Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—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
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic

Definitions

• the present invention is excellent in handling workability including transportability when the content of the organic solvent is small, and even when diluted with a large amount of organic solvent in the production process of the releasable sheet, the sheet-like substrate such as plastic film is wetted
• the present invention relates to a solvent-type curable organopolysiloxane composition capable of forming a release coating layer having excellent properties / coating properties, good release strength, and excellent stability over time, a release sheet using the composition, and a method for producing the same.
• the silicone composition for forming a releasable cured film used in such a method is a silicone comprising an alkenyl group-containing organopolysiloxane and an organohydrogenpolysiloxane as main components and curing by an addition reaction in the presence of a platinum catalyst. Compositions are known.
• Such silicone-based release agents can be roughly classified into non-solvent type containing no organic solvent, solvent type diluted with an organic solvent and applied to a substrate, and water-based emulsion type according to the solvent.
• a release coating layer is formed on a plastic film, such as protective films, release films for forming dielectric ceramic layers, separator films for adhesives, and separator films for functional films.
• a solvent-type silicone-based release agent is strongly required.
• Patent Document 1 and Patent Document 2 propose solventless silicone-based release agents using alkenyl group-containing organopolysiloxanes with relatively low polymerization degree and low viscosity, but these release agents When thinly applied on a plastic film, the coated layer tends to be repelled, and a uniform coated surface may not be obtained. In addition, it is difficult to apply a water-repellent plastic film to a water-based emulsion-type release agent.
• Patent Documents 3 to 5 a solvent type hydrosilylation reactive silicone release agent having a higher alkenyl group having a higher alkenyl group such as a hexenyl group and containing an organopolysiloxane having a high degree of polymerization
• the functional film using it is proposed. Since these solvent type silicone-based release agents can be applied as they are on a plastic film and the wettability / coating property is sufficiently improved, in particular, a release coating layer was formed on the plastic film. It is extremely useful in providing a functional film.
• release agents based on organopolysiloxanes containing a higher alkenyl group represented by a hexenyl group have a high curing speed under relatively low temperature heating of 100 ° C. or less, and an excellent release performance to adhesive substances.
• a cured film having the following there is an advantage that the plastic film is less likely to be damaged by heating accompanying the formation of the cured film.
• silicone-based release agents are excellent in wettability / coatability to plastic films etc., in recent years, from the viewpoint of environmental load reduction, reduction of the amount of use of organic solvents or regulation of the amount of use It is widely sought in the industry.
• solvent-based release agents containing organopolysiloxanes with a high degree of polymerization a large amount of organic solvent is required to apply to sheet-like substrates such as plastic films.
• the viscosity of the silicone-based release agent becomes excessive, resulting in extremely poor supplyability to the production line and handling workability.
• the present invention has been made to solve the above-mentioned problems, and it is possible to reduce the amount of organic solvent used in the whole production process of a peelable sheet without causing disadvantages in industrial production, and a plastic film Solvent-type curable organopolysiloxane composition which can be uniformly applied to sheet-like substrates such as, and which can form a release layer having good release properties, a release sheet using the same, and a method for producing the same Intended to provide.
• the present inventors have at least 3 alkenyl groups having 4 to 12 carbon atoms in the molecule, and contain vinyl (CH 2 CHCH—) in the alkenyl groups.
• One or more organopolysiloxanes having an amount of 0.1 to 5.0% by mass and a viscosity at 25 ° C.
• the above-mentioned solvent type curable organopolysiloxane composition has wettability / applicability to a plastic film or the like, a release layer, by selecting the kind of curing reactive group and a specific viscosity range for the component (A). Even though it is excellent in releasability, it is excellent in handling workability and transportability even if it has a low organic solvent content and a solvent type curable organopolysiloxane composition with a high solid content concentration is designed, and a releasable sheet production line Further dilution with the desired organic solvent can be used.
• the organic solvent it may be used as a solvent-diluted release agent composition raw material, or may be used as the release agent composition itself.
• the solvent-diluted release agent composition raw material can be easily transported and handled to the manufacturing line in the form of a product having a low organic solvent content, and a small amount of organic solvent can be used in the manufacturing line equipped with a solvent recovery step.
• a peelable sheet can be efficiently produced only by recycling.
