component B), more preferably from 0.06 to 0.19% of an alkenyl group (vinyl and/or hexenyl). Preferably component (B) has 20,000 to 130,000 mPa. s viscosity. The percentage by weight of alkenyl groups as defined herein is based on the weight of the vinyl group.

Ingredient (C) is an organohydrogen polyoxyalkylene having 1 mPa at 25 ° C. s to 1,000mPa. a viscosity of s and having at least 2 hydrogen atoms bonded to the oxime in each molecule and having an alkyl group or a phenyl group having 1 to 8 carbon atoms as the organic hydrogen polyoxygen An organic group bonded to a hydrazine in an alkene which functions as a crosslinking agent for crosslinking with the component (A). Crosslinking is carried out by a hydrogen addition reaction with a hydrazine-bonded hydrogen atom in the component and a hydrazine-bonded alkenyl group in the component (A). In the case of the component (B) containing an oxime-bonded alkenyl group, the hydrazone-bonded alkenyl group in the component (B) is also involved in the hydrazine hydrogen addition reaction. should. Therefore, at least two hydrogen atoms bonded to the oxime must be present in each molecule, and preferably at least three hydrogen atoms bonded to the oxime must be present in each molecule.

The bonding position of the hydrogen atom bonded to the oxime is not particularly limited, and for example, the hydrogen atom bonded to the oxime may be bonded at the end position of the molecular chain, the side chain position, or both.

The content of the hydrogen atom bonded to the oxime is preferably from 0.1% by weight to 20% by weight, and more preferably from 0.5% by weight to 18% by weight.

The organic group bonded to the oxime includes a phenyl group and an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and the like, and the total number of such organic groups Preferably, at least 50% is an alkyl group having from 1 to 8 carbon atoms. From the viewpoint of the properties of the cured coating layer and ease of production, a methyl group is preferred among such alkyl groups. Examples of the molecular structure of the component (C) are a linear chain, a branched chain, a branched form, and a cyclic form.

Ingredient (C) has a temperature of 1 to 1,000 mPa at 25 ° C. s and preferably 5 to 500 mPa. s viscosity. The basis of this viscosity is as follows: when the viscosity at 25 ° C is less than 1 mPa. When s, component (C) is easily volatilized from the organopolyoxane composition; when the viscosity is greater than 1,000 mPa. s, the organopolyoxane composition requires a long curing time.

Examples of this component (C) are trimethylsiloxy-endblocked methylhydrogen polysiloxanes, dimethyl methoxyoxane terminated with trimethyl methoxy group and a Trimethylsiloxy-endblocked dimethylsiloxane.methylhydrogensiloxane copolymers, copolymers of dimethylhydrogenated dimethylsiloxane and methylhydroquinone (dimethylhydrogensiloxy-endblocked dimethylsiloxane) .methylhydrogensiloxane copolymers), cyclic methyl hydrogen polyoxyalkylene (cyclic methylhydrogenpolysiloxanes), cyclic methylhydrogensiloxane. dimethylsiloxane copolymers, tris(dimethylhydrogensiloxy)methylsilane And tetra(dimethylhydrogensiloxysilane).

A plurality of components (C) different from each other may also be used together for the preparation of the same composition.

The amount of the component (C) to be added is sufficient to make the molar ratio (SiH/vi ratio) of the hydrogen atom bonded to the oxime in the component (C): the component (A) and the component (B) to 0.8: 1 to 5:1, and preferably the amount of the component (C) is sufficient to make the molar ratio from 0.9:1 to 3:1. Preferably, the molar ratio SiH/vi is > or equal to 0.8. Preferably, the molar ratio SiH/vi is > or equal to 1.2. More preferably, the molar ratio SiH/vi is > or equal to 1.5. Preferably, the molar ratio SiH/vi is < or equal to 5, preferably < or equal to 3. These ratios help to reduce migration. When the molar ratio is less than the above lower limit value, the curability is lowered, and when the molar ratio exceeds the above upper limit value, a large peeling resistance value is generated and practical releasability is not obtained (practical releasability) ).

