[go: up one dir, main page]

WO2024247069A1 - Composition de silicone pour feuille antiadhésive, et feuille antiadhésive - Google Patents

Composition de silicone pour feuille antiadhésive, et feuille antiadhésive Download PDF

Info

Publication number
WO2024247069A1
WO2024247069A1 PCT/JP2023/019985 JP2023019985W WO2024247069A1 WO 2024247069 A1 WO2024247069 A1 WO 2024247069A1 JP 2023019985 W JP2023019985 W JP 2023019985W WO 2024247069 A1 WO2024247069 A1 WO 2024247069A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
groups
group
mol
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2023/019985
Other languages
English (en)
Japanese (ja)
Inventor
謙児 山本
理 土田
健 中山
イルグォン チャン
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Chemical Co Ltd
Original Assignee
Shin Etsu Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shin Etsu Chemical Co Ltd filed Critical Shin Etsu Chemical Co Ltd
Priority to PCT/JP2023/019985 priority Critical patent/WO2024247069A1/fr
Priority to TW113119451A priority patent/TW202500677A/zh
Publication of WO2024247069A1 publication Critical patent/WO2024247069A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to a silicone composition for release sheets and a release sheet obtained using the composition.
  • a cured film of a silicone composition is formed on the surface of a sheet-like substrate such as paper or plastic film to impart release properties to adhesive materials.
  • a well-known method for forming a cured coating of a silicone composition on the surface of a substrate is to use a platinum compound as a catalyst to cause an addition reaction between an alkenyl-containing organopolysiloxane and an organohydrogenpolysiloxane to form a release coating on the surface of the substrate.
  • a platinum compound as a catalyst to cause an addition reaction between an alkenyl-containing organopolysiloxane and an organohydrogenpolysiloxane to form a release coating on the surface of the substrate.
  • Patent Document 1 reports the addition of an organopolysiloxane containing epoxy groups as a method for improving adhesion to substrates by using a small amount of additive. However, this method only describes adhesion to substrates under high temperature and high humidity conditions, and no evaluation is performed immediately after curing or when stored at room temperature. Furthermore, there is no description of the effect of adding an organopolysiloxane containing epoxy groups on release properties.
  • Patent Document 2 the adhesion to the substrate is improved by adding a reaction product of a liquid polyorganosiloxane containing alkenyl groups and silanol groups with a hydrolyzable silane containing an epoxide group.
  • this method also does not consider the effect of the addition on the release properties.
  • Patent Document 3 a low molecular weight siloxane containing an alkenyl group is added, irradiated with ultraviolet light, and then the coating is cured by heating, improving adhesion to the substrate without affecting the peelability.
  • this method requires a UV irradiation device in addition to a heating dryer.
  • release sheet performance that includes a smaller release force than conventional products as well as high durability that can maintain good adhesion to substrates even under harsh environments such as high temperatures and high humidity during the molding process of the release sheet.
  • existing release sheet compositions tend to have poorer adhesion to substrates the smaller the release force, and there are hardly any compositions that can satisfy the requirements for long-term adhesion under even harsher environments. This is thought to be because many of the materials that are effective in achieving light release, such as those used as various migration components, act to reduce adhesion to the substrate, and the reality is that it is difficult to achieve both light release and excellent adhesion to substrates.
  • Patent Document 4 a silicone composition using a combination of an epoxy group-containing siloxane with a specific structure and an organohydrogensiloxane can achieve both easy release and excellent adhesion to substrates.
  • further improvements may be required depending on the application.
  • the present invention has been made in consideration of the above circumstances, and aims to provide a silicone composition for release sheets that can form a cured film (release film) that has excellent adhesion to the substrate and provides a small release force by not increasing the release force, and that can maintain the adhesion of the film to the substrate for a long period of time even in harsh environments such as high temperature and high humidity.
  • the object is to provide a release sheet obtained from the composition of the present invention.
  • the present invention has been made in order to solve the above problems, and provides an addition-curable silicone composition for release sheets, comprising: (A) 100 parts by mass of an organopolysiloxane having at least two alkenyl groups per molecule, an alkenyl group content of 0.001 to 0.2 mol/100 g, and a 30% by mass toluene diluted viscosity at 25° C.
  • the silicone composition for release sheets of the present invention contains the above-mentioned components (A), (B), (C) and (D) in the prescribed amounts, and is therefore capable of forming a cured film (release film) that has excellent adhesion to substrates, particularly plastic film substrates such as polyester films. Furthermore, the cured film obtained from the silicone composition for release sheets of the present invention is capable of exhibiting a small release force, and while exhibiting such a small release force, is capable of having good adhesion to substrates, and is capable of maintaining good adhesion to substrates for long periods of time even when placed under harsh conditions of high temperature and high humidity, as well as under room temperature conditions.
  • the silicone composition for release sheets of the present invention is preferably an organopolysiloxane in which the (B3) compound comprises, as essential units, R 9 (3-g1) R 8 g1 SiO 1/2 siloxane units (M R8R9 units) or R 9 SiO 3/2 siloxane units (T R9 units) (wherein R 8 are independently alkenyl groups, R 9 are independently an unsubstituted or halogen atom or cyano group-substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, and g1 is a number from 0 to 3), in which the molar ratio of M R8R9 units/T R9 units is 2/8 to 8/2, and the molecular terminals are M R8R9 units or some of the terminals are silanol groups or alkoxy groups.
  • the compound (B1) is preferably an organopolysiloxane which is a partial hydrolysis condensation product of an organoalkoxysilane represented by the following general formula (1-1) and at least one of organoalkoxysilanes represented by the following general formulas (1-2), (1-3), and (1-4), or a mixture thereof.
  • R1 may be the same or different and is a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and no aliphatic unsaturated bond, which may contain an oxygen atom;
  • R12 is an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms; and n is an integer from 3 to 10.
  • the (B1) compound By including such a (B1) compound, the strength of the cured product can be improved and a greater adhesion-improving effect can be achieved.
  • the (B3) compound has a higher alkenyl group content and lower viscosity than the (A) component, which limits molecular movement within the composition and has excellent reactivity with SiH groups, improving curability and reducing the number of remaining SiH groups, resulting in a light release effect. Furthermore, it is believed that the crosslinking density increases as the crosslinking reaction progresses, improving adhesion to the substrate immediately after curing.
  • the (B1) compound is preferably a partial hydrolysis condensate of an organoalkoxysilane mixture containing organoalkoxysilanes represented by the above general formulas (1-1) and (1-4) as essential components and organoalkoxysilanes represented by the above general formulas (1-2) and (1-3) as optional components, and is an organopolysiloxane having a linear, branched or cyclic siloxane structure, or a mixture thereof.
  • the strength of the cured product can be further improved and a greater adhesion improvement effect can be achieved.
  • the strength of the cured product can be improved and a greater adhesion-improving effect can be achieved. Since it is difficult to obtain a sufficient adhesion-improving effect by using the (B2) compound alone, it is speculated that this is due to the fact that the (B1) and (B3) compounds increase the strength of the adhesion-improving layer formed at the interface between the silicone cured coating and the substrate, and strengthen the bond between the adhesion-improving layer and the substrate and the silicone cured coating.
  • the silicone composition for release sheets of the present invention is preferably a composition in which the (B2) compound and the (B3) compound are blended in such a manner that the number of moles of hydrogen atoms bonded to silicon atoms in the (B2) compound divided by the number of moles of alkenyl groups in the (B3) compound is 1.6 or more parts by mass.
  • This blend ratio can achieve a higher adhesion improvement effect.
  • the present invention also provides a release sheet obtained by applying the silicone composition for release sheets of the present invention to a paper substrate or a film substrate and curing the composition.