• the present invention “[1] (A) molecule has at least 3 alkenyl groups of 4 to 12 carbon atoms in the molecule, and the content of vinyl (CH 2 CHCH—) moiety in the alkenyl group is 0.1 to 5
• a solvent type curable organopolysiloxane composition comprising (D) a hydrosilylation reaction inhibitor, and (E) an organic solvent.
• Component (A) is at least one organopolysiloxane having a viscosity of 10,000 to 50,000 mPa ⁇ s at 25 ° C., and the content of the organic solvent (E) is that of the entire composition
• Component (A) is an organopolysiloxane containing a hexenyl group as the alkenyl group having 4 to 12 carbon atoms, and the content of the organopolysiloxane having an alkenyl group having less than 4 carbon atoms in the composition
• the solvent-type curable organopolysiloxane composition according to [1] or [2], wherein the component (A) is 5.0% by mass or less of the component (A).
• the amount is such that the silicon-bonded hydrogen atoms in component (B) will be 1.0 to 10.0 moles relative to 1 mole of the carbon-carbon double bond in component (A).
• the solvent-type curable organopolysiloxane composition according to any one of [1] to [3].
• [5] The solvent type curable organopolysiloxane according to any one of [1] to [4], which is a release agent composition used for forming a release coating layer or a solvent dilution type release agent composition raw material Composition.
• [6] The viscosity of the whole composition at 25 ° C.
• the content of the (E) organic solvent is in the range of 1 to 50% by mass of the whole composition, and when used for forming a release coating layer, the same or different (E) organic solvent is further added
• the present invention “[8] Peeling having a release coating layer formed by curing the solvent-type curable organopolysiloxane composition according to any one of [1] to [7] on at least one surface of a sheet-like substrate Sex sheet. [9] The peelable sheet of [8], wherein the sheet-like substrate is a plastic film. [10] to [8] or [9] used in one or more applications selected from a protective film, a release film for forming a dielectric ceramic layer, a separator film for an adhesive, and a separator film for a functional film The peelable sheet as described. ".
• the present invention is “[11] A method for producing a peelable sheet according to any one of [8] to [10], including the following steps: Process (I): (A) At least 3 alkenyl groups having 4 to 12 carbon atoms are contained in the molecule, and the content of the vinyl (CH 2 CHCH—) moiety in the alkenyl groups is 0.1 to 5.0 mass% And one or more organopolysiloxanes having a viscosity of 5,000 to 100,000 mPa ⁇ s at 25 ° C. (B) organohydrogenpolysiloxanes having two or more silicon-bonded hydrogen atoms (Si-H) in one molecule, (C) hydrosilylation reaction catalyst, The composition at 25 ° C.
• the solvent type curable organopolysiloxane composition of the present invention By using the solvent type curable organopolysiloxane composition of the present invention, production of a series of peelable sheets from transportation of raw materials for release agent composition to recovery / recycling of organic solvent without causing disadvantages in industrial production It is possible to reduce the environmental load in the industrial production process by reducing the amount of organic solvent used in the entire process. Furthermore, by using the solvent type curable organopolysiloxane composition of the present invention, the wettability / coating property to a plastic film etc. is good, and good peeling characteristics including light peeling strength and its temporal stability are obtained. It is possible to provide a releasable sheet provided with a uniform releasable layer even if it is a sheet-like substrate such as a plastic film. In addition, by using the solvent-type curable organopolysiloxane composition of the present invention, it is possible to provide a method of producing a peelable sheet capable of improving industrial production efficiency and
• the composition of the present invention may be used as a solvent-diluted release agent composition raw material, or may be used as the release agent composition itself depending on the content of the (E) organic solvent. That is, it is shipped or transported to a production site of a peelable sheet as a release agent composition raw material having a low content of organic solvent and excellent in handling workability, and in the production line, the same or different (E) organic as the raw material It is possible to dilute with a solvent and uniformly apply to a sheet-like substrate such as a plastic film.
• the component (A) has at least 3 alkenyl groups having 4 to 12 carbon atoms in the molecule, and the content of the vinyl (CH 2 CHCH—) moiety in the alkenyl group is 0.1 to 5.
• Organopolysiloxanes that contain substantially no or no groups.