The component (D) is a catalyst which promotes a hydrazine hydrogen addition reaction between a hydrogen atom bonded to hydrazine in the component (C) and a hydrazine-bonded alkenyl group in the component (A), and the catalyst is used. The addition reaction between the component (A) and the component (C) causes crosslinking. When the component (B) contains one or more fluorene-bonded alkenyl groups per molecule, the catalyst also promotes a hydrazine hydrogen addition reaction with the hydrazone-bonded alkenyl group in the component (B).

The component (D) is not particularly limited, except that the component (D) is a catalyst for a hydroquinone addition reaction, and a specific example of the component (D) may be a platinum-based catalyst such as chloroplatinic acid, Alcohol-modified chloroplatinic acid, chloroplatinic acid/olefin complex (chloroplatinic acid/olefin) Complexes), chloroplatinic acid/ketone complexes, platinum/alkenylsiloxane complexes, platinum tetrachloride, platinum fine powder, supported on a carrier (eg Solid platinum, platinum black, platinum olefin complex, platinum carbonyl complex, and powdered thermoplastic resin containing the platinum catalyst listed above (for example, methyl methacrylate resin) on aluminum powder or vermiculite powder , polycarbonate resin, polystyrene resin, polyoxyl resin, and the like).

Other examples are ruthenium catalysts such as [Rh(O ₂ CCH ₃ ) ₂ ] ₂ Rh(O ₂ CCH ₃ ) ₃ , Rh ₂ (C ₈ H ₁₅ O ₂ ) ₄ , Rh(C ₅ H ₇ O ₂ ) ₃ Rh(C ₅ H ₇ O ₂ )(CO) ₂ , Rh(CO)[Ph ₃ P](C ₅ H ₇ O ₂ ), RhX ₃ [(R ₆ ) ₂ S] ₃ , (R ₇₃ P) ₂ Rh(CO) _X , (R ₇₃ P) ₂ Rh(CO)H, Rh ₂ X ₂ Y ₄ , H _a Rh _b (E) _c Cl _d , and Rh[O(CO)R ₃ ] _3-n (OH) _n (wherein X is a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom; Y is an alkyl group, CO or C ₈ H ₁₄ ; R ₆ is an alkyl group, a cycloalkyl group or an aryl group; R ₇ Is an alkyl group, an aryl group, an alkoxy group or an aryloxy group; E is an olefin; a is 0 or 1; b is 1 or 2; c is an integer from 1 to 4; d is 2, 3 or 4; 0 or 1) and a ruthenium catalyst such as Ir(OOCCH ₃ ) ₃ , Ir(C ₅ H ₇ O ₂ ) ₃ , [Ir(Z)(E) ₂ ] ₂ , and [Ir(Z)(Diene) ₂ ] (In the formula, Z is a chlorine atom, a bromine atom, an iodine atom or an alkoxy group; E is an olefin; and Dien is a cyclooctadiene).

From the standpoint of accelerating the reaction, it is preferred to use chloroplatinic acid, platinum/vinyl alkane complex and platinum olefin complex, and chloroplatinic acid/divinyltetramethyldioxane. Complex, chloroplatinic acid/tetramethyltetravinylcyclotetraoxane complex and platinum/alkenyl alkane complex, such as platinum/divinyltetramethyldioxane complex Platinum/tetramethyltetravinylcyclotetraoxane complexes and the like are particularly preferred.

Ingredient (D) is added in a catalytic amount, usually from 1 to 1,000 ppm, preferably from 5 to 500 ppm, each of which is a solventless release coating organopolyoxane group according to the present invention. The amount of metal in the component (D) of the total weight of the product.