  • the release sheet of the present invention is obtained by applying the silicone composition for release sheets of the present invention to a substrate and curing it, so the cured film obtained by curing can exhibit a small release force and good adhesion to the substrate, and this good adhesion to the substrate can be maintained for a long period of time even when placed under harsh conditions of high temperature and high humidity, just as at room temperature.
  • the silicone composition for release sheets of the present invention not only produces a non-adhesive cured film with excellent adhesion to the substrate, but also produces good release properties with almost no change in the non-adhesiveness of the cured film before and after adhesion improvement.
  • Conventional adhesion improvement methods inevitably affect the release properties, but a release sheet formed with a cured film of the silicone composition for release sheets of the present invention can improve adhesion to the substrate with almost no effect on the release properties.
  • the cured film produced by the silicone composition for release sheets of the present invention can maintain good adhesion to the substrate for a long period of time even when placed under harsh conditions of high temperature and high humidity.
  • release sheet should be understood in a broad sense, and may be, for example, a release paper containing a paper substrate, or a release film containing a film made of plastic, etc.
  • composition for the release sheet should also be understood in a broad sense, and may be, for example, a silicone composition for release paper, or a silicone composition for release film.
  • component (A) which is an organopolysiloxane having at least two alkenyl groups per molecule, an alkenyl group content of 0.001 to 0.2 mol/100 g, and a viscosity at 25° C.
  • a compound (B1) which is an organopolysiloxane containing 10 mol % or more of siloxane units having a glycidyl group and/or a glycidoxy group bonded to a silicon atom via a carbon atom in one molecule, 0.002 to 0.02 mol/100 g of silanol groups, 0.5 to 2.5 mol/100 g of alkoxy groups, and an average degree of polymerization of 3 to 50;
  • Component (B) containing 0.05 to 2.0 parts by mass of a (B2) compound which is an organohydrogensiloxane having at least three hydrogen atoms, an average degree of polymerization of 10 to 200, and in which 5 to 20 mol % of the substituents are aryl groups, and 0.05 to 3.0 parts by mass of a (B3) compound which is an organopolysiloxane
  • a component (C) which is an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule and which is different from the compound (B2): the number of moles of hydrogen atoms bonded to silicon atoms in the component (C) corresponds to 0.5 to 15 times the number of moles of alkenyl groups in the composition; It has been discovered that a cured coating film having excellent adhesion to a substrate can be obtained by using a composition containing a catalytic amount of (D) a platinum group metal catalyst and 0 to 20,000 parts by mass of an organic solvent.
  • the composition of the present invention can simultaneously achieve both a small release force and excellent adhesion to substrates, and the company has also discovered that this excellent adhesion to substrates can be sustained for a long period of time, which has led to the creation of the present invention.
  • the addition-curable silicone composition for release sheets of the present invention comprises: (A) 100 parts by mass of an organopolysiloxane having at least two alkenyl groups per molecule, an alkenyl group content of 0.001 to 0.2 mol/100 g, and a 30% by mass toluene diluted viscosity at 25° C.
  • the organic solvent (E) is an optional component since the blending amount may be 0 parts by mass per 100 parts by mass of component (A). Furthermore, the silicone composition for release sheets of the present invention may contain other optional components in addition to the components (A), (B), (C), and (D). Specific examples of the optional components are described below.
  • the component (A) used in the present invention is an organopolysiloxane having at least two alkenyl groups in one molecule, an alkenyl group content of 0.001 to 0.2 mol/100 g, and a viscosity at 25° C. when diluted with 30% by mass of toluene of 0.001 to 70 Pa s, and is preferably represented by the following general formula (5):
  • R 5 may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms and no aliphatic unsaturated bond, or an alkenyl group having 2 to 12 carbon atoms which may have an oxygen atom inserted therein, and at least two of R 5 are alkenyl groups.
  • the monovalent hydrocarbon group having 1 to 20 carbon atoms and no aliphatic unsaturated bonds include alkyl groups, preferably having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, and butyl groups; cycloalkyl groups, preferably having 5 to 8 carbon atoms, such as cyclohexyl groups; aryl groups, preferably having 6 to 10 carbon atoms, such as phenyl and tolyl groups; aralkyl groups, preferably having 7 to 10 carbon atoms, such as benzyl groups; and monovalent hydrocarbon groups having 1 to 10 carbon atoms selected from hydroxypropyl, cyanoethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups have been replaced with hydroxyl, cyano, halogen atoms, or the like.
  • the monovalent hydrocarbon group having 1 to 20 carbon atoms and no aliphatic unsaturated bonds is preferably an alkyl group or an aryl group, and more preferably a methyl group, ethyl group, propyl group, or phenyl group.
  • the organopolysiloxane of component (A) has two or more alkenyl groups per molecule. That is, the organopolysiloxane of component (A) has at least two alkenyl groups per molecule. If there are fewer than two alkenyl groups, there is a high possibility that uncrosslinked molecules will remain even after curing, which is undesirable as it reduces the curing properties.
  • the organopolysiloxane of component (A) can have, for example, up to 2000 alkenyl groups per molecule.
  • the alkenyl group content per 100 g of the organopolysiloxane of component (A) is 0.001 to 0.2 mol, and more preferably 0.002 to 0.15 mol. If this content is less than 0.001 mol, the curing properties may decrease, and if it exceeds 0.2 mol, it may cause heavy peeling.
  • the viscosity of component (A) at 25°C is 0.001 to 70 Pa ⁇ s when diluted with 30% by mass toluene, preferably 0.005 to 60 Pa ⁇ s when diluted with 30% by mass toluene, and more preferably 0.01 to 50 Pa ⁇ s when diluted with 30% by mass toluene. If it is less than 0.001 Pa ⁇ s, the composition will not have sufficient coatability, and if it exceeds 70 Pa ⁇ s, workability will decrease.
  • the viscosity can be measured using a rotational viscometer (same below).
  • h, i, j, and k are selected from positive numbers within the above viscosity range, and in particular, h is a positive number of 2 or more, preferably 2 to 300, i is a positive number of 30 or more, preferably 50 to 19,998, and more preferably 100 to 14,700, j is a number of 0 or more, preferably 0 to 100, k is a number of 0 or more, preferably 0 to 100, and 32 ⁇ h+i+j+k ⁇ 20,000, and preferably 100 ⁇ h+i+j+k ⁇ 15,000.
  • component (A) examples include, but are not limited to, the following. Note that Me, Vi, and Ph in the following formula represent a methyl group, a vinyl group, and a phenyl group, respectively.
  • the component (B) used in the present invention is an adhesion improving component, and is a component containing the following compounds (B1), (B2) and (B3).
  • Compound (B1) is a compound that has the effect of improving adhesion when blended with the composition of the present invention, and is an organopolysiloxane that contains, per molecule, 10 mol % or more of siloxane units having a glycidyl group and/or glycidoxy group bonded to a silicon atom via a carbon atom, contains 0.002 to 0.02 mol/100 g of silanol groups, contains 0.5 to 2.5 mol/100 g of alkoxy groups, and has an average degree of polymerization of 3 to 50.
  • Compound (B1) is used in an amount of 0.1 to 8 parts by mass per 100 parts by mass of component (A).
  • the (B1) compound is highly effective in maintaining the adhesion of the cured film (peeling film) obtained using the composition of the present invention to the substrate even under heated and humidified conditions (high temperature and high humidity environments), and is a component that is blended in with the expectation of improving adhesion, especially under harsh usage conditions.
  • the average degree of polymerization is the weight average degree of polymerization in terms of polystyrene measured by gel permeation chromatography (GPC).
  • the organopolysiloxane of compound (B1) is an organopolysiloxane containing 10 mol% or more of siloxane units having glycidyl groups and/or glycidoxy groups bonded to silicon atoms via carbon atoms in one molecule, and if the siloxane units are less than 10 mol%, the adhesive effect to the substrate cannot be obtained.
  • the upper limit of the content of the siloxane units is not particularly limited, but can be, for example, 100 mol%.
  • the organopolysiloxane which is the compound (B1), contains 0.002 to 0.02 moles/100 g of silanol groups. If the content of the silanol groups is less than 0.002 moles/100 g, sufficient adhesion to the substrate cannot be obtained. On the other hand, if the content of the silanol groups exceeds 0.02 moles/100 g, there is a risk of adversely affecting the release properties.
  • the content of the silanol groups is preferably 0.003 to 0.02 moles/100 g.