• the alkenyl group having 4 to 12 carbon atoms bonded to the silicon atom of the component (A) is preferably an alkenyl group having 4 to 8 carbon atoms, contains a hexenyl group, and vinyl in the hexenyl group (CH 2 CHCH—
• the content of the part) is preferably in the range of 0.1 to 4.0% by mass, and more preferably in the range of 0.1 to 3.0% by mass. If the number of alkenyl groups having 4 to 12 carbon atoms in the molecule is less than 3 (for example, 2 or 1), the crosslink density of the cured product may be reduced, and the release performance of the release coating layer may be insufficient. And poor adhesion to the substrate may occur.
• a sheet-like substrate made of a thermoplastic resin material such as a plastic film in the curing process
• organic groups in the component (A) are not particularly limited, and examples thereof include a hydroxyl group (silanol group), an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, and a phenyl group.
• Ru a hydroxyl group
• the other organic group is preferably a methyl group or a phenyl group, but from the viewpoint of improving peelability etc., a fluorine atom-substituted alkyl group having 3 or more carbon atoms (eg And trifluoropropyl group etc.).
• Component (A) is characterized in that the viscosity at 25 ° C. is in the range of 5,000 to 100,000 mPa ⁇ s, and the viscosity is more preferably in the range of 10,000 to 50,000 mPa ⁇ s, 10,000 to 50,000 The range of 30,000 mPa ⁇ s is particularly preferred.
• the viscosity range of the component (A) is in the above range, a composition having a small content of organic solvent is prepared without impairing the coatability as a solvent type composition and the release performance of the obtained release coating layer. Also in the case where it is done, the handling workability in the industrial process is sufficient.
• the viscosity at 25 ° C is the viscosity of the component (A) measured at 25 ° C using a rotational viscometer.
• Component (A) above can be selected from linear organopolysiloxanes, branched organopolysiloxanes, and linear or branched organopolysiloxanes containing a partial cyclic structure, but it is industrial From the viewpoint, a linear organopolysiloxane represented by the following chemical formula (1) is preferable.
• each R 11 independently represents an unsubstituted or substituted C 1 -C 20 alkyl group (for example, a methyl group), or an aryl group having 6 to 22 carbon atoms
• a phenyl group or the like or a hydroxyl group is preferable, and a methyl group or a phenyl group is preferable.
• R a is an alkenyl group having 4 to 12 carbon atoms, and a hexenyl group is particularly preferable.
• R is a group represented by R 11 or R a .
• m is a number of 0 or more
• n is a number of 1 or more.
• m, n and R each have at least three alkenyl groups having 4 to 12 carbon atoms in the organopolysiloxane molecule represented by the above formula (1), and the viscosity at 25 ° C. is 5,000 to The number is preferably in the range of 100,000 mPa ⁇ s, and the number is preferably such that the content of the vinyl (CH 2 ) CH—) moiety in the alkenyl group is 0.1 to 4.0% by mass.
• R at both ends of Formula (1) is both an alkenyl group (R a ) having 4 to 12 carbon atoms
• the content of the vinyl (CH 2 CHCH—) moiety in the alkenyl group is represented by the following formula : ⁇ (Molecular weight of vinyl moiety of Ra : about 27) ⁇ (m + 2) ⁇ / total molecular weight ⁇ 100 (% by mass)
• Component (A) is particularly preferably an organopolysiloxane represented by the following chemical formula (2) and having a hexenyl group at both ends of the molecular chain and in the side chain.
• m1 is a number of 0 or more
• n1 is a positive number
• a vinyl (CH 2 CHCH—) moiety content in the range of 0.5 to 3.0% by mass, more preferably 1.0 to 2.0% by mass.
• m1 + n1 is a number such that the viscosity at 25 ° C. of the organopolysiloxane represented by the formula (2) is in the range of 5,000 to 100,000 mPa ⁇ s, and more preferably 10,000 to 50,000 mPa ⁇ s. It is the number which becomes s.)
• Component (A) may be composed of only one organopolysiloxane described above, and may be used in combination of two or more organopolysiloxanes differing in structure, degree of polymerization, content of alkenyl group, etc. It is also good.
• the composition of the present invention cures by a curing reaction including a hydrosilylation reaction, the wettability / coating property improvement to plastic films etc. is improved, and the heating temperature is 70 to 100 ° C. at a low temperature for a short time.
• the content of the component in the composition is 5.0 mass% with respect to the component (A) that the organopolysiloxane having an alkenyl group having less than 4 carbon atoms bonded to a silicon atom is not substantially contained % Or less, preferably 3.0% by mass or less, preferably, the content of the component is 5.0% by mass or less, preferably 3.0% by mass or less based on the whole composition.