In addition to the above components, the solventless release coating organopolyoxane composition of the present invention preferably further comprises a hydrazine hydrogen addition reaction inhibitor (E) whereby the composition is thermosetting while inhibiting the gelation reaction and It inhibits curing at ambient temperature and improves storage stability. Examples of such hydrazine addition reaction inhibitors are acetylenic compounds, ene-yne compounds, organic nitrogen compounds, organophosphorus compounds, and oxime compounds and specific examples May be alkynyl alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyne 3-Alcohol (3,5-dimethyl-1-hexyn-3-ol), 3-methyl-1-pentyn-3-ol, 3-phenyl-1-pentyn-3-ol Phenylbutynol and the like; and, for example, 3-methyl-3-penten-1-yne, 3,5-dimethyl-1-hexyne 3-(3-dimethyl-1-hexyn-3-ene), benzotriazole, 1-ethynyl-1-cyclohexanol, and methylethylene Methylcyclocyclosiloxanes. The amount of the hydrazine addition reaction inhibitor added is usually in the range of 0.001 to 5 parts by weight and the amount added is preferably in the range of 0.01 to 2 parts by weight (each case is relative to 100 parts by weight of the component (A) In terms of, and depending on the type of the hydrogen addition reaction inhibitor, the nature and amount of the hydrazine hydrogen addition catalyst, the alkenyl content in the component (A), and the hydrogen atom bonded to the hydrazine in the component (C) The content is appropriately selected.

The composition of the present invention can be produced by uniformly mixing the above components (A) to (D), or the above components (A) to (E), or such components and any other optional components. The order of addition of the individual components is not particularly limited; however, if the composition is not used immediately after mixing, the mixture of the component (A), the component (B) and the component (C) is preferably stored separately from the component (D), and It is best to mix the two before using them. In the example in which the composition contains the component (A) to the component (E), it is preferred to also The type of the component (E) and the amount of the component (E) are adjusted so that the composition does not crosslink at ambient temperature, but is crosslinked and cured under heating.

By uniformly coating the above-described solventless release coating organopolyoxane composition of the present invention on the surface of any of the different sheet-like substrates, and being suitable for the component (A) and the component (C) or the component (A), The component (B) and the component (C) are heated under the condition of crosslinking by a hydroquinone addition reaction, and can form an excellent slip on the surface of the sheet-like substrate and exhibit appropriate peeling resistance to the viscous substance. The release release coating may be, for example, cellophane, cardboard, clay coated paper, polyolefin laminated paper (especially polyethylene laminated paper), thermoplastic resin film (for example, polyester film, polyethylene) Film, polypropylene film, polyamide film), natural fiber fabric, synthetic fiber fabric, metal foil (for example, aluminum foil), and the like.

Usually 50 ° C to 200 ° C is a temperature suitable for curing the solvent-free release coating organopolyoxane composition of the present invention on a sheet-like substrate, but when the substrate has good heat resistance, a curing temperature higher than 200 ° C can be used. . The heating method is not particularly limited, and an embodiment of the heating method may be heating in a hot air circulating oven, radiant heating through an elongated oven or using an infrared lamp or a halogen lamp. It can also be cured by ultraviolet radiation under heat and exposure. When the component (D) is a platinum/alkenyl alkane complex catalyst, even when the amount of the catalyst added is from 50 to 200 ppm relative to the total amount of the composition, it can be easily A cured coating exhibiting excellent adhesion to the sheet-like substrate and excellent peeling properties with respect to the viscous material is obtained in a short time (i.e., at 100 ° C to 150 ° C for 40 seconds to 1 second).

The solventless release coating organic polyoxane composition of the present invention is particularly suitable for coating on at least one side of a sheet-like substrate using a multi-roller coater. Regarding the organopolyoxane group which can be applied to the solventless release coating of the present invention by coating and curing the surface of the sheet substrate A viscous substance of a release sheet or a release film formed by the object, and the viscous substance may be, for example, any one of various pressure-sensitive adhesives and various adhesives, and the embodiment of the viscous substance is an acrylic resin type. Pressure-sensitive adhesive, rubber-type pressure-sensitive adhesive, and polyoxynized pressure-sensitive adhesive, and acrylic resin adhesive, synthetic rubber adhesive, polyoxygenated adhesive, epoxy resin adhesive And polyurethane adhesives. Other examples are asphalt, viscous foods such as paralysis (ie, rice cake), paste and paste, and bird lime. A preferred coating method of the present invention is a multi-roller coater with an in-situ double-sided coating process.

