WO2020149239A1 - Composition de résine de silicone ayant une aptitude au décollage et film anti-adhésif revêtu de celle-ci - Google Patents

Composition de résine de silicone ayant une aptitude au décollage et film anti-adhésif revêtu de celle-ci Download PDF

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Publication number
WO2020149239A1
WO2020149239A1 PCT/JP2020/000719 JP2020000719W WO2020149239A1 WO 2020149239 A1 WO2020149239 A1 WO 2020149239A1 JP 2020000719 W JP2020000719 W JP 2020000719W WO 2020149239 A1 WO2020149239 A1 WO 2020149239A1
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Prior art keywords
resin composition
polyorganosiloxane
silicone resin
easy
weight
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PCT/JP2020/000719
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English (en)
Japanese (ja)
Inventor
伊藤　大輔
修平 三田
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アイカ工業株式会社
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Priority to KR1020217025547A priority Critical patent/KR20210114029A/ko
Publication of WO2020149239A1 publication Critical patent/WO2020149239A1/fr

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    • 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
    • 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
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
    • 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
    • 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 disclosure relates to a releasable silicone resin composition having good adhesiveness to an easy-adhesion-treated film or an untreated polyester film that has not been subjected to an easy-adhesion treatment.
  • An easy-adhesion layer or an easy-adhesion-treated untreated polyester film is applied to an untreated polyester film to form a silicone layer, the silicone layer side of the release film is adhered to glass, and when the release film is peeled together after a long time,
  • the present invention relates to a releasable silicone resin composition that causes little increase in adhesive strength over time and is less likely to cause so-called adhesive residue on the glass surface, and a release film coated with the same.
  • a fixing sheet that can be easily re-attached, can be peeled with a slight peeling force when re-peeling, and adhesive residue does not occur
  • the adhesive layer is made of a polyester resin having a hydroxyl value of 10 to 45 or an acrylic resin having a hydroxyl value of 10 to 45
  • the silicone layer is made of a linear polyorganosiloxane having vinyl groups only at both ends.
  • a fixing sheet has been proposed which is characterized in that at least one kind of silicone selected from silicones made of polyorganosiloxane is crosslinked with an organohydrogenpolysiloxane, and the silicone layer contains silicone oil (Patent Document 1). 1).
  • the silicone oil migrates to the interface with the glass and inhibits the reaction between the SiH group that did not contribute to the addition reaction of silicone and the OH group on the glass surface, thereby fixing the fixing sheet. Since adhesive residue is prevented when the sheet is peeled off again, unreacted organohydrogenpolysiloxane and silicone oil may remain on the glass surface when the fixed sheet is peeled off, which may contaminate the glass surface. There is a problem called.
  • the polyester resin or acrylic resin forming the easily adhesive layer has a high hydroxyl value of 10 to 45, and the polyester resin or acrylic resin having a hydroxyl value of less than 10 is: Since the adhesive force between the easily-adhesive layer and the silicone layer formed by this is weakened, there is a problem that it is difficult to use for forming the easily-adhesive layer. When the easy-adhesion layer is formed on the upper side, there is a problem that the silicone layer described in Patent Document 1 cannot be applied.
  • a base film is coated with a polyester resin having a hydroxyl value of 3 to 45 mgKOH/g on at least one side to form an easily adhesive layer.
  • Silicone resin having the general formula of SiO 1/2 units and SiO 4/2 units, and the molar ratio of SiO 1/2 units to SiO 4/2 units being 0.5:1.0 to 0.8:1.0 (C), a polyorganohydrogensiloxane (D) having a viscosity of 10 to 100 cSt/25° C. and having a hydrogen atom directly bonded to a silicon atom in a side chain, and a curing catalyst (E) necessary for an addition reaction,
  • a releasable silicone resin composition comprising a reactive functional group-containing hydrolyzable silane compound (F) and an aluminum chelate compound (G), and a release film having a silicone layer formed by coating the releasable silicone resin composition.
  • Patent Document 2 has been proposed (Patent Document 2).