• it means that it is in the range of 0 to 1.0% by mass.
• Component (B) is an organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms (Si-H) in one molecule, and is a crosslinking agent of the present composition. It is a crosslinking agent of the said component (A).
• Component (B) preferably has at least three silicon-bonded hydrogen atoms in one molecule, and the bonding position of the hydrogen atoms in the molecule is not particularly limited.
• the content of silicon-bonded hydrogen atoms is preferably 0.1 to 2.0% by mass, preferably 0.5 to 1.8% by mass, based on the total weight of the curable organopolysiloxane composition. It is more preferable that Further, as the organic group to be bonded to the silicon atom contained in the component (B) other than a hydrogen atom, alkyl groups such as methyl group, ethyl group, propyl group, butyl group and octyl group are exemplified. Is preferred. Further, as the molecular structure of the organohydrogenpolysiloxane of the component (B), any of linear, branched and branched cyclic, or a combination of one or more thereof is exemplified. The number of silicon-bonded hydrogen atoms in one molecule is the average value of all the molecules.
• the viscosity at 25 ° C. of the component (B) is 1 to 1,000 mPa ⁇ s, preferably 5 to 500 mPa ⁇ s. If the viscosity of the component (B) at 25 ° C. is less than 1 mPa ⁇ s, the component (B) easily volatilizes from the curable organopolysiloxane composition containing it and exceeds 1,000 mPa ⁇ s. And the curing time of the curable organopolysiloxane composition containing such component (B) will be long.
• Such component (B) is not particularly limited.
• both terminal trimethylsiloxy group-capped dimethylsiloxane / methyl hydrogen siloxane copolymer both terminal dimethyl hydrogensiloxy group-capped dimethylsiloxane / methyl hydrogen siloxane co-weight
• Examples are coalescing, dimethylpolysiloxane terminated with dimethylpolysiloxane, methylpolysiloxane polysiloxane terminated with dimethylsiloxy terminal, cyclic methylhydrogenpolysiloxane, and cyclic methylhydrogensiloxane / dimethylsiloxane copolymer.
• component (B) may be used in combination of two or more types of organohydrogenpolysiloxanes having different structures.
• the compounding amount of the component (B) in the curable organopolysiloxane composition of the present invention is such that the silicon-bonded hydrogen atom in the component (B) is one mole of the carbon-carbon double bond in the component (A). And 1.0 to 10.0 mol, preferably 1.0 to 4.0, or 1.0 to 3.0.
• this molar ratio is smaller than the above lower limit value, the curability of the resulting curable composition is lowered, and when it exceeds the above upper limit, the peeling resistance of the obtained release coating layer becomes large, and the good peeling performance is obtained There is a risk that it can not be obtained.
• Component (C) is a hydrosilylation reaction catalyst, which promotes the addition reaction (hydrosilylation reaction) of a silicon-bonded alkenyl group present in the curable organopolysiloxane composition with a silicon-bonded hydrogen atom. .
• the preferred hydrosilylation reaction catalyst is a platinum group metal-containing hydrosilylation reaction catalyst, specifically, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complex of chloroplatinic acid, complex of chloroplatinic acid and ketones A complex of chloroplatinic acid and vinylsiloxane, platinum tetrachloride, fine platinum powder, solid platinum supported on a support of alumina or silica, platinum black, olefin complex of platinum, alkenyl siloxane complex of platinum, platinum Examples thereof include platinum complexes of a thermoplastic organic resin powder such as a methyl complex resin, a polycarbonate resin, a polystyrene resin, a silicone resin and the like containing a carbonyl complex and these platinum catalysts.
• a platinum group metal-containing hydrosilylation reaction catalyst specifically, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complex of chloroplatinic acid, complex of chloro
• complexes of chloroplatinic acid and divinyltetramethyldisiloxane complexes of chloroplatinic acid and tetramethyltetravinylcyclotetrasiloxane, platinum divinyltetramethyldisiloxane complex, platinum tetramethyltetravinylcyclotetrasiloxane complex, etc.
• a platinum alkenyl siloxane complex can be preferably used.
• a non-platinum-based metal catalyst such as iron, ruthenium or iron / cobalt may be used as a catalyst for promoting the hydrosilylation reaction.