  • the organopolysiloxane which is the compound (B1), contains 0.5 to 2.5 mol/100g of alkoxy groups. If the content of the alkoxy groups is less than 0.5 mol/100g, sufficient adhesion to the substrate cannot be obtained. On the other hand, if the content of the alkoxy groups exceeds 2.5 mol/100g, there is a risk of adversely affecting the release properties.
  • the content of the alkoxy groups is preferably 0.6 to 2.0 mol/100g.
  • the organopolysiloxane compound (B1) has an average degree of polymerization of 3 to 50, preferably 3 to 20. If the average degree of polymerization is less than 3, the adhesion to the substrate is insufficient, and if the average degree of polymerization is more than 50, the adhesion to the substrate decreases, or the workability decreases.
  • the organopolysiloxane of the (B1) compound may be linear, branched, or cyclic, or may be a mixture thereof, but is preferably a partial hydrolysis condensate of an organoalkoxysilane.
  • the alkoxysilanes having a glycidyl group and/or a glycidoxy group bonded to a silicon atom via a carbon atom are preferably unit trifunctional organoalkoxysilanes, and more preferably organoalkoxysilanes represented by the following general formula (1-1):
  • R1 may be the same or different and is a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and no aliphatic unsaturated bond, which may contain an oxygen atom.
  • n is an integer from 3 to 10.
  • organoalkoxysilanes include the following:
  • organoalkoxysilanes to be co-hydrolyzed and condensed with the above alkoxysilanes at least one of the organoalkoxysilanes represented by the following general formulae (1-2), (1-3), and (1-4) is preferably used, and more preferably, trifunctional and tetrafunctional alkoxysilanes represented by the following general formulae (1-3) and (1-4) are used.
  • the strength of the cured product is improved, and further, by appropriately reducing the solubility and dispersibility of the (B1) compound in the silicone cured film layer, which has excellent release properties and is mainly composed of a linear structure, the (B1) compound is more likely to gather near the interface between the substrate and the silicone cured film, which is thought to provide a greater adhesion improvement effect.
  • R1 may be the same or different, and is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and no aliphatic unsaturated bond, which may contain an oxygen atom, or a hydrogen atom; R12 is an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms.
  • organoalkoxysilanes that are co-hydrolyzed and condensed with alkoxysilanes having a glycidyl group and/or a glycidoxy group bonded to a silicon atom via a carbon atom
  • organoalkoxysilanes of the general formula (1-1) include the following:
  • the hydrogen atom on the monovalent organic group having a glycidoxy group may be replaced by a substituent.
  • the substituent here is preferably one other than an epoxycyclohexyl group.
  • epoxycyclohexyl groups include a 3,4-epoxycyclohexylmethyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, and a 3-(3,4-epoxycyclohexyl)propyl group.
  • R1 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms that does not have an aliphatic unsaturated bond and may contain an unsubstituted or substituted oxygen atom.
  • the hydrocarbon group represented by R1 include alkyl groups such as methyl, ethyl, propyl, and butyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl and tolyl groups; aralkyl groups such as benzyl and phenethyl groups; and groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups have been substituted with hydroxy groups, such as a hydroxypropyl group.
  • R1 is preferably a hydrogen atom or an alkyl group, and more preferably an alkyl group having 1 to 5 carbon atoms.
  • siloxane units formed by the partial hydrolysis condensation reaction of organoalkoxysilanes represented by the above general formulas (1-1) to (1-4) are represented as T E , D, T, and Q, respectively, and the (B1) compound can be represented by the average formula D a T E b T c Q d .
  • a+b+c+d is 3 to 50
  • b/(a+b+c+d) is 0.1 to 1
  • a, c and d are each independently 0 to 35
  • the molecular ends that do not form siloxane bonds with other siloxane units are alkoxy groups or silanol groups.
  • the (B1) compound preferably does not have an alkenyl group in the molecule.
  • the adhesion effect to the substrate can be improved.
  • the amount of compound (B1) is in the range of 0.1 to 8 parts by mass, and preferably in the range of 0.1 to 7 parts by mass, per 100 parts by mass of the organopolysiloxane of component (A). If it is less than 0.1 part by mass, it is not possible to improve adhesion to the substrate, and if it exceeds 8 parts by mass, it may affect the release properties and reduce the strength of the cured film. Furthermore, if it exceeds 8 parts by mass, it may not be possible to maintain excellent adhesion to the substrate for a long period of time under harsh environments.
  • More preferred examples include: etc.
  • the (B1) compound is a partial hydrolysis condensate of an organoalkoxysilane mixture, which contains organoalkoxysilanes represented by the above general formulas (1-1) and (1-4) as essential components and organoalkoxysilanes represented by the above general formulas (1-2) and (1-3) as optional components, and which is an organopolysiloxane having a linear, branched or cyclic siloxane structure, or a mixture thereof.
  • organoalkoxysilane mixture which contains organoalkoxysilanes represented by the above general formulas (1-1) and (1-4) as essential components and organoalkoxysilanes represented by the above general formulas (1-2) and (1-3) as optional components, and which is an organopolysiloxane having a linear, branched or cyclic siloxane structure, or a mixture thereof.
  • Compound (B2) is an organohydrogensiloxane having at least three hydrogen atoms bonded to silicon atoms in one molecule, an average degree of polymerization of 10 to 200, and 5 to 20 mol % of the substituents being aryl groups, and by using it in combination with compounds (B1) and (B3), the adhesion improving effect is further enhanced.
  • the adhesion improving effect cannot be obtained, and although there is no upper limit, it is preferably in the range of 0.5 to 1.5 mol/100g, more preferably 0.7 to 1.3 mol/100g, and if it exceeds 1.5 mol/100g, the releasability of the cured coating decreases.
  • the adhesion-improving effect can be obtained even when the (B2) compound is used alone, it is speculated that when it is used in combination with the (B1) and (B3) compounds, the (B1) and (B3) compounds increase the strength of the adhesion-improving layer that they form at the interface between the silicone cured coating and the substrate, thereby strengthening the bond between the adhesion-improving layer and the substrate and the silicone cured coating.
  • the average degree of polymerization is from 10 to 200. If it is less than 10, the effect of improving adhesion is low, while if it exceeds 200, the stability is reduced, which are undesirable.
  • the average degree of polymerization of the (B2) compound is more preferably from 20 to 150.
  • the aryl group accounts for 5 to 20 mol % of the substituents, and if it is less than 5 mol %, the effect of improving adhesion is insufficient, while if it exceeds 20 mol %, the compatibility with other components decreases, which is undesirable. It is more preferable that the aryl group accounts for 8 to 18 mol % of the substituents of the organohydrogensiloxane.
  • the preferred structure of compound (B2) is an organohydrogensiloxane having a linear or branched structure whose main chain is composed mainly of siloxane units H(R12)SiO2 /2 , where R12 may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • organohydrogensiloxanes represented by the following general formula (2-1) or (2-2), or mixtures thereof.
  • R12 may be the same or different and is an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, 5 to 20 mol % of the total number of substituents, which is the sum of H groups directly bonded to Si and R12, are aryl groups, and m+n is an integer of 2 to 198.
  • the amount of the (B2) compound is 0.05 to 2.0 parts by mass, more preferably 0.06 to 1.5 parts by mass, per 100 parts by mass of (A). If it is less than 0.05 parts by mass, the effect of improving adhesion is small, and if it exceeds 2.0 parts by mass, it may affect the release characteristics, such as causing heavy release. It is preferable that the number of moles of hydrogen atoms bonded to silicon atoms in the (B2) compound is 1.6 or more relative to the number of moles of alkenyl groups in the (B3) compound, more preferably 1.6 to 15, and even more preferably 1.7 to 10, in the amount of the (B2) compound.
  • (B2) compounds include the following:
  • Compound (B3) is an organopolysiloxane having an alkenyl group content of 0.3 mol/100 g or more and a viscosity of 0.01 to 1 Pa ⁇ s at 25° C. Compound (B3) is used in an amount of 0.05 to 3.0 parts by mass per 100 parts by mass of component (A).
  • the monofunctional siloxane unit has the formula: R 9 (3-g1) R 8 g1 SiO 1/2 (hereinafter referred to as M R8R9 unit).
  • the trifunctional siloxane unit of the following formula is an essential unit: R 9 SiO 3/2 (hereinafter referred to as T R9 unit).
  • organopolysiloxanes in which the molar ratio of M 3 R8R9 units/T 3 R9 units is 2/8 to 8/2, it is preferable that the molecular ends are bonded with M 3 R8R9 units, but it is acceptable for some of the ends to form silanol groups or alkoxy groups.