The compositions of the present invention can be used to form cured coatings which exhibit excellent surface slip and exhibit excellent low release properties for viscous materials, particularly as process paper, asphalt A cured release coating former for wrapping paper and various plastic films. Further, a sheet-like substrate having a release coating formed by curing the composition of the present invention is particularly suitable for use in process paper, packaging or wrapping paper as a paste or adhesive substance, pressure sensitive tape, pressure sensitivity. Labels and the like.

Example

The examples and comparative examples are provided below to clearly describe the present invention; however, the present invention is not limited to the following examples. In the following examples and comparative examples, parts are parts by weight, and ppm represents one part per million by weight (weight-ppm). Herein, PDMS means polydimethylsiloxane. The silicone 1 to polyoxy 5 and polyoxy 9 shown in Table 1 below are commercially available from Dow-Corning Corporation.

Preparation of oxane 6 to oxane 8

The vinyl polymer synthesis process (noisee 6-8) was carried out according to the formulation shown in Table 2 below, including the following steps:

(1) Set the equipment and clean it with a nitrogen cleaning system for 20 minutes. The nitrogen stream (1 bubble / 2 seconds) was then slowed down to inert the system.

(2) The octamethylcyclotetraoxane, tetramethyltetravinylcyclotetraoxane, and PDMS (10 mPa.s) were charged through a funnel.

(3) Heating to 100 ° C and subsequent filling of dimethyloxane dipotassium salt, followed by heating to 165 ° C and maintaining this temperature for 3 hours.

(4) After the viscosity was stabilized, the neutralizing agent was added at 165 ° C and maintained at 165 ° C for 30 minutes.

(5) Using a rotary evaporator to remove unreacted volatile matter.

evaluation method:

(1) Coating Curing NNN*: The bath was coated on a polyethylene-coated kraft paper (PEK) substrate, and then cured at 110 °C. The minimum cure time required to form a non-smear, non-rub of, and non-migration coating is recorded in seconds.

*NNN is an abbreviation for non-smear, non-rub of, and non-migration.

(2) Coating Weight (CW): The weight of the coating of polyfluorene was measured by X-ray using an Oxford Laboratory-x3500 apparatus. Uncoated PEK was used as a blank control and calibrated by a PEK substrate coated with known PSMD. For details, see FINAT Test Method No. 7 (FINAT Technical Manual, 7th Edition, 2005).

(3) Slip: Two to three volunteers slid over the sample with their fingers to test the smoothness, and the samples were ranked in a smooth order.

(4) Dynamic friction coefficient (COF): The COF was tested on a texture analyzer TA-XT2. Use a pulley to convert the direction of movement of the probe to a horizontal direction. Cover the bottom surface of the load cell with a sheet of paper. The cured release coating is held and the surface with the release coating is brought into contact with the bottom of the load cell. Then, the drag was carried out under the conditions of a load of 156.09 g and a drag speed = 2.50 mm/sec (mm/s), and the force (g, g) required for dragging was measured. The force (g) required to drag the 156.09 gram load is defined as the coefficient of dynamic friction (COF) of the cured coating.

(5) Anchorage: The coating weight (CW) of the polyfluorene oxide was detected by X-ray using an Oxford Laboratory-x 3500 apparatus. The sample was then rubbed for 30 cycles at a rate of 30 cycles/minute using an abrasion tester (Elcometer 1720). Finally, the coating weight was measured again. The relative anchorage rate can be recorded as CW-post/CW-front x100%.

(6) Peel force (RF): The peel force of the Tesa 7475 standard tape peeled off from the substrate was measured using a 180 degree peel test, which was laminated on the coated release coating and applied to the laminated sample. A load of 20 g/cm 2 was applied and left at room temperature or 70 ° C for 20 hours. After aging for 20 hours, the sample was moved to room temperature, the load was removed and waited for 30 minutes. Subsequently, the peel force was tested using ChemInstruments AR-1500. See FINAT Test Method No. 10 (FINAT Technical Manual, 7th Edition, 2005) for details.

