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WO2023195268A1 - Composition adhésive sensible à la pression de silicone, adhésif sensible à la pression de silicone, film adhésif sensible à la pression, dispositif d'affichage d'image et procédé d'évaluation d'adhésif sensible à la pression de silicone - Google Patents

Composition adhésive sensible à la pression de silicone, adhésif sensible à la pression de silicone, film adhésif sensible à la pression, dispositif d'affichage d'image et procédé d'évaluation d'adhésif sensible à la pression de silicone Download PDF

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Publication number
WO2023195268A1
WO2023195268A1 PCT/JP2023/007158 JP2023007158W WO2023195268A1 WO 2023195268 A1 WO2023195268 A1 WO 2023195268A1 JP 2023007158 W JP2023007158 W JP 2023007158W WO 2023195268 A1 WO2023195268 A1 WO 2023195268A1
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Prior art keywords
sensitive adhesive
pressure
silicone pressure
silicone
film
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PCT/JP2023/007158
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English (en)
Japanese (ja)
Inventor
誠也 内田
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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Priority claimed from JP2022164689A external-priority patent/JP2023155125A/ja
Application filed by Shin Etsu Chemical Co Ltd filed Critical Shin Etsu Chemical Co Ltd
Publication of WO2023195268A1 publication Critical patent/WO2023195268A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00