  • R8 is independently an alkenyl group, among which vinyl group is industrially preferred.
  • R9 is independently an unsubstituted or halogen atom or cyano group-substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, among which methyl group and phenyl group are industrially preferred.
  • g1 is a number from 0 to 3, preferably 1 or 2.
  • the compound (B3) is an organopolysiloxane having a molar ratio of the M R8R9 units to the T R9 units of 2/8 to 8/2, preferably 3/7 to 7/3.
  • a molar ratio of 2/8 or more is expected to have an effect of improving adhesion, while a molar ratio of 8/2 or less is preferred because it facilitates industrial production.
  • the (B3) compound may contain difunctional R9 (2-g2) R8g2SiO2 /2 siloxane units (wherein g2 is 0, 1 or 2, referred to as D3R8R9 units) or tetrafunctional SiO4 /2 siloxane units (Q units), but when stronger adhesion is required, particularly in release films, siloxanes that do not contain these and have a molar ratio of M3R8R9 / T3R9 units of 2/8 to 8/2 are preferred.
  • D3R8R9 units or Q units it is preferable to use them in small amounts relative to both the M3R8R9 units and the T3R9 units.
  • the amount of alkenyl groups in the organopolysiloxane of the compound (B3) is preferably 0.3 to 2.5 mol/100 g, more preferably 0.35 to 2.0 mol/100 g, and even more preferably 0.4 to 1.5 mol/100 g, expressed as the alkenyl group content per 100 g of organopolysiloxane. If this content is too small, the effect of improving adhesion may be small. If it is equal to or less than the above upper limit, a good pot life is obtained, which is preferable.
  • the organopolysiloxane of the compound (B3) preferably has a viscosity at 25° C.
  • the degree of polymerization falls within this viscosity range. If the viscosity is less than 0.01 Pa ⁇ s, the effect of improving adhesion may be small, and if it exceeds 1 Pa ⁇ s, the solubility or dispersibility in the composition may decrease.
  • the amount of the (B3) compound is 0.05 to 3.0 parts by weight, and preferably 0.1 to 2.5 parts by weight, per 100 parts by weight of the (A) component. If it is less than 0.05 parts by weight, the effect of improving adhesion to the substrate may be small, whereas if it exceeds 3.0 parts by weight, the releasability of the cured coating may decrease.
  • the (B3) compound is preferably blended so that the ratio of the number of moles of SiH groups in the (B2) compound to the number of moles of alkenyl groups in the (B3) compound (SiH groups/alkenyl groups) is at least 1.6, more preferably from 1.6 to 15, and even more preferably from 1.7 to 10, in order to achieve both an improvement in adhesion and the releasability of the cured coating.
  • the silicone composition for a release sheet of the present invention further contains (C) an organohydrogenpolysiloxane that has at least two hydrogen atoms bonded to silicon atoms in each molecule and is different from the compound (B2) described above.
  • the organohydrogenpolysiloxane of component (C) has at least two hydrogen atoms bonded to silicon atoms (hereinafter also referred to as "SiH groups") in each molecule, and a cured coating is formed by addition reaction of these SiH groups with the alkenyl groups in component (A) and compound (B3).
  • SiH groups silicon atoms
  • the organohydrogenpolysiloxane of component (C) is not particularly limited as long as it has at least two hydrogen atoms bonded to silicon atoms in one molecule and is different from compound (B2). Specific differences from compound (B2) include, for example, that the amount of aryl groups in the substituents is less than 5 mol%.
  • Such component (C) examples include those represented by the average composition formula (7) below.
  • R 7 s H t SiO (4-s-t)/2 (7)
  • R 7 may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, specifically, a methyl group, an ethyl group, an alkyl group preferably having 1 to 6 carbon atoms, such as a propyl group or a butyl group; a cycloalkyl group preferably having 5 to 8 carbon atoms, such as a cyclohexyl group; an aryl group preferably having 6 to 10 carbon atoms, such as a phenyl group or a tolyl group; a hydroxy group in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups have been substituted with a hydroxy group, a cyano group, a halogen atom, or the like; Examples include a propyl group, a cyanoethyl group, a 3-
  • s is a positive number between 0.5 and 2, preferably between 0.6 and 1.5
  • t is a positive number between 0.1 and 2, preferably between 0.2 and 1.5
  • s+t is preferably 3.0 or less, and more preferably 0.5 to 2.7.
  • organohydrogenpolysiloxanes represented by the above formula (7) include polymers or copolymers having at least one of R 7 HSiO 2/2 units (R 7 is the same as above, the same below), HSiO 3/2 units, and R 7 2 HSiO 1/2 units, and optionally further containing at least one of R 7 2 SiO 2/2 units, R 7 SiO 3/2 units, and R 7 3 SiO 1/2 units, but it is preferable that one molecule has at least 2 R 7 HSiO 2/2 units or R 7 2 HSiO 1/2 units in total, preferably 10 to 100. Also, any amount of SiO 4/2 units may be contained.
  • the content of SiH groups in the organopolysiloxane of component (C) is preferably 0.1 to 1.7 mol/100 g, and more preferably 0.2 to 1.6 mol/100 g.
  • the organohydrogenpolysiloxane may be linear, branched, or cyclic, or may be a mixture of these.
  • the viscosity of component (C) at 25°C is preferably 0.001 to 10 Pa ⁇ s, and more preferably 0.005 to 5 Pa ⁇ s. If the viscosity of component (C) is 0.001 to 10 Pa ⁇ s, it is possible to achieve both appropriate curing properties and workability.
  • component (C) examples include, but are not limited to, the following: In the following formula, Me and Ph represent a methyl group and a phenyl group, respectively.
  • the amount of component (C) blended is an amount in which the number of moles of hydrogen atoms bonded to silicon atoms is 0.5 to 15 times the number of moles of alkenyl groups in the composition, and preferably an amount equivalent to 1 to 10 times.
  • the number of moles of hydrogen atoms bonded to silicon atoms is an amount equivalent to 0.5 to 15 times the number of moles of alkenyl groups, thereby making it possible to further enhance curability and adhesion to the substrate while maintaining light releasability.
  • the (B2) compound contains a Si-H group, and therefore contains a hydrogen atom bonded to a silicon atom. Therefore, the hydrogen atoms bonded to silicon atoms in the composition include hydrogen atoms bonded to the silicon atoms of the (C) component and the (B2) compound. It is preferable that the number of moles of hydrogen atoms bonded to silicon atoms in the composition of the present invention is an amount equivalent to 0.5 to 15 times the total number of moles of alkenyl groups in the (A) component and the (B3) compound.
  • the total number of moles of hydrogen atoms bonded to silicon atoms in the (C) component and the (B2) compound is in the range of 0.5 to 15 times, and particularly 1 to 13 times, the total number of moles of alkenyl groups in the (A) component and the (B3) compound.
  • the amount of component (C) to be blended is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, per 100 parts by mass of component (A), in order to obtain an appropriate crosslink density.
  • the platinum group metal catalyst of component (D) is a catalyst for promoting the addition reaction between component (A) and compound (B3) and compound (B2) and component (C), and is a catalyst for promoting the so-called hydrosilylation reaction. Any promoter known to those skilled in the art may be used.
  • platinum group metal catalysts include, for example, platinum, palladium, rhodium, ruthenium, and other catalysts. Among these, platinum catalysts are particularly preferred.
  • platinum catalyst examples include chloroplatinic acid, alcohol or aldehyde solutions of chloroplatinic acid, complexes of chloroplatinic acid with various olefins or vinylsiloxanes, and platinum Examples include various olefin or vinyl siloxane complexes.
  • the amount of component (D) used is a catalytic amount, but in order to obtain a good cured coating, it is generally in the range of 10 to 1,000 ppm, particularly 20 to 500 ppm, calculated as the mass of platinum group metal relative to the mass of component (A). It is preferable to set the above.
  • the silicone composition of the present invention may contain an organic solvent for dilution as an optional component.
  • the organic solvent of component (E) is used in an amount of 0 to 20,000 parts by weight per 100 parts by weight of component (A).
  • the silicone composition of the present invention may be a solvent-free composition obtained by blending the above-mentioned components (A), (B), (C), and (D) with predetermined amounts of optional components. Diluting with an organic solvent provides practical advantages such as improved coating workability and improved coating film condition, including the thickness of the coating film and the surface finish condition.
  • Usable organic solvents include aromatic hydrocarbon compounds such as toluene and xylene, aliphatic hydrocarbon compounds such as hexane, heptane and isoparaffin, ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester compounds such as ethyl acetate and butyl acetate, and ether compounds such as diisopropyl ether and 1,4-dioxane, but any compound that can dissolve silicone is acceptable. It is also possible to use the solvent by dispersing and diluting it in water at any ratio.