(7) Subsequent adhesion strength (SAS, migration index): The test sample was laminated on the coated release coating using Nitto Denko 31B tape, and a load of 20 g/cm 2 was applied and continued at 70 ° C for 20 hours. After 20 hours, the load was removed and left at room temperature for 30 minutes. Subsequently The 31B tape was transferred to a PET substrate and left for another hour. Peel force was tested using ChemInstruments AR-1500. In the SAS test, the 31B tape was laminated on the PTFE substrate and treated with the same method as the peeled coating sample. The SAS value was recorded as RF release coating / RFPTFE x 100%. See FINAT Test Method No. 11 (FINAT Technical Manual, 7th Edition, 2005) for details.

Composition of the composition of the examples:

In the present invention, the performance behavior of the exfoliation composition formed by mixing the branched siloxane 1 and the high molecular weight decane 4 to 8 is systematically compared. Phenoxide 9 was used as a crosslinking agent in the various formulations shown in Table 3 below:

As shown in Table 4 below, in the present invention, the peeling composition of the linear polyorganosiloxane is compared (the use of decane 2 and decane 3 as the base polymer and subsequent mixing with the high molecular weight oxirane 5) Performance behavior:

Example 1 (comparative)

program:

96 parts of decane, 1,4 part of 1-ethynyl-1-cyclohexanol (ETCH) and 4 parts of decane 4 were uniformly mixed. Then 2.84 parts of decane 9 were added and mixed well. Finally, chloroplatinic acid/1,3-divinyl-1,1,3,3,-tetramethyldioxane complex was added to provide 60 ppm of platinum metal in the final composition, and then uniformly mixed. To form a solvent-free polyoxynitride release coating bath. The bath was coated on a PEK substrate using a knife coater (Euclid Tool & Machine Company 900-M-1N101), and then the coated substrate was placed in an oven at 110 ° C for heat curing. After the release coating on the PEK substrate was cured for 22 seconds, a fully cured release coating was obtained, and then CW, slip, COF, fixation, peel force, and SAS properties were evaluated. The results are shown in Table 5. This cured coating performance is particularly poor in SAS evaluation when using a siloxane having no pendant vinyl group.

Example 2 (actual)

program:

96 parts of decane, 1,4 part of 1-ethynyl-1-cyclohexanol (ETCH) and 4 parts of decane 5 were uniformly mixed. Then 2.89 parts of decane 9 was added and mixed well. most Thereafter, chloroplatinic acid/1,3-divinyl-1,1,3,3,-tetramethyldioxane complex was added to provide 60 ppm of platinum metal in the final composition, and then uniformly mixed. To form a solvent-free polyoxynitride release coating bath. The bath was coated on a PEK substrate using a knife coater (Euclid Tool & Machine Company 900-M-1N101), and then the coated substrate was placed in an oven at 110 ° C for heat curing. After the release coating on the PEK substrate was cured for 22 seconds, a fully cured release coating was obtained, and then CW, slip, COF, fixation, peel force, and SAS properties were evaluated. The results are shown in Table 5. As shown in the table, the performance of the cured coating achieved sufficient performance in all evaluation items.

Example 3 (actual)

program:

96 parts of oxane 1, 0.24 parts of 1-ethynyl-1-cyclohexanol (ETCH) and 4 parts of decane 6 were uniformly mixed. Then 2.89 parts of decane 9 was added and mixed well. Finally, chloroplatinic acid/1,3-divinyl-1,1,3,3,-tetramethyldioxane complex was added to provide 60 ppm of platinum metal in the final composition, and then uniformly mixed. To form a solvent-free polyoxynitride release coating bath. The bath was coated on a PEK substrate using a knife coater (Euclid Tool & Machine Company 900-M-1N101), and then the coated substrate was placed in an oven at 110 ° C for heat curing. After the release coating on the PEK substrate was cured for 22 seconds, a fully cured release coating was obtained, and then CW, slip, COF, fixation, peel force, and SAS properties were evaluated. The results are shown in Table 5. As shown in the table, the performance of the cured coating achieved sufficient performance in all evaluation items.