  • One aspect of the present disclosure provides a peelable silicone resin composition having good adhesion to the easy-adhesion layer even when the easy-adhesion layer formed on the easy-adhesion treated film has a hydroxyl value of less than 10.
  • the adhesiveness is unlikely to become insufficient with time, and the absolute value of the peel strength, which indicates the adhesiveness to glass, does not increase to a large extent with time, which is sufficient.
  • a releasable silicone resin composition having excellent releasability for a long time is provided.
  • a release film obtained by applying the release silicone composition of the present disclosure to an untreated polyester film that has not been subjected to an easy adhesion treatment has sufficient release properties and tackiness. It is to provide a releasable silicone resin composition which has properties and is less likely to leave an adhesive residue on the glass surface and does not easily contaminate the glass surface, and a release film coated with the same.
  • One embodiment of the present disclosure is to apply the polyester resin having a hydroxyl value of 3 to 45 mgKOH/g on at least one side of a base film to form an easy-adhesion layer on the easy-adhesion layer.
  • a releasable silicone resin composition wherein the base film is a polyester film and is applied to the surface on which the easily adhesive layer is not formed,
  • a linear or branched polyorganosiloxane (B) having vinyl groups at both ends and having a weight average molecular weight of 1 to 100,000;
  • a polyorganohydrogensiloxane (C) having a hydrogen atom directly bonded to a silicon atom other than the terminal,
  • a curing catalyst (D) necessary for the addition reaction
  • the content of OH group is 0.1 to 5.0% by weight
  • the compound is composed of SiO 1/2 unit and SiO 4/2 unit represented by the general formula: SiO 1/2 unit/SiO 4
  • a peelable silicone resin composition containing a polyorganosiloxane (G) having a molar ratio of /2 unit of 0.5 to 1.0.
  • one aspect of the present disclosure provides a peelable silicone resin composition in which the reactive functional group-containing hydrolyzable silane compound (E) is 3-glycidoxypropyltrimethoxysilane.
  • one aspect of the present disclosure provides a peelable silicone resin composition in which the aluminum chelate compound (F) is aluminum trisethylacetoacetate.
  • the reactive functional group-containing hydrolyzable silane compound (E) is a total combination of a polyorganosiloxane (A), a polyorganosiloxane (B), and a polyorganohydrogensiloxane (C).
  • a releasable silicone resin composition comprising 0.8 to 3.5 parts by weight based on 100 parts by weight.
  • the aluminum chelate compound (F) is used in a total amount of 100 parts by weight of the polyorganosiloxane (A), the polyorganosiloxane (B), and the polyorganohydrogensiloxane (C).
  • a peelable silicone resin composition comprising 0.08 to 0.35 parts by weight is provided.
  • one aspect of the present disclosure is on the easy-adhesion layer of an easy-adhesion treated film, wherein an easy-adhesion layer is formed by applying a polyester resin having a hydroxyl value of 3 to 45 mgKOH/g on at least one surface of a base film, or Provided is a release film in which a silicone film is formed by applying the above-mentioned release silicone resin composition on the surface where a base film is a polyester film and an easily adhesive layer is not formed.
  • the releasable silicone resin composition according to one aspect of the present disclosure has good adhesion even if the easy-adhesion layer provided on at least one surface of the easy-adhesion treated film is formed of a polyester resin having a hydroxyl value of less than 10. There is an effect of having a sex.
  • the peelable silicone resin composition of one embodiment of the present disclosure has an effect that the adhesiveness is unlikely to be insufficient with time even for an untreated polyester film that has not been subjected to an easy-adhesion treatment, and has an adhesiveness to glass. Since the absolute value of the peel strength indicating is small to a large extent over time, there is an effect of having sufficient peelability for a long period of time.
  • the peelable silicone resin composition of one embodiment of the present disclosure the silicone layer side of a release film obtained by forming a silicone layer on an easily-adhesive-treated film or an untreated polyester film is adhered to glass and allowed to stand for a long time. Even if the peeling film is peeled off from the glass after the peeling, there is an effect that adhesive residue hardly occurs on the glass surface.