  • the blending amount is preferably 100 to 20,000 parts by mass, and more preferably 200 to 10,000 parts by mass, per 100 parts by mass of component (A).
  • the composition of the present invention can contain a release force controlling component (F).
  • a release force controlling component (F) As the component (F), the following component (F1) and/or the following component (F2) can be used, and the blending amount can be 0.1 to 20 parts by mass per 100 parts by mass of the component (A). By including the component (F) in this amount, it is possible to appropriately control the release force while maintaining adhesion to the substrate.
  • (F1) Release force controlling component containing an acrylic-silicone graft copolymer
  • Component (F1) is a release force controlling component containing an acrylic-silicone graft copolymer. By incorporating this component, a very small release force can be obtained and an excellent cured coating (release coating) with a high residual adhesion rate of the peeled pressure-sensitive adhesive sheet can be provided.
  • the acrylic-silicone graft copolymer used in the present invention is a copolymer having a weight average molecular weight of 1,000 to 100,000, which is obtained by radical polymerization of an organopolysiloxane compound (a) having an acrylic group and/or a methacrylic group (hereinafter also referred to as a (meth)acrylic group) and a radically polymerizable monomer (b) having one radically polymerizable group per molecule.
  • the weight-average molecular weight of the copolymer is 1,000 to 100,000, preferably 1,500 to 50,000, and more preferably 2,000 to 30,000, in terms of polystyrene, as measured by gel permeation chromatography (hereinafter abbreviated as "GPC") using toluene as the developing solvent.
  • GPC gel permeation chromatography
  • Organopolysiloxane compound having (meth)acrylic groups Organopolysiloxane compound having (meth)acrylic groups
  • the organopolysiloxane compound (a) used in the present invention is not particularly limited as long as it has a (meth)acrylic group, but from the standpoints of ease of copolymerization with the radically polymerizable monomer (b) having one radically polymerizable group in one molecule, ease of synthesis of the organopolysiloxane compound itself, and the effect of the release force controlling component, it is preferable that the organopolysiloxane compound (a) is a radically polymerizable silicone macromonomer represented by the following general formula (3):
  • R2 is a hydrogen atom or a methyl group
  • X is a group (divalent functional group) selected from an oxygen atom, an NH group, and a sulfur atom.
  • Y is a divalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, which may have an oxygen atom inserted therein.
  • alkylene groups such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene and octamethylene, arylene groups such as phenylene, combinations of two or more of these groups (alkylene-arylene groups, etc.), -CH 2 CH 2 -O-CH 2 CH 2 -, -CH 2 CH 2 -O-CH 2 CH 2 -, -CH(CH 3 )CH 2 -O-CH(CH 3 )CH 2 -, -CH 2 CH 2 CH 2 CH 2 -O-CH 2 CH 2 CH 2 -, and the like.
  • Y is preferably an ethylene group, a propylene group, or a butylene group.
  • f is an integer of
  • R3 may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms, a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, or a substituent represented by the following general formula (4):
  • R 4 may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms, a hydrogen atom, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms.
  • g is an integer of 0 to 300.
  • R 3 and R 4 specific examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms for R 3 and R 4 include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl and tolyl groups, aralkyl groups such as benzyl and phenethyl groups, and hydroxypropyl groups, cyanoethyl groups, 3-chloropropyl groups, and 3,3,3-trifluoropropyl groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with hydroxy groups, cyano groups, halogen atoms, and the like.
  • alkyl groups such as methyl, ethyl, propyl, and butyl groups
  • cycloalkyl groups such as cyclohexyl groups
  • aryl groups
  • alkoxy group having 1 to 10 carbon atoms include methoxy groups, ethoxy groups, propoxy groups, and butoxy groups.
  • R 3 is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 5 carbon atoms.
  • R 4 is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 5 carbon atoms.
  • g is an integer of 0 to 300, preferably 0 to 100, and more preferably 0 to 50.
  • component (a) examples include, but are not limited to, the following.
  • Me, OMe, and Ph in the following formula represent a methyl group, a methoxy group, and a phenyl group, respectively.
  • the radically polymerizable monomer (b) used in the present invention may be used alone or in combination of two or more kinds, and is not particularly limited as long as it is a compound having one radically polymerizable group in one molecule.
  • component (b) examples include compounds having one radical polymerizable group per molecule, such as acrylic, methacrylic, styryl, cinnamate, vinyl, and allyl. Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and isobornyl.
  • (meth)acrylic acid ester compounds such as perfluorobutylethyl (meth)acrylate, trifluoropropyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, etc.; epoxy group-containing radical polymerizable monomers such as glycidyl (meth)acrylate, ⁇ -methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, etc.; 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, etc.
  • Examples include hydroxyl group-containing radical polymerizable monomers such as dimethylpropyl (meth)acrylate and 2-hydroxybutyl (meth)acrylate; radical polymerizable silane compounds such as ⁇ -methacryloxypropyl trimethoxysilane, ⁇ -methacryloxypropyl methyl dimethoxysilane, ⁇ -methacryloxypropyl dimethyl methoxysilane, ⁇ -methacryloxypropyl triethoxysilane, ⁇ -methacryloxypropyl methyl diethoxysilane, ⁇ -methacryloxypropyl tributoxysilane, ⁇ -methacryloxypropyl triisopropenoxysilane, ⁇ -acryloxypropyl trimethoxysilane, acryloxymethyl trimethoxysilane, ⁇ -acryloxypropyl triethoxysilane, ⁇ -acryloxypropyl methyl diethoxysilane, styryl trimethoxys
  • the composition contains an alkyl (meth)acrylate having 1 to 30 carbon atoms, and more preferably methyl (meth)acrylate.
  • the polymerization mass ratio [(a)/(b)] of the organopolysiloxane compound (a) having a (meth)acrylic group to the radical polymerizable monomer (b) having one radical polymerizable group in one molecule is The polymerization mass ratio [(a)/(b) is preferably in the range of 30/70 to 99/1, more preferably 40/60 to 97/3, and further preferably 50/50 to 95/5. ) is within the range of 30/70 to 99/1, sufficient compatibility with the silicone composition can be exhibited while maintaining a light release effect, and as a result, the release force controlling component (F) can be separated. This can prevent this from happening.
  • the solution polymerization method is particularly preferred because it is easy to adjust the molecular weight of the resulting acrylic-silicone graft copolymer to an optimal range.
  • Solvents that can be used in this case include one or a mixture of two or more of aromatic hydrocarbons such as benzene, toluene, xylene, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; and alcohols such as ethanol, isopropanol, n-butanol, isobutanol, etc.
  • the polymerization temperature is preferably in the range of 50 to 180°C, and more preferably in the range of 60 to 120°C. Under these temperature conditions, the polymerization reaction can be completed in about 1 to 10 hours.
  • the method for extracting the copolymer from the copolymer solution examples include evaporating the solvent, adding a poor solvent such as water or methanol to the copolymer solution, precipitating the copolymer, and drying it.
  • the blending amount is preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 15 parts by mass, per 100 parts by mass of component (A).
  • component (F) is blended in the above preferred blending amount, both excellent light release effect and excellent curability can be achieved.
  • the component (F2) is a phenylmethylpolysiloxane having a linear structure, and may have no functional groups or may have alkoxy groups and/or silanol groups at the terminals.
  • the (F2) component is preferably an organopolysiloxane having a viscosity of 0.01 to 70 Pa ⁇ s when diluted with 30% by mass of toluene at 25°C.
  • the (F2) component having a viscosity in this range it is possible to achieve both excellent peel force control effects and excellent productivity.
  • the silicone composition of the present invention is obtained by blending the above-mentioned components (A), (B1), (B2), (B3), (C), and (D) in predetermined amounts, but may further contain the above-mentioned optional components (E) and (F) in the preferred amounts, and may further contain other components in any amounts as required.
  • Components known as those normally used in silicone-based release agent compositions may be added in the usual blending amounts.
  • Other optional components include, for example, various organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, oxime compounds, organic chloro compounds, and the like that can be used as known pot life extenders.
  • examples include acetylene alcohols 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 3-methyl-3-1-penten-1-yne and 3,5-dimethyl-1-hexyn-3-yne, reaction products of these acetylene compounds with alkoxysilanes, siloxanes, or hydrogensilanes, vinyl siloxanes such as tetramethylvinylsiloxane cyclics, organic nitrogen compounds such as benzotriazole, and other organic phosphorus compounds, oxime compounds, and organic chromium compounds.