• the addition amount of the component (C) to the curable organopolysiloxane composition may be a catalytic amount, and generally, the component (C) contains relative to the total mass of the curable organopolysiloxane composition of the present invention
• the amount of platinum-based metal is preferably in the range of 1 to 1,000 ppm, and more preferably in the range of 5 to 500 ppm.
• Component (D) is a hydrosilylation reaction inhibitor, and in the curable organopolysiloxane composition of the present invention, gelation and curing at normal temperature are suppressed to improve storage stability, and heating at 70 ° C. or higher Sometimes it is a component that develops hardening.
• a hydrosilylation reaction inhibitor an acetylene type-compound, an enyne compound, an organic nitrogen compound, an organic phosphorus compound, and an oxime compound are illustrated.
• Specific compounds include 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, 2-phenyl-3 Alkyne alcohols such as -butyn-2-ol and 1-ethynyl-1-cyclohexanol (ETCH); 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, Enyne compounds such as 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 3-methyl-3-penten-1-yne, and 3,5-dimethyl-3-hexene-1-yne; 1-ethynyl- 1-trimethylsiloxycyclohexane, bis (2,2-dimethyl-3-butynoxy) dimethylsilane, methyl (tris (1,1-dimethyl-2-propynyloxy) C)) Silane, 1,3,5,7-Tetramethyl
• the addition amount of the (D) hydrosilylation reaction inhibitor to the curable organopolysiloxane composition is usually in the range of 0.001 to 5 parts by mass of the component (D) per 100 parts by mass of the component (A).
• Type of component (D) properties and amount of hydrosilylation reaction catalyst used, content of C 4 -C 12 alkenyl group in component (A), weight of silicon-bonded hydrogen atoms in component (B), and curability
• the preferred amount of component (D) to be used can be readily determined.
• the (D) hydrosilylation reaction inhibitor described above may be used alone, or two or more types may be used in combination.
• the curable organopolysiloxane composition diluted using the recovered solvent is not intended for the (D) hydrosilylation reaction inhibitor described above.
• curing defects may occur due to mixing, such problems may be caused by, for example, selecting the type and boiling point difference between the organic solvent and the hydrosilylation reaction inhibitor by the method proposed by the present applicant in JP 2010-018751 A, etc. It is possible to solve by doing.
• the curable organopolysiloxane composition according to the present invention is a solvent type, and contains (E) an organic solvent, and in order to improve handling workability and coatability, component (A) A composition containing (D) and other optional components is used after being dispersed or dissolved.
• a low viscosity liquid organopolysiloxane other than any organic solvent eg, a chain or cyclic organopolysiloxane having a low viscosity of about 0.5 to 10 mPas at 25 ° C.
• Organic solvents include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, octane and isoparaffin, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate And ester solvents such as isobutyl acetate, ether solvents such as diisopropyl ether and 1,4-dioxane, cyclic groups having a polymerization degree of 3 to 6 such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane Polysiloxanes and halogenated hydrocarbons such as trichloroethylene, perchloroethylene, trifluoromethylbenzene, 1,3-bis (trifluoromethyl) benzene and methylpentafluoro
• the solvent-type curable organopolysiloxane composition of the present invention contains the components (A) to (E) described above, and may further contain (F) a photopolymerization initiator.
• Component (F) is a component that imparts energy ray curability such as ultraviolet light to the curable organopolysiloxane composition of the present invention, and by using heat curing by addition reaction and energy ray curing in combination, lower temperature and short time
• the curing reaction can be carried out in the case where it is necessary to minimize the heating time according to the type of the substrate and the purpose of use, damage to the sheet-like substrate due to heat is reduced, and the present invention There are cases where the adhesion of the release layer to the sheet-like substrate can be further improved.
• the silicone component migrates from the surface of the cured film of the release layer according to the present invention, and the release sheet is prevented from being contaminated by the silicone component (this is referred to as transferability of silicone), and the transferability of silicone is further reduced.
• the curable organopolysiloxane composition containing the photopolymerization initiator (F) may be a curing method in which energy rays are irradiated and cured after heat curing reaction, and energy rays are irradiated. It may be a curing method in which a heat curing reaction is performed after that, or may be a curing method in which heating / energy ray irradiation is simultaneously performed.
• Such a component (F) is appropriately selected from compounds known as compounds which generate radicals upon irradiation of energy rays such as ultraviolet rays, for example, organic peroxides, carbonyl compounds, organic sulfur compounds, azo compounds, etc. Can be used.