  • the peelable silicone resin composition according to one embodiment of the present disclosure has an effect that the glass surface is unlikely to be contaminated due to the fact that silicone oil that easily migrates is not used.
  • the easy-adhesion layer formed on the base film is formed of a polyester resin having a hydroxyl value of 10 mg/KOH or less, or the base film is a polyester film.
  • an untreated polyester film in which the easy-adhesion layer is not formed has an effect that the adhesiveness between the silicone layer and the base film is sufficient and is not easily peeled off. Adhesion to glass, and when the release film is peeled off from the glass after a longer period of time, it has sufficient adhesiveness and releasability, and has the effect that adhesive residue does not easily occur on the glass surface. The effect is that the surface is less likely to be contaminated.
  • the polyorganosiloxane (A) used in one embodiment of the present disclosure is a linear or branched polyorganosiloxane having a vinyl group bonded to a silicon atom other than the terminal and having a weight average molecular weight of 300 to 1,000,000. And is used in combination with the polyorganosiloxane (B) shown below.
  • the polyorganosiloxane (A) since the polyorganosiloxane (A) has a large molecular weight, it is used to develop viscoelastic adhesiveness to the easy-adhesion layer formed on the easy-adhesion-treated film or the untreated polyester film surface.
  • the polyorganosiloxane (A) is cured by an addition reaction with the organohydrogensiloxane (C) and the curing catalyst (D) shown below, and the organic groups other than the vinyl group which are bonded to the silicon atom may be different or the same. Specific examples thereof include a methyl group, an ethyl group, and a phenyl group.
  • a vinyl group is bonded to a part of silicon atoms other than terminals of polydimethylsiloxane ((methyl bonded to silicon atoms other than terminals). Some of the groups are substituted with vinyl groups).
  • the weight average molecular weight of the polyorganosiloxane is preferably from 300 to 1,000,000 as measured by GPC. If it is less than 300,000, the viscosity of the composition becomes too low, and if it exceeds 1,000,000, the viscosity of the composition becomes too high. Becomes insufficient.
  • the vinyl group is preferably contained in an amount of 0.01% by weight or more.
  • the vinyl group content is preferably 5.0% by weight or less.
  • the polyorganosiloxane (B) used in one embodiment of the present disclosure is a linear or branched polyorganosiloxane having vinyl groups at both ends and having a weight average molecular weight of 1 to 100,000. Used in combination with the organosiloxane (A). In particular, since the polyorganosiloxane (B) has a small molecular weight, it is used for exhibiting tackiness to the easy-adhesion layer formed on the easy-adhesion-treated film.
  • the polyorganosiloxane (B) is cured by an addition reaction with the following organohydrogensiloxane (C) and the curing catalyst (E), as in the case of the polyorganosiloxane (A), to give a silicon atom other than a vinyl group.
  • the organic groups to be bonded may be different or the same. Specific examples thereof include a methyl group, an ethyl group, and a phenyl group. Specific examples include polydimethylsiloxane having vinyl groups at both ends.
  • the weight average molecular weight of the polyorganosiloxane is preferably from 1 to 100,000 as measured by GPC, and when it is less than 10,000, the crosslink density becomes high and adhesion to a substrate such as glass becomes insufficient, and when it exceeds 100,000, the composition The viscosity becomes high and the coatability becomes insufficient.
  • the polyorganohydrogensiloxane (C) used in one embodiment of the present disclosure is a polyorganohydrogensiloxane having a hydrogen atom directly bonded to a silicon atom other than the terminal, and the viscosity is preferably 10 to 100 cSt/25°C. ..
  • the polyorganohydrogensiloxane (C) is crosslinked and cured by the addition reaction of the above polyorganosiloxane (A) and polyorganosiloxane (B) and the curing catalyst (E).