  • the amount to be added may be any amount that provides a good pot life, and generally, 0.01 to 10 parts by mass per 100 parts by mass of component (A) is preferred, and 0.05 to 5 parts by mass is more preferred.
  • composition of the present invention When the composition of the present invention is made into an emulsion composition, a surfactant and a high molecular weight emulsifier can be blended, and the appropriate blending amount is in the range of 0.1 to 10 parts by mass per 100 parts by mass of component (A).
  • antioxidants such as known antioxidants, pigments, stabilizers, antistatic agents, defoamers, adhesion improvers other than component (B), thickeners, and inorganic fillers such as silica can be added.
  • the silicone composition for release sheets is preferably prepared by mixing the above-mentioned components (A), (B1), (B2), and (B3), component (C), and any optional components uniformly in advance, and then adding component (D) immediately before use.
  • Another preparation method is to mix components (A), (C) and any optional components uniformly in advance, and then add adhesion improving components (B) (compounds (B1), (B2) and (B3)) and component (D) immediately before use, which is advantageous for optimizing the release properties of the cured product.
  • adhesion improving components B
  • component (D) component (D) immediately before use
  • a method of separately adding the compounds (B1), (B2), and (B3) is also preferably used. Since the compounds (B1), (B2), and (B3) exhibit their adhesion-improving effects in different situations, it is desirable to adjust the amounts of the compounds (B1), (B2), and (B3) added to the optimum amounts according to the use conditions of the composition from the standpoints of adhesion, release properties, and cost.
  • the compounds (B1), (B2) and/or (B3) may be used as an additive composition in which they are mixed with other components.
  • the release sheet of the present invention is obtained by applying the silicone composition for release sheets of the present invention to a paper substrate or a film substrate and curing the composition.
  • the release sheet of the present invention can include, for example, a sheet-like substrate such as a paper substrate or a film substrate, and a cured product (cured film) of the silicone composition for release sheets of the present invention formed on the substrate.
  • a sheet-like substrate such as a paper substrate or a film substrate
  • a cured product (cured film) of the silicone composition for release sheets of the present invention formed on the substrate.
  • the silicone composition for release sheets of the present invention can be used as is or further diluted with the above-mentioned dilution solvent or water within the above-mentioned range, and then coated at 0.01 to 100 g/m2 onto one or both sides of a sheet-like substrate such as paper or film using a coating method such as coating with a comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater, gravure coater, wire bar coater , screen coating, dip coating, cast coating, etc., and then heated at 50 to 200° C. for 1 to 120 seconds to form a cured coating on the substrate.
  • a coating method such as coating with a comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater, gravure coater, wire bar coater , screen coating, dip coating, cast coating, etc.
  • substrates examples include polyethylene laminated paper, glassine paper, fine paper, kraft paper, various coated papers such as clay-coated paper, synthetic papers such as Yupo, polyethylene films, polypropylene films such as CPP and OPP, polyester films such as polyethylene terephthalate film (PET film), polyamide films, polyimide films, polylactic acid films, polyphenol films, polycarbonate films, etc.
  • PET film polyethylene terephthalate film
  • the substrate surface may be corona-treated, etched, or plasma-treated.
  • Viscosity at 25°C is 100 Pa ⁇ s.
  • Viscosity at 25°C when diluted with 30% by mass toluene is 0.10 Pa ⁇ s
  • Alkenyl group content 0.003 mol/100 g
  • (A-2) 0.03 mol % of dimethylvinylsiloxane units represented by (CH 3 ) 2 (CH 2 ⁇ CH)SiO 1/2 , 0.12 mol % of methylvinylsiloxane units represented by (CH 3 )(CH 2 ⁇ CH)SiO 2/2 ; 1.5 mol % of diphenylsiloxane units represented by (C 6 H 5 ) 2 SiO 2/2 ,
  • An organopolysiloxane that is composed of 98.35 mol% dimethylsiloxane units represented by ( CH3 ) 2SiO2 /2 and has an average of 10 alkenyl groups per molecule.
  • the viscosity at 25°C when diluted with 30% by weight of toluene is 10 Pa ⁇ s.
  • Alkenyl group content 0.002 mol/100 g
  • Component (B) Component (B) Compound (B1-1) Tetraethoxysilane 166.7 parts by mass (0.7 moles) 3-Glycidoxypropyltrimethoxysilane 47.3 parts by mass (0.2 moles) Methyltriethoxysilane 17.8 parts by mass (0.1 mole) An epoxy group-containing siloxane oligomer obtained by partial hydrolysis and condensation of 15 parts by mass (0.83 moles) of water in the presence of hydrochloric acid at 80°C for 5 hours.
  • Viscosity at 25°C is 0.02 Pa ⁇ s Average degree of polymerization: 5 20 mol% of siloxane units having epoxy groups bonded to silicon atoms via carbon atoms
  • the silanol content was 0.015 mol/100 g, and the amount of silanol was measured by the Grignard method in which the amount of methane generated was determined using methylmagnesium iodide.
  • Alkoxy group content 1.4 mol/100 g
  • (b1-3) Compound: 3-glycidoxypropyltrimethoxysilane, 236.3 parts by mass (1 mole) An epoxy group-containing siloxane oligomer obtained by partial hydrolysis and condensation of 9 parts by mass (0.5 moles) of water in the presence of hydrochloric acid at 70°C for 5 hours. Viscosity at 25°C is 0.005 Pa ⁇ s Average degree of polymerization: 2 100 mol% of siloxane units having epoxy groups bonded to silicon atoms via carbon atoms Silanol group content: 0.015 mol/100 g Alkoxy group content: 0.9 mol/100 g
  • (C) Component (C-1) 4 mol % of trimethylsiloxane units represented by (CH 3 ) 3 SiO 1/2 ;
  • An organohydrogenpolysiloxane consisting of 96 mol% methylhydrogensiloxane units represented by ( CH3 )HSiO2 /2 , with a viscosity of 0.02 Pa ⁇ s at 25°C.
  • Examples 1 to 12 and Comparative Examples 1 to 11> Using the above-mentioned components (A) to (E) and (G) as raw materials, coating compositions were prepared according to the following procedure. Components (A), (B), (C), (E), and (G) were placed in a flask according to the compounding ratios shown in Tables 1 to 6, and dissolved by stirring. Component (D) was added to the resulting solution so that the amount was 30 ppm, calculated as platinum mass, relative to component (A), and the mixture was stirred and mixed to obtain a coating composition.
  • the obtained composition was applied to a 38 ⁇ m thick PET film using an applicator to a solid thickness of 30 ⁇ m, and then heated in a hot air dryer at 130°C for 60 seconds to form a release agent layer (cured film), and the resulting release film (coated product) was used for evaluation.
  • the release film immediately after heating was used, and for evaluation of peel strength and residual adhesion rate, the release film aged at 25°C for 24 hours was used.
  • peeling force N/50 mm
  • a 25 mm wide adhesive tape (tesa7475 tape, product name manufactured by Tesa Tape. Inc.) was attached to the surface side of the cured film of the release film, and the tape was heated for 20 hours in a 70° C. dryer under a load of 20 g/cm 2. After cooling in air for about 30 minutes, the tesa7475 tape was peeled off from the release film and attached to a SUS stainless steel plate, pressed with a 2 kg tape roller once and left at 25° C.
  • tesa7475 tape product name manufactured by Tesa Tape. Inc.
  • the tesa7475 tape was pulled at an angle of 180° and a peeling speed of 0.3 m/min using a tensile tester, and the force (N/25 mm) required to peel the tesa7475 tape from the SUS stainless steel plate, i.e., the adhesive force F, was measured.
  • H/V molar ratio 1 is the value obtained by dividing the number of moles of SiH groups in C by the total number of moles of vinyl groups in A + B3, 0.5 to 15 H/V molar ratio 2 is the value obtained by dividing the number of moles of SiH groups in B2 by the number of moles of vinyl groups in B3.
  • Adhesion 1 is the evaluation result after one week at 25°C and 50% RH.
  • Adhesion 2 is the evaluation result after one day at 60°C and 90% RH.
  • Adhesion 3 is the evaluation result after one week at 60°C and 90% RH.
  • H/V molar ratio 1 is the value obtained by dividing the number of moles of SiH groups in C by the total number of moles of vinyl groups in A + B3, 0.5 to 15 H/V molar ratio 2 is the value obtained by dividing the number of moles of SiH groups in B2 by the number of moles of vinyl groups in B3.
  • Adhesion 1 is the evaluation result after one week at 25°C and 50% RH.
  • Adhesion 2 is the evaluation result after one day at 60°C and 90% RH.
  • Adhesion 3 is the evaluation result after one week at 60°C and 90% RH.
  • H/V molar ratio 1 is the value obtained by dividing the number of moles of SiH groups in C by the total number of moles of vinyl groups in A + B3, 0.5 to 15 H/V molar ratio 2 is the value obtained by dividing the number of moles of SiH groups in B2 by the number of moles of vinyl groups in B3.
  • Adhesion 1 is the evaluation result after one week at 25°C and 50% RH.