Example 4 (actual)

program:

96 parts of decane, 1,4 part of 1-ethynyl-1-cyclohexanol (ETCH) and 4 parts of decane 7 were uniformly mixed. Then 2.89 parts of decane 9 was added and mixed well. Finally, chloroplatinic acid/1,3-divinyl-1,1,3,3,-tetramethyldioxane complex was added to provide 60 ppm of platinum metal in the final composition, and then uniformly mixed. To form a solvent-free polyoxynitride release coating bath. The bath was coated on a PEK substrate using a knife coater (Euclid Tool & Machine Company 900-M-1N101), and then the coated substrate was placed in an oven at 110 ° C for heat curing. After the release coating on the PEK substrate was cured for 22 seconds, a fully cured release coating was obtained, and then CW, slip, COF, fixation, peel force, and SAS properties were evaluated. The results are shown in Table 5. As shown in the table, the performance of the cured coating achieved sufficient performance in all evaluation items.

Example 5 (comparative)

program:

96 parts of decane, 1,4 part of 1-ethynyl-1-cyclohexanol (ETCH) and 4 parts of decane 8 were uniformly mixed. Then 2.93 parts of decane 9 were added and mixed well. Finally, chloroplatinic acid/1,3-divinyl-1,1,3,3,-tetramethyldioxane complex was added to provide 60 ppm of platinum metal in the final composition, and then uniformly mixed. To form a solvent-free polyoxynitride release coating bath. The bath was coated on a PEK substrate using a knife coater (Euclid Tool & Machine Company 900-M-1N101), and then the coated substrate was placed in an oven at 110 ° C for heat curing. After the release coating on the PEK substrate was cured for 22 seconds, a fully cured release coating was obtained, and then CW, slip, COF, fixation, peel force, and SAS properties were evaluated. The results are shown in Table 5. This cured coating performance is particularly poor in slip feel evaluation when using a decane 8 having an excess of vinyl at the overhang position as compared to the other examples.

Example 6 (comparative)

program:

100 parts of decane 1 and 0.25 parts of 1-ethynyl-1-cyclohexanol (ETCH) were uniformly mixed. Then 2.98 parts of decane 9 was added and mixed well. Finally, chloroplatinic acid/1,3-divinyl-1,1,3,3,-tetramethyldioxane complex was added to provide 60 ppm of platinum metal in the final composition, and then uniformly mixed. To form a solvent-free polyoxynitride release coating bath. The bath was coated on a PEK substrate using a knife coater (Euclid Tool & Machine Company 900-M-1N101), and then the coated substrate was placed in an oven at 110 ° C for heat curing. After the release coating on the PEK substrate was cured for 22 seconds, a fully cured release coating was obtained, and then CW, slip, COF, fixation, peel force, and SAS properties were evaluated. The results are shown in Table 5. The performance of the cured coating lacking the component (B) was poor in terms of slip feel evaluation and had a higher COF than other practical examples.

Example 7 (actual)

program:

48 parts of oxane 2, 48 parts of decane 3, 0.22 parts of 1-ethynyl-1-cyclohexanol (ETCH) and 4 parts of decane 5 were uniformly mixed. Then 3.81 parts of decane 9 were added and mixed well. Finally, chloroplatinic acid/1,3-divinyl-1,1,3,3,-tetramethyldioxane complex was added to provide 60 ppm of platinum metal in the final composition, and then uniformly mixed. To form a solvent-free polyoxynitride release coating bath. The bath was coated on a PEK substrate using a knife coater (Euclid Tool & Machine Company 900-M-1N101), and then the coated substrate was placed in an oven at 110 ° C for heat curing. After curing the release coating on the PEK substrate for 22 seconds, a fully cured release coating was obtained, followed by CW, slip, COF, fixing rate, peel force and SAS Performance is evaluated. The results are shown in Table 5. As shown in the table, the performance of the cured coating achieved sufficient performance in all evaluation items.