  • the silicon atom to which the hydrogen atom is directly bonded is preferably at a position other than the terminal in order to develop adhesiveness, and when the hydrogen atom is bonded to the silicon atom at the terminal, the hardness of the cured product becomes high and the peeling property becomes high. Becomes insufficient.
  • the crosslink density will be low and the curability will be lowered, and if it exceeds 100 cSt/25°C, the crosslink density will be high and the adhesion to the base film will be low.
  • the content of hydrogen atoms bonded to silicon atoms is preferably 1.0 mmol/g to 20.0 mmol/g, and when it is 1.0 mmol/g or more, curability is improved. If the content of hydrogen atoms is more than 20.0 mmol/g, the tack of the surface of the cured product will be too strong. In order to obtain good adhesion to the polyester film, the hydrogen atom content is more preferably 1.5 mmol/g or more.
  • the organo group bonded to the silicon atom include a methyl group, an ethyl group and a phenyl group.
  • the polyorganohydrogensiloxane may be, for example, linear or branched, and specific examples thereof include methylphenylhydrogenpolysiloxane.
  • the curing catalyst (D) used in one embodiment of the present disclosure is used for causing an addition reaction between the polyorganosiloxane (A) and the polyorganosiloxane (B) and the polyorganohydrogensiloxane (C).
  • a known metal, metal compound, metal complex or the like having a catalytic activity for the hydrosilylation reaction, which is an addition reaction, can be used.
  • platinum, a platinum compound, or a complex thereof are examples of platinum, a platinum compound, or a complex thereof.
  • the compounding amount of the curing catalyst (D) is preferably 1 ppm to 50 ppm, more preferably 5 to 20 ppm, based on the entire composition. If it is less than 1 ppm, the curability is deteriorated, and if it exceeds 50 ppm, it becomes a factor that the transparency of the cured product is decreased.
  • Reactive functional group-containing hydrolyzable silane compound (E) The reactive functional group-containing hydrolyzable silane compound (E) used in one embodiment of the present disclosure improves the adhesiveness with time to the easy-adhesion layer formed on the easy-adhesion-treated film or the untreated polyester film.
  • the content of the reactive functional group-containing hydrolyzable silane compound (E) is 100 parts by weight of the total amount of the polyorganosiloxane (A), the polyorganosiloxane (B) and the polyorganohydrogensiloxane (C).
  • 0.8 to 3.5 parts by weight is preferable, and if less than 0.8 parts by weight, the adhesiveness with time becomes insufficient, and if it exceeds 3.5 parts by weight, the adhesiveness to glass increases with time. The peelability becomes poor.
  • the aluminum chelate compound (F) used in one embodiment of the present disclosure acts as a condensation catalyst of the hydrolyzable group of the above-mentioned reactive functional group-containing hydrolyzable silane compound, and the adhesiveness to glass with time increases. It is used to prevent the peelability from decreasing. Specific examples thereof include ethyl acetoacetate aluminum diisopropylate, ethyl acetoacetate aluminum dibutyrate, diethyl acetoacetate aluminum butyrate, aluminum trisethylacetoacetate, alkyl acetoacetate aluminum diisopropylate, and the like, and two or more alone. May be used as a mixture.
  • the amount of the aluminum chelate compound (F) to be blended is 0.08 to 0 with respect to 100 parts by weight of the total amount of the polyorganosiloxane (A), the polyorganosiloxane (B) and the polyorganohydrogensiloxane (C). 0.35 parts by weight is preferable, and if it is less than 0.08 parts by weight, the adhesiveness to glass increases with time and the releasability becomes insufficient, and if it exceeds 0.35 parts by weight, the adhesiveness to glass decreases with time. To do.
  • OH group content is from the general formula SiO 1/2 units and SiO 4/2 units of 0.1 to 5.0 wt%, SiO 1
  • the molar ratio of /2 unit/SiO 4/2 unit is 0.5 to 1.0, and it is used as a tackifier for improving the initial adhesiveness to glass of the peelable silicone resin composition according to one embodiment of the present disclosure. At the same time, it can be added in order to suppress the increase in the adhesiveness to glass over time. If the OH content exceeds 5.0% by weight, the curability of the composition will deteriorate. If the molar ratio of SiO 1/2 unit/SiO 4/2 unit is less than 0.5 or more than 1.0, the improvement of the adhesive strength may be insufficient.