  • Adhesion 2 is the evaluation result after one day at 60°C and 90% RH.
  • Adhesion 3 is the evaluation result after one week at 60°C and 90% RH.
  • H/V molar ratio 1 is the value obtained by dividing the number of moles of SiH groups in C by the total number of moles of vinyl groups in A + B3, 0.5 to 15 H/V molar ratio 2 is the value obtained by dividing the number of moles of SiH groups in B2 by the number of moles of vinyl groups in B3.
  • Adhesion 1 is the evaluation result after one week at 25°C and 50% RH.
  • Adhesion 2 is the evaluation result after one day at 60°C and 90% RH.
  • Adhesion 3 is the evaluation result after one week at 60°C and 90% RH.
  • H/V molar ratio 1 is the value obtained by dividing the number of moles of SiH groups in C by the total number of moles of vinyl groups in A + B3, 0.5 to 15 H/V molar ratio 2 is the value obtained by dividing the number of moles of SiH groups in B2 by the number of moles of vinyl groups in B3.
  • Adhesion 1 is the evaluation result after one week at 25°C and 50% RH.
  • Adhesion 2 is the evaluation result after one day at 60°C and 90% RH.
  • Adhesion 3 is the evaluation result after one week at 60°C and 90% RH.
  • H/V molar ratio 1 is the value obtained by dividing the number of moles of SiH groups in C by the total number of moles of vinyl groups in A + B3, 0.5 to 15 H/V molar ratio 2 is the value obtained by dividing the number of moles of SiH groups in B2 by the number of moles of vinyl groups in B3.
  • Adhesion 1 is the evaluation result after one week at 25°C and 50% RH.
  • Adhesion 2 is the evaluation result after one day at 60°C and 90% RH.
  • Adhesion 3 is the evaluation result after one week at 60°C and 90% RH.
  • Examples 1 to 12 of the present invention are shown in Tables 1 to 3 above, and the results of Comparative Examples 1 to 11 are shown in Tables 4 to 6 above. From the results in Tables 1 to 3, it can be seen that the compositions of Examples 1 to 12 of the present invention have excellent curability and can exhibit excellent adhesion to the substrate, and in many of the Examples, a release agent layer (cured film) was formed that was able to maintain this excellent adhesion for a long period of time even in severe environments such as high temperature and high humidity. In addition, it is shown that the addition of an adhesion improver does not increase the peel force, and it can be seen that a release agent layer was provided that did not significantly impair the adhesiveness of the pressure-sensitive adhesive tape.
  • compositions of Comparative Examples 1 and 11 did not contain the component (B).
  • the composition of Comparative Example 2 did not contain the compound (B1).
  • the composition of Comparative Example 4 did not contain the compound (B2).
  • the composition of Comparative Example 6 did not contain the compound (B3).
  • the release agent layers obtained from the compositions of Comparative Examples 1, 2, 4, 6, and 11 were unable to maintain adhesion to the substrate for a long period of time under the harsh environment of 60° C. and 90% RH.
  • Comparative Example 3 was a composition in which the amount of (B1) compound was too high
  • Comparative Example 5 was a composition in which the amount of (B2) compound was too high
  • Comparative Example 7 was a composition in which the amount of (B3) compound was too high.
  • Examples 11 and 12 are compositions in which the compounding ratio of (B2) compound and (B3) compound in Examples 1 and 2 was changed, and the value obtained by dividing the number of moles of SiH groups in (B2) compound by the number of moles of vinyl groups in (B3) compound was 1.5, which was smaller than the value of 3.8 in Examples 1 and 2.
  • the release agent layers obtained from the compositions of Examples 11 and 12 were able to maintain adhesion to the substrate for a long period of time under the harsh environment of 60°C and 90% RH, but were slightly inferior to the release agent layers obtained from the compositions of Examples 1 and 2.
  • the (b1-3) compound used in Comparative Example 8 had an average degree of polymerization of 2. As a result, the release agent layer obtained from the composition of Comparative Example 8 was unable to maintain adhesion to the substrate for a long period of time under harsh conditions.
  • the (b1-4) compound used in Comparative Example 9 and the (b1-5) compound used in Comparative Example 10 were organosiloxanes composed only of monofunctional siloxane units and difunctional siloxane units, and were different from the (B1-1) and (B1-2) compounds, which were organosiloxanes composed of trifunctional siloxane units and tetrafunctional siloxane units, and did not contain silanol groups or alkoxy groups.
  • the release agent layers obtained from the compositions of Comparative Examples 9 and 10 were unable to maintain adhesion to the substrate for a long period of time under the harsh environment of 60°C and 90% RH.
  • the compound (B1-2) used in Example 8 is different from the compound (B1-1) in that it is composed only of trifunctional siloxane units and does not contain tetrafunctional siloxane units.
  • the release agent layer obtained from the composition of Example 8 was able to maintain adhesion to the substrate for a long period of time even in an environment of 60°C and 90% RH, which is severe, but the results were slightly inferior to those of the release agent layer obtained from the composition of Example 7.
  • An addition-curable silicone composition for release sheets (A) 100 parts by mass of an organopolysiloxane having at least two alkenyl groups per molecule, an alkenyl group content of 0.001 to 0.2 mol/100 g, and a 30% by mass toluene diluted viscosity at 25° C.
  • An addition-curable silicone composition for release sheets comprising: [2]: The silicone composition for release sheets according to the above item [1], characterized in that the compound (B3) is an organopolysiloxane which contains R9 (3-g1) R8g1SiO1 / 2siloxane units ( M2R8R9 units) and R9SiO3 / 2siloxane units ( T2R9 units) (wherein R8 is independently an alkenyl group, R9 is independently an unsubstituted or halogen atom or cyano group-substituted monovalent hydrocarbon group which does not contain an aliphatic unsaturated bond, and g1 is a number from 0 to 3), in which the molar ratio of M2R8R9 units/ T2R9 units is 2/8 to 8/2, and the molecular terminals are M2R8R9 units or some of the terminals are silanol groups or alkoxy groups.
  • R9 3-g1
  • the compound (B1) is an organopolysiloxane which is a partial hydrolysis condensation product of an organoalkoxysilane represented by the following general formula (1-1) and at least one of organoalkoxysilanes represented by the following general formulas (1-2), (1-3), and (1-4), or a mixture thereof.
  • R1 may be the same or different and is a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and no aliphatic unsaturated bond, which may contain an oxygen atom; R12 is an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms; and n is an integer from 3 to 10.
  • (B1) compound is a partial hydrolysis condensate of an organoalkoxysilane mixture containing organoalkoxysilanes represented by the above general formulas (1-1) and (1-4) as essential components and organoalkoxysilanes represented by the above general formulas (1-2) and (1-3) as optional components, and is an organopolysiloxane having a linear, branched or cyclic siloxane structure, or a mixture thereof.
  • the present invention is not limited to the above-described embodiments.
  • the above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included within the technical scope of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de silicone pour une feuille antiadhésive, la composition comprenant : (A) un organopolysiloxane ayant deux groupes alcényle ou plus dans une molécule, la teneur en groupes alcényle se situant dans une plage prédéterminée; (B1) un organopolysiloxane qui contient, dans une molécule, une quantité prédéterminée ou plus d'une unité siloxane ayant un groupe glycidyle et/ou un groupe glycidoxy se liant à un atome de silicium par l'intermédiaire d'un atome de carbone, contient des groupes silanol en une quantité dans une plage prédéterminée, contient des groupes alcoxy en une quantité dans une plage prédéterminée, et a un degré moyen de polymérisation dans une plage prédéterminée; (B2) un organohydrogénosiloxane ayant, dans une molécule, trois atomes d'hydrogène ou plus se liant chacun à un atome de silicium et ayant un degré de polymérisation dans une plage prédéterminée, une partie dans une plage prédéterminée de substituants étant des groupes aryle; (B3) un organopolysiloxane ayant une teneur en groupe alcényle tombant dans une quantité prédéterminée ou plus; (C) un organohydrogénosiloxane différent de B2; et (D) un catalyseur à base de métal du groupe du platine. Par conséquent, la présente invention concerne une composition de silicone pour une feuille antiadhésive, qui présente une excellente adhérence à un matériau de base, qui peut maintenir l'adhérence dans des environnements difficiles, et qui peut former un film durci ayant une faible force de pelage.
PCT/JP2023/019985 2023-05-29 2023-05-29 Composition de silicone pour feuille antiadhésive, et feuille antiadhésive Pending WO2024247069A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP2023/019985 WO2024247069A1 (fr) 2023-05-29 2023-05-29 Composition de silicone pour feuille antiadhésive, et feuille antiadhésive
TW113119451A TW202500677A (zh) 2023-05-29 2024-05-27 剝離片用矽氧組成物及剝離片