• Specific compounds include acetophenone, propiophenone, benzophenone, xanthol, fluorein, benzaldehyde, anthraquinone, triphenylamine, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4 -Allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4-dimethoxybenzophenone, 4-chloro-4-benzylbenzophenone, 3-chloroxanthone, 3,9- Dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, Zyl methoxy ketal, 2-chlorothioxanthone, die
• benzophenone, 4-methoxyacetophenone, 4-methylbenzophenone, diethoxyacetophenone and 1-hydroxycyclohexyl phenyl ketone are preferable as the component (E).
• Particularly preferred components (E) include diethoxyacetophenone and 1-hydroxycyclohexyl phenyl ketone.
• the above (F) photopolymerization initiators may be used alone or in combination of two or more.
• the amount thereof is not particularly limited, but is in the range of 0.01 to 10 parts by mass, preferably in the range of 0.01 to 2.5 parts by mass, with respect to 100 parts by mass of the component (A). If the compounding amount of the component (F) is within the above range, the release coating layer obtained by curing the composition of the present invention can be cured at a low temperature and in a short time, and the migration of silicone is improved. And physical properties such as strength.
• an adhesion promoter comprising an alkoxysilane compound such as 3-glycidoxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane
• light stabilizers such as triazoles and benzophenones
• flame retardants such as phosphates, halogens, phosphoruss, and antimonys
• an antistatic agent such as surfactant type, silicone type, organic boron type, conductive polymer type, metal oxide type, vapor deposited metal type, etc. You may process.
• the composition of the present invention is prepared by uniformly mixing the components (A) to (E), the component (F) according to the choice of option and curing system, and further other optional components when they are used. be able to.
• the order of addition of each component is not particularly limited, but when the composition obtained is not used immediately after mixing, a mixture of component (A) and component (B) and component (C) It is preferable to store them separately and to mix them immediately before use.
• the composition comprising the above-mentioned respective components, by adjusting the compounding amount of the component (D), it is designed not to crosslink at normal temperature but to rapidly crosslink and cure when heated to the intended curing temperature.
• the compositions are particularly preferred.
• the relationship of the usage-amount of (E) organic solvent and the suitable usage method of this composition is mentioned later.
• the solvent-type curable organopolysiloxane composition of the present invention should be used as a solvent-diluted release agent composition starting material excellent in handling workability including transportability in a state in which the content of the organic solvent is small. Can.
• the solvent-type curable organopolysiloxane composition of the present invention should be used as a solvent-diluted release agent composition starting material excellent in handling workability including transportability in a state in which the content of the organic solvent is small.
• it is excellent in wettability / coating property to a sheet-like substrate such as a plastic film etc.
• it can be used as a release agent composition which can form the release coating layer excellent in the temporal stability.
• the viscosity of the entire composition is maintained to such an extent that there is no hindrance to handling or solvent dilution in the production process of the releasable sheet, and the transportation cost It is preferable to design as a composition having a low content of the (E) organic solvent from the viewpoint of reducing the amount of the organic solvent used and the amount of the new organic solvent used.
• the component (A) can maintain the wettability / coating property to the sheet-like substrate, and is designed to have a viscosity that can be handled even when the content of the (E) organic solvent is small.
• the content of the (E) organic solvent is in the range of 1 to 50% by mass of the whole composition, and a composition having a large solid content can be designed.
• the content of the organic solvent (E) is in the range of 1 to 40% by mass of the whole composition from the viewpoint of handling workability in the production process of the peelable sheet of the present composition and reduction of solvent consumption and solvent dilution.
• the content of the organic solvent (E) is preferably in the range of 2 to 15% by mass, and more preferably in the range of 3 to 12% by mass, based on the whole composition.
• the viscosity range of the component (A) exceeds the upper limit, the overall viscosity of the composition is too high when the content of the (E) organic solvent is 50% by mass or less of the whole composition, and the handling workability in the production process And may cause problems with solvent dilution, including bath adjustment.
• the solvent-diluted release agent composition raw material described above is excellent in handling workability including transportability, and by reducing the amount of use of a novel organic solvent, the environmental load can be suppressed as a whole of the production process of the peelable sheet, It is highly useful as a single product or product material. Moreover, when designing the production process mentioned later, use of the said solvent dilution type peeling agent composition raw material is suitable, and can provide the production process of the small environmental load with a small release sheet.