  • other optional components include alkyne alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and ethynylcyclohexanol; 3-methyl- Enyne compounds such as 3-pentene-1-yne, 3,5-dimethyl-3-hexene-1-yne; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane
  • a reaction inhibitor such as 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, 1,3 divinyltetramethyldisiloxane, benzotriazole may be contained.
  • the content of the reaction inhibitor is 100 parts by weight of the total blend of the polyorganosiloxane (A), the polyorganosiloxane (B) and the polyorganohydrogensiloxane (C) as a content not to suppress the curability due to the addition reaction. On the other hand, it is preferably in the range of 0.0001 to 1 part by weight.
  • viscosity adjustment as other optional components, calcium carbonate, silica sand, talc, carbon black, titanium oxide, zinc oxide, kaolin, silicon dioxide for adjusting the hardness, It may contain an inorganic filler such as melamine, an organic filler, a reinforcing material such as glass fiber for reinforcing the cured resin, and hollow bodies such as shirasu balloon and glass balloon for weight reduction and viscosity adjustment. Can be added.
  • antioxidants, organic pigments, fluorescent pigments, corrosion inhibitors, antioxidants and the like can be used as appropriate.
  • a release film according to one embodiment of the present disclosure is obtained by applying a polyester-based resin having a hydroxyl value of 3 to 45 mgKOH/g on at least one surface of a base film such as a polyester film to form an easy-adhesion layer to obtain an easy-adhesion-treated film.
  • the thickness of the easy-adhesion layer of the easy-adhesion treated film is preferably in the range of 0.05 to 5.0 ⁇ m, and if it is less than 0.05 ⁇ m, the easy-adhesion effect cannot be sufficiently obtained, and if it exceeds 5.0 ⁇ m, the easy-adhesion layer itself Adhesiveness to the base film is reduced.
  • a coating method for the easily adhesive layer coating liquid and the silicone layer coating liquid typified by a three-offset gravure coater or a five-roll coater, a direct gravure coater, a bar coater, an air knife coater, etc. are appropriately used. To be done.
  • the film is an easy-adhesion-treated film having an easy-adhesion treatment, and the film is an untreated polyester film even if it is coated with a polyester resin. Included in the definition of. If the hydroxyl value of the polyester resin in the easy-adhesion layer exceeds 45 mgKOH/g, curing of the composition will be poor.
  • the hydroxyl value serves as an index of the polarity of the easy-adhesion layer, and the higher the hydroxyl group, the higher the polarity, and the higher the adhesiveness between the present composition and the easy-adhesion layer.
  • a separator such as a resin film or coated paper to the silicone layer surface in order to prevent dirt and foreign matter from adhering to the surface of the silicone layer and to improve the handling property of the release film.
  • Examples and Comparative Examples As the polyorganosiloxane (A), a linear polydimethylsiloxane having a weight average molecular weight of 300 to 1,000,000 and a vinyl group bonded to a part of silicon atoms other than terminals (vinyl group content: 0.07 wt.
  • polyorganosiloxane (a) a linear polydimethylsiloxane having a weight average molecular weight of 300 to 1,000,000 and a vinyl group at both ends (vinyl group content: 0.01% by weight)
  • polyorganosiloxane (B) a linear polydimethylsiloxane having a weight average molecular weight of 1 to 100,000 is used as a polyorganohydrogensiloxane (C) having a viscosity of 10 to 100 cSt/25° C. and a silicon atom other than the terminal end.
  • Polyorganohydrogensiloxane having hydrogen atoms directly bonded (hydrogen atom content 14 mmol/g), platinum-vinyl dimer complex (Pt: 0.2% wt) as a curing catalyst (D), reactive functional group-containing
  • hydrolyzable silane compound E
  • aluminum trisethylacetoacetate is used as the aluminum chelate compound (F)
  • the OH group content is 1% by weight as the polyorganosiloxane (G).