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2023/019985 WO2024247069A1 (fr) 2023-05-29 2023-05-29 Composition de silicone pour feuille antiadhésive, et feuille antiadhésive

Publications (1)

Publication Number Publication Date
WO2024247069A1 true WO2024247069A1 (fr) 2024-12-05

Family

ID=93657069

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/019985 Pending WO2024247069A1 (fr) 2023-05-29 2023-05-29 Composition de silicone pour feuille antiadhésive, et feuille antiadhésive

Country Status (2)

Country Link
TW (1) TW202500677A (fr)
WO (1) WO2024247069A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007009072A (ja) * 2005-06-30 2007-01-18 Shin Etsu Chem Co Ltd 剥離フィルム用シリコーン組成物
JP2008520804A (ja) * 2004-11-18 2008-06-19 ダウ・コ−ニング・コ−ポレ−ション シリコーン剥離コーティング組成物
JP2011236289A (ja) * 2010-05-07 2011-11-24 Shin-Etsu Chemical Co Ltd 剥離フィルム用シリコーン組成物
WO2016060084A1 (fr) * 2014-10-17 2016-04-21 信越化学工業株式会社 Additif fortement antiadhésif pour feuille antiadhésive, composition d'organopolysiloxane pour feuille antiadhésive et feuille antiadhésive
JP2018538372A (ja) * 2015-09-25 2018-12-27 エルケム・シリコーンズ・フランス・エスアエスＥＬＫＥＭ ＳＩＬＩＣＯＮＥＳ Ｆｒａｎｃｅ ＳＡＳ 可撓性基材用の不粘着性コーティングを製造するための架橋性シリコーン組成物及びこの組成物に含有される付着促進用添加剤
WO2021192100A1 (fr) * 2020-03-25 2021-09-30 信越化学工業株式会社 Composition de silicone pour feuilles anti-adhésive, et feuille anti-adhésive

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008520804A (ja) * 2004-11-18 2008-06-19 ダウ・コ−ニング・コ−ポレ−ション シリコーン剥離コーティング組成物
JP2007009072A (ja) * 2005-06-30 2007-01-18 Shin Etsu Chem Co Ltd 剥離フィルム用シリコーン組成物
JP2011236289A (ja) * 2010-05-07 2011-11-24 Shin-Etsu Chemical Co Ltd 剥離フィルム用シリコーン組成物
WO2016060084A1 (fr) * 2014-10-17 2016-04-21 信越化学工業株式会社 Additif fortement antiadhésif pour feuille antiadhésive, composition d'organopolysiloxane pour feuille antiadhésive et feuille antiadhésive
JP2018538372A (ja) * 2015-09-25 2018-12-27 エルケム・シリコーンズ・フランス・エスアエスＥＬＫＥＭ ＳＩＬＩＣＯＮＥＳ Ｆｒａｎｃｅ ＳＡＳ 可撓性基材用の不粘着性コーティングを製造するための架橋性シリコーン組成物及びこの組成物に含有される付着促進用添加剤
WO2021192100A1 (fr) * 2020-03-25 2021-09-30 信越化学工業株式会社 Composition de silicone pour feuilles anti-adhésive, et feuille anti-adhésive

Also Published As

Publication number Publication date
TW202500677A (zh) 2025-01-01

Similar Documents

Publication Publication Date Title
TWI707891B (zh) 剝離片用輕剝離添加劑及剝離片用有機聚矽氧烷組成物以及剝離片
JP6350672B2 (ja) 剥離シート用重剥離添加剤及び剥離シート用オルガノポリシロキサン組成物並びに剥離シート
JP6485262B2 (ja) 剥離紙又は剥離フィルム用シリコーン組成物、剥離紙及び剥離フィルム
JP5525121B2 (ja) 表面の性質の改変された硬化型シロキサン組成物
EP2125957A1 (fr) Compositions de couche de séparation au silicone
TWI883136B (zh) 剝離片用矽氧組成物及剝離片
WO2024247069A1 (fr) Composition de silicone pour feuille antiadhésive, et feuille antiadhésive
TWI855119B (zh) 鉑族金屬系觸媒及硬化性有機聚矽氧烷組成物以及剝離片
CN121195041A (zh) 剥离片用有机硅组合物及剥离片
TW202523775A (zh) 剝離薄片用之硬化性有機聚矽氧烷組成物，及剝離薄片

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23939548

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2025523711

Country of ref document: JP

Kind code of ref document: A