• the viscosity of the entire composition at 25 ° C. is 20 to 50,000 mPa ⁇ s in order to obtain good coatability to a sheet-like substrate such as a plastic film
• the viscosity of the whole composition is particularly preferably 20 to 20,000 mPa ⁇ s and 50 to 10,000 mPa ⁇ s in practice.
• the content of the organic solvent (E) is the entire composition, using the solvent-diluted release agent composition raw material described above or the above-mentioned components (A) to (D) other optional components.
• the content of the (E) organic solvent is preferably in the range of 70 to 95% by mass of the whole composition, and 80 to 95% by mass, 85 to 95 You may prepare in the range of mass%.
• the organic solvent used for the release agent composition raw material and the organic solvent used for dilution may be the same or different.
• a final release agent composition is prepared by preparing a release agent composition raw material using toluene as an organic solvent, and diluting with heptane as an additional organic solvent in a release sheet production process. You may Needless to say, the present composition may be prepared as a release agent composition from the beginning, and may itself be handled as a single release agent composition product.
• the solvent-type curable organopolysiloxane composition of the present invention is uniformly coated on the surface of various sheet-like substrates, and sufficient for the component (A) and the component (B) to hydrosilylate and crosslink. Under conditions, when heated, irradiated with energy rays (eg, ultraviolet rays, electron beams, etc.), or a combination of these, it is possible to form a release coating layer consisting of a cured silicone coating (ie, cured organopolysiloxane) coating on the surface It is.
• energy rays eg, ultraviolet rays, electron beams, etc.
• the type of the sheet-like substrate is not particularly limited, and high-quality paper, art paper, cast-coated paper, synthetic paper, thermal paper, paperboard, cardboard, clay-coated paper, polyolefin-laminated paper (polyethylene laminated paper), natural Textile fabrics, synthetic textile fabrics, artificial leather fabrics, metal foils and plastic films can be used, and in particular, plastic films are preferred.
• the type of synthetic resin used for the plastic film is not particularly limited, and examples thereof include polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, nylon, cycloolefin polymer and polymethyl methacrylate. .
• a film of heat-resistant synthetic resin such as polyimide, polyetheretherketone, polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamide imide, polyether sulfone or the like is preferable.
• a transparent plastic film a transparent material such as polyethylene, polypropylene, polystyrene, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, PEN may be used.
• the solvent-type curable organopolysiloxane composition of the present invention is excellent in the wettability / coating property to the above-mentioned plastic film, and can form a uniform release coating layer.
• the form in particular of a sheet-like base material is not restrict
• the thickness of these sheet-like substrates is generally 10 to 300 ⁇ m, preferably 15 to 200 ⁇ m, and particularly preferably 20 to 125 ⁇ m.
• the above-mentioned solvent-type curable organopolysiloxane composition is also excellent in low-temperature curability at 100 ° C. or less, so even if it is a thin synthetic paper or plastic film, it hardly causes any damage due to heating and has relatively low heat resistance. Even a substrate has the advantage of being able to form the desired release coating layer.
• the method for applying the solvent-type curable organopolysiloxane composition of the present invention to a sheet-like substrate can be carried out using any known method, and for example, a gravure coating method, a bar coating method, a spray coating Methods such as spin coating, knife coating, roll coating, and die coating can be used.
• the curing temperature is preferably in the range of 50 to 200 ° C., and in the light of prevention of damage to plastic films and industrial production efficiency, the range of 60 to 150 ° C. is preferable.
• the present composition contains a higher alkenyl group such as a hexenyl group, it has an advantage of being excellent in low temperature curability at 100 ° C. or less (for example, in the range of 70 to 100 ° C.).
• the thickness of the release coating layer obtained by curing is not particularly limited, but is 0.01 to 3 ⁇ m. Is preferably, and more preferably 0.03 to 1 ⁇ m. If the thickness of the release coating layer is less than 0.01 ⁇ m, it may not exhibit sufficient function as a release layer. On the other hand, when the thickness of the release coating layer exceeds 3 ⁇ m, blocking may occur when the obtained release sheet is wound into a roll.
• the release coating layer formed by curing the solvent-type curable organopolysiloxane composition of the present invention has a relatively low release resistance value, has a light release strength or slight adhesion to a substrate, and is not a component (A) It has the advantage that the time-dependent change of peeling force is small compared with the peeling layer which uses a vinyl group etc.