Example 8 (comparative)

program:

50 parts of oxime 2, 50 parts of decane 3 and 0.23 parts of 1-ethynyl-1-cyclohexanol (ETCH) were uniformly mixed. Then 3.94 parts of decane 9 was added and mixed well. Finally, chloroplatinic acid/1,3-divinyl-1,1,3,3,-tetramethyldioxane complex was added to provide 60 ppm of platinum metal in the final composition, and then uniformly mixed. To form a solvent-free polyoxynitride release coating bath. The bath was coated on a PEK substrate using a knife coater (Euclid Tool & Machine Company 900-M-1N101), and then the coated substrate was placed in an oven at 110 ° C for heat curing. After the release coating on the PEK substrate was cured for 22 seconds, a fully cured release coating was obtained, and then CW, slip, COF, fixation, peel force, and SAS properties were evaluated. The results are shown in Table 5. Compared to other practical examples, the performance of the cured coating lacking the component (B) was poor in the evaluation of the slip feel, but the peeling force of the coating was improved, and the SAS evaluation was poor.

a. Coating weight b. Volunteers use the finger to add blind test, 1# best, 2# good, 3# poor

Industrial application

The solventless release coating organic polyoxane composition of the present invention can be used to form a cured coating on the surface of a sheet-like substrate, and the cured coating exhibits excellent slip and excellent peeling for adhesive substances Sex. The sheet-like substrate having the cured coating formed by the composition of the present invention can be used for process paper, paper for packaging or wrapping adhesive materials, pressure sensitive adhesive tape, pressure sensitive adhesive label, and the like.

Claims (11)