  • the coating liquid is applied onto the easy-adhesion layer of a 75 ⁇ m-thick polyester easy-adhesion treated film having an easy-adhesion layer in which a polyester resin having a hydroxyl value of 5 mgKOH/g is applied and cured on one side,
  • a silicone layer is formed by coating the untreated surface of an untreated polyester film having a thickness of 75 ⁇ m and having a thickness after drying of 20 ⁇ m and curing at 130° C. for 90 seconds.
  • a release film coated with the releasable silicone resin compositions of Examples and Comparative Examples was obtained.
  • a 2 kg hand roller was reciprocated once on the release film to press-bond the silicone layer. Then, the release film was slowly peeled off, and the silicone layer of the release film was rubbed with a fingertip under the condition of 23°C. At this time, those in which the silicone layer was wholly peeled from the easy-adhesion layer were evaluated as x, those which were partially peeled were evaluated as ⁇ , and those which were not peeled were evaluated as ⁇ .

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Abstract

Cette invention concerne une composition de résine de silicone ayant une aptitude au décollage, comprenant : (A) un polyorganosiloxane ayant un groupe vinyle lié à un atome de silicium non terminal et ayant une masse moléculaire moyenne en poids de 300 000 à 1 000 000 ; (B) un polyorganosiloxane ayant des groupes vinyle aux deux extrémités et ayant une masse moléculaire moyenne en poids de 10 000 à 100 000 ; (C) un polyorganohydrogénosiloxane ayant un atome d'hydrogène directement lié à un atome de silicium non terminal ; (D) un catalyseur de durcissement ; (E) un composé de silane hydrolysable portant un groupement fonctionnel réactif ; et (F) un composé de chélate d'aluminium. L'invention concerne en outre un film anti-adhésif revêtu de la composition de résine de silicone ayant une aptitude au décollage.
PCT/JP2020/000719 2019-01-15 2020-01-10 Composition de résine de silicone ayant une aptitude au décollage et film anti-adhésif revêtu de celle-ci WO2020149239A1 (fr)

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Citations (5)

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JP2010196011A (ja) * 2009-02-27 2010-09-09 Shin-Etsu Chemical Co Ltd 付加硬化型自己接着性シリコーンゴム組成物
JP2016098286A (ja) * 2014-11-20 2016-05-30 アイカ工業株式会社 剥離性シリコーン樹脂組成物及びこれを塗布した剥離フィルム
JP2016222791A (ja) * 2015-05-29 2016-12-28 フジコピアン株式会社 両面粘着フィルム及びそれを用いた情報表示画面用の保護部材
JP2017066194A (ja) * 2015-09-28 2017-04-06 アイカ工業株式会社 剥離性シリコーン樹脂組成物及びこれを塗布した剥離フィルム
JP2017537177A (ja) * 2014-10-16 2017-12-14 ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ シリコーン組成物及び本組成物から製造される感圧接着剤層を有する感圧接着剤フィルム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010196011A (ja) * 2009-02-27 2010-09-09 Shin-Etsu Chemical Co Ltd 付加硬化型自己接着性シリコーンゴム組成物
JP2017537177A (ja) * 2014-10-16 2017-12-14 ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ シリコーン組成物及び本組成物から製造される感圧接着剤層を有する感圧接着剤フィルム
JP2016098286A (ja) * 2014-11-20 2016-05-30 アイカ工業株式会社 剥離性シリコーン樹脂組成物及びこれを塗布した剥離フィルム
JP2016222791A (ja) * 2015-05-29 2016-12-28 フジコピアン株式会社 両面粘着フィルム及びそれを用いた情報表示画面用の保護部材
JP2017066194A (ja) * 2015-09-28 2017-04-06 アイカ工業株式会社 剥離性シリコーン樹脂組成物及びこれを塗布した剥離フィルム

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