• the releasable sheet using the composition of the present invention is selected from a releasable paper, a protective film, a releasable film for forming a dielectric ceramic layer forming material, a separator film for an adhesive and a separator film for a functional film. Can be suitably used for one or more of the following.
• the solvent-type curable organopolysiloxane composition of the present invention should be used as a solvent-diluted release agent composition starting material excellent in handling workability including transportability in a state in which the content of the organic solvent is small.
• the transportation cost and the amount of use of the novel organic solvent can be reduced, and the whole process can provide a method of producing a peelable sheet with low environmental impact.
• the peelable sheet of the present invention can be obtained by a manufacturing method comprising the following steps.
• the type of substrate is not particularly limited, but the same substrate as the sheet-like substrate described above is exemplified, and a plastic film is particularly preferable.
• step (II) applying the release agent composition prepared in step (I) onto a substrate such as a plastic film
• step (III) Curing the release agent composition applied in step (II) on a substrate such as a plastic film under conditions of 50 to 200 ° C. to form a release coating layer
• step (IV ) A step of recovering the (E) organic solvent volatilized in step (III).
• the amount of dilution with an organic solvent, the coating method to a plastic film, the configuration of a release sheet, etc. are as described above, and the curing conditions in step (II) or step (III) design a more preferable range within the above range It is possible.
• the step of recovering the (E) organic solvent is optional, but can be easily achieved by using a known solvent recovery method.
• a method of separating from air coexisting with solvent vapor that is, a condensation method, a compression method, an absorption method, an adsorption method, and a method combining these may be used.
• Each curable organopolysiloxane composition was coated on the surface of a PET film (manufactured by Mitsubishi Chemical Corporation, 50 microns thick) with a Mayer bar in an amount of 0.2 g / m 2 in terms of solid content.
• an acrylic adhesive [Oribine BPS 5127, trade name made by Toyo Chem Co., Ltd.] is applied on the cured film surface to a wet thickness of 70 ⁇ m. It was uniformly applied and dried at 70 ° C. for 2 minutes. Subsequently, a PET film (manufactured by Mitsubishi Chemical Corporation, 50 microns thick) was attached thereto, and a load of 20 g / cm 2 was applied thereto, and the film was left at 23 ° C. and 50% humidity for 1 day.
• an acrylic adhesive [Oribine BPS 5127, trade name made by Toyo Chem Co., Ltd.] is applied on the cured film surface to a wet thickness of 70 ⁇ m. It was uniformly applied and dried at 70 ° C. for 2 minutes. Subsequently, a PET film (manufactured by Mitsubishi Chemical Corporation, 50 microns thick) was attached thereto, and a load of 20 g / cm 2 was applied thereto, and the film was left at 23
• Example 1 Comparative Examples 1 to 4
• the curable organopolysiloxane compositions (1) to (5) prepared in Preparation Examples 1 to 5 were evaluated by the method shown in [Evaluation of coatability]. Moreover, about the peeling force, it evaluated by the method shown to [peeling force evaluation]. The results are shown in Table 1.
• Example 1 has substantially uniform coatability, and since the change with time of the peeling force is small, the gum-like siloxane component is not used. It has the advantage of being excellent in peelability and coatability.
• the comparative example 2 which uses a vinyl group instead of a hexenyl group, although a fixed improvement is seen regarding coating property, a time-dependent change of peeling force is large and it is unsuitable practically.
• Example 2 Comparative Example 5
• Table 2 The viscosities of the curable organopolysiloxane compositions (6) and (7) prepared in Preparation Examples 6 and 7 were measured, and are shown in Table 2.
• Example 2 in Comparative Example 5 using the component (A-4), when a composition having a handleable viscosity of 5500 mPa ⁇ s is designed, the silicone active component is 30% by mass, and a large amount of organic matter is obtained. The use of a solvent (toluene) is required.
• Example 2 in which the component (A-1) is used, when a composition having a handleable viscosity of 5500 mPa ⁇ s is designed, the silicone active component is 90% by mass, and the concentration of the active component is high.
• a solvent-diluted release agent composition raw material can be designed. It is needless to say that (C) hydrosilylation reaction catalyst can be added to the same composition in the amount necessary for curing and at the desired timing as in the other examples and the like.

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• 2018
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