One has 50 to 3,000 mPa. s one of the viscosity-free solvent-free release coating organopolyoxane compositions comprising: (A) 100 parts by weight of an organopolyaluminane fluid having a concentration of 10 mPa at 25 ° C. s to 1,000mPa. a viscosity of s and an alkenyl content of from 0.10% by weight to 3.0% by weight; (B) from 0.5 part by weight to 15 parts by weight of the mono-diorganopolysiloxane, the diorganopoly group represented by the following average structural formula (1) Oxyalkane, and the diorganopolyoxyalkylene has a 10,000 mPa at 25 ° C. s to 150,000mPa. a viscosity of s and an alkenyl content of 0.05% by weight to 0.30% by weight: R ^c ₃ SiO(R ^b R ^c SiO _2/2 ) _n1 (R ^c ₂ SiO _2/2 ) _n2 SiR ^c ₃ (1) wherein R ^b is an alkenyl group having 2 to 8 carbon atoms; R ^c is an alkyl group having 1 to 8 carbon atoms or a phenyl group; n1 is a number providing an alkenyl content of 0.05% by weight to 0.30% by weight; n2 is a numerical value A number of at least 1; and n1+n2 is provided to provide 10,000 mPa at 25 °C. s to 150,000mPa. The number of s viscosity; (C) an organohydrogen polyoxyalkylene having an organic hydrogen polyoxyalkylene of 1 mPa at 25 ° C. s to 1,000mPa. a viscosity of s, and the organic hydrogen polyoxyalkylene has at least two hydrogen atoms bonded to the oxime in each molecule, wherein the organic group bonded to the oxime has 1 to 8 carbon atoms An alkyl group or a phenyl group, and the amount of the organic group bonded to the hydrazine is sufficient to cause a hydrogen atom bonded to the hydrazine in the organohydrogen polyoxyalkylene: the alkenyl group in the component (A) and the component (B) The molar ratio is from 0.8:1 to 5:1; and (D) a catalytic amount of a hydrogen addition reaction catalyst. The solventless release coating organopolyoxane composition of claim 1, wherein the component (B) has an alkenyl group content of from 0.05% by weight to 0.20% by weight. The solventless release coating organopolyoxane composition according to claim 1, wherein the component (A) is 100 parts by weight of at least one organopolyoxane fluid, and the at least one organopolyoxane fluid is selected from the group consisting of a group consisting of a linear organopolyoxane, a branched organopolyoxane, a mixture of organopolyoxyalkylenes having a different alkenyl content of from 0.10% by weight to 3.0% by weight, and A mixture of a linear organopolyoxane and a branched organopolyoxane. The solvent-free release coating organopolyoxane composition of claim 1, wherein component (A) is polydimethyl methoxyoxane having (A-1) an alkenyl group only at a molecular terminal and (A-2) a mixture of polydimethylsiloxanes having an alkenyl group at the molecular end and side chain positions. The solvent-free release coating organopolyoxane composition of claim 1, wherein component (A) comprises at least one organopolyoxane fluid having a branched structure and 10mPa at 25°C. s to 1,000mPa. a viscosity of s, the at least one organopolyoxane fluid comprising a oxoxane unit (i) to a oxoxane unit (iii), and the at least one organopolyoxane fluid has a plurality of decane oxides a straight chain portion of unit (ii) and a branching point comprising a oxoxane unit (i), wherein the end of the linear portion is blocked by the oxirane unit (iii): (i) silicon _4/2 siloxane units represented by: 1 or more; (ii) to silicon siloxane units of formula R ₂ SiO _2/2 represented by: 15 to 995; (iii) the formula R ^a R ₂ SiO ₁ a oxoxane unit represented by _/2 , wherein R ^a is a group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and having 2 to 8 carbon atoms. An alkenyl group, a phenyl group, an alkoxy group having 1 to 8 carbon atoms, and a hydroxyl group; and R is a group selected from the group consisting of alkyl groups having 1 to 8 carbon atoms, having An alkenyl group of 2 to 8 carbon atoms, and a phenyl group, wherein at least 0.10% by weight to 3.0% by weight of R ^a and R in the molecule are alkenyl groups having 2 to 8 carbon atoms, and in the molecule at least 50% of the total number of R ^a and R having from 1 to 8 Alkyl group carbon atoms. The solventless release coating organopolyoxane composition of claim 5, wherein component (A) comprises at least one organopolyoxane fluid having a branched structure and is in the following average oxane unit form ( 2) represents the at least one organopolyoxane fluid: (R ^a R ₂ SiO _1/2 ) ₄ (R ₂ SiO _2/2 ) _m (SiO _4/2 ) (2) wherein R ^a is selected from the following a group in the group consisting of: an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a phenyl group, an alkoxy group having 1 to 8 carbon atoms, and a hydroxyl group; R is a group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and a phenyl group; at least 3.0% by weight in the molecule R ^a and R are alkenyl groups having 2 to 8 carbon atoms; at least 50% of the total number of R ^a and R in the molecule are alkyl groups having 1 to 8 carbon atoms; and m = 15 to 995. The solventless release coating organopolyoxane composition of claim 5, wherein component (A) is an organopolyoxane having a branched structure and is represented by the following average oxane unit (3) Represents the organopolyoxane: [(R ^b R ^c ₂ SiO _1/2 ) _n (R ^d R ^c ₂ SiO _1/2 ) _1-n ] ₄ (R ^b R ^c SiO _2/2 ) _m1 (R ^c ₂ SiO _2/2 ) _{m 2} (SiO _4/2 ) (3) wherein R ^b is an alkenyl group having 2 to 8 carbon atoms; R ^c is an alkyl group having 1 to 8 carbon atoms or a phenyl group; ^d is a group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a hydroxyl group; having at least three R in the molecule ^b ; at least 50% of the total number of R ^b , R ^c and R ^d in the molecule is an alkyl group having 1 to 8 carbon atoms; n is 0 or 1; m 1 is a number having a value of at least 1; m 2 is a value at least A number of 0; and m1+m2=15 to 995. The solvent-free release coating organopolyoxane composition according to any one of claims 1 to 7, wherein the composition additionally comprises: (E) 0.001 to 5 parts by weight of a hydrazine hydrogen addition reaction inhibitor, And the composition does not cure at ambient temperature and cures under heat. A sheet type having a cured release coating layer formed by curing a solventless release coating organopolyoxane composition according to any one of claims 1 to 8 in a film form on a sheet type substrate Substrate. A sheet-type substrate having a cured release coating according to claim 9, wherein the sheet-type substrate is cellophane, clay coated paper, polyolefin laminated paper, thermoplastic resin film or metal foil. A method for producing a sheet-type substrate having a cured release coating, which comprises using a multi-roller coater to form a solventless release coating of an organopolyoxane according to any one of claims 1 to 8. The object is coated on at least one side of the sheet-type substrate.