Definitions

  • the present invention relates to a silicone pressure-sensitive adhesive composition, a silicone pressure-sensitive adhesive, a pressure-sensitive adhesive film, an image display device, and a method for evaluating silicone pressure-sensitive adhesives.
  • silicone-based pressure-sensitive adhesives Compared to acrylic adhesives, silicone-based pressure-sensitive adhesives have superior tack, adhesion, and holding power required for pressure-sensitive adhesives.
  • silicone has the characteristics of excellent heat resistance, cold resistance, and electrical properties, so it is widely used in various adhesive products such as electrical insulation tape, heat-resistant tape, and masking tape.
  • Silicone pressure-sensitive adhesives can be classified into addition reaction curing types, condensation reaction curing types, and peroxide curing types based on their curing mechanism. Among these, addition reaction curing types are widely used because they have good reactivity and do not generate by-products.
  • silicone-based pressure-sensitive adhesives are being studied for use in the field of display elements such as smart devices (Patent Document 1).
  • Patent Document 2 discloses a silicone-based pressure-sensitive adhesive that leaves little adhesive residue on the adherend surface, but the adhesive strength in a 180° peel test is as low as 0.05 to 4 N/25 mm, which is not sufficient. do not have.
  • Patent Documents 3 and 4 are characterized by less adhesive residue on the adherend surface, but the adhesive strength is still not sufficient. Furthermore, there is no mention of the coloring of the pressure-sensitive adhesive, and the appearance and transparency are unknown.
  • the evaluation method for adhesive residue on the adhesive layer is ambiguous, based on senses such as visual observation and finger touch, and the essential evaluation of whether or not the adhesive layer remains is difficult. A method is needed.
  • the present invention was made in view of the above circumstances, and provides a pressure-sensitive adhesive that has both high adhesive strength and excellent peelability (less adhesive residue), has little coloring and is highly transparent, and a pressure-sensitive adhesive.
  • the purpose is to provide an evaluation method.
  • a silicone pressure sensitive adhesive composition comprising: (A) A linear organopolysiloxane represented by the following average formula (1) and having a content of alkenyl groups bonded to silicon atoms of 0.0010 to 0.010 mol/100 g, (In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, which may be the same or different from each other, and n is a number from 3,000 to 15,000.
  • R 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, which may be the same or different from each other, and m is a number from 0 to 200.
  • R 3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, hydroxyl group, carbon (1 to 4 alkoxy groups or halogen atoms) and (SiO 4/2 ) units, and the ratio of (R 3 3 SiO 1/2 ) units to (SiO 4/2 ) units is 0.5.
  • :3-dimensional network organopolysiloxane in the range of 1 to 1.8:1,
  • D hydrosilylation reaction catalyst, as well as,
  • E A silicone pressure sensitive adhesive composition is provided that includes an antioxidant.
  • the silicone pressure-sensitive adhesive composition specified in this way can be used as a silicone pressure-sensitive adhesive composition that has both excellent adhesive strength and removability, and provides a silicone pressure-sensitive adhesive with little coloring. .
  • the number of hydrogen atoms bonded to silicon atoms in the component (B) is preferably 0.2 to 50 per alkenyl group in the component (A).
  • the resulting silicone pressure-sensitive adhesive will have better adhesive strength and releasability.
  • the antioxidant contains two or more kinds of antioxidants.
  • the antioxidant contains a phenolic antioxidant and a thioether antioxidant.
  • the present invention also provides a silicone pressure-sensitive adhesive obtained by curing the silicone pressure-sensitive adhesive composition described above.
  • Such a silicone pressure-sensitive adhesive has both excellent adhesive strength and releasability, and has little coloring.
  • the silicone pressure-sensitive adhesive of the present invention has an adhesive force of 5.0 N/25 mm or more at a room temperature of 23° C. and a pulling speed of 300 mm/min in a 180° peel test specified in JIS Z 0237. It is preferable.
  • Such a silicone pressure-sensitive adhesive has sufficient adhesive strength.
  • the silicone pressure-sensitive adhesive of the present invention was tested in a 180° peel test specified in JIS Z 0237 of a polyethylene terephthalate film on the adhered surface after the peel test, at a room temperature of 23°C and a pulling speed of 300 mm/min. It is preferable that the adhesive force is 0.1 N/25 mm or less.
  • Such a silicone pressure-sensitive adhesive has excellent releasability.
  • the silicone pressure-sensitive adhesive of the present invention preferably has a b * value of 0.15 or less at a thickness of 300 ⁇ m in the L * a * b * color system defined in JIS Z 8781-4.
  • Such a silicone pressure-sensitive adhesive has little yellow coloring and has excellent transparency.
  • the present invention provides a pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer made of the silicone pressure-sensitive adhesive described above.
  • Such a pressure-sensitive adhesive film has both excellent adhesive strength and removability, and has little discoloration.
  • the present invention provides an image display device including a pressure-sensitive adhesive layer made of the above-mentioned silicone pressure-sensitive adhesive.
  • Such an image display device has excellent reliability and visibility.
  • the present invention also provides a method for evaluating silicone pressure-sensitive adhesives, comprising: (1) a first step of preparing a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer made of a silicone pressure-sensitive adhesive on one side of a base material; (2) After the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film is crimped onto the surface of a stainless steel plate according to JIS Z 0237, the pressure-sensitive adhesive film is peeled off at a 180° angle to the stainless steel plate at a tensile speed of 300 mm/min.
  • a polyethylene terephthalate film is crimped within the range after peeling off the pressure-sensitive adhesive film on the stainless steel plate after the second step, and then the polyethylene terephthalate film is crimped at a tensile speed of 300 mm/min.
  • a method for evaluating a silicone pressure-sensitive adhesive is provided, which includes a fourth step of determining the quality of the silicone pressure-sensitive adhesive based on the adhesive strength.
  • the fourth step is a step of determining the quality of the silicone pressure-sensitive adhesive based on whether the adhesive force satisfies 0.1 N/25 mm or less.
  • the silicone pressure-sensitive adhesive composition of the present invention provides a silicone pressure-sensitive adhesive that has both high adhesive strength and excellent releasability (less adhesive residue), and has little coloring, so it has excellent reworkability and transparency.
  • the silicone pressure-sensitive adhesive composition of the present invention having such excellent properties is useful for laminating pressure-sensitive adhesive films and image display devices.
  • the inventors of the present invention have discovered that by using a specific addition-curing silicone composition, a silicone pressure-sensitive adhesive with excellent adhesive strength and removability, and with little coloring can be created.
  • the present invention was completed by discovering that the present invention can be obtained, and also by discovering a method for quantitatively evaluating pressure-sensitive adhesives.
  • a silicone pressure sensitive adhesive composition comprising: (A) A linear organopolysiloxane represented by the following average formula (1) and having a content of alkenyl groups bonded to silicon atoms of 0.0010 to 0.010 mol/100 g, (In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, which may be the same or different from each other, and n is a number from 3,000 to 15,000.
  • R 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, which may be the same or different from each other, and m is a number from 0 to 200.
  • R 3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, hydroxyl group, carbon (1 to 4 alkoxy groups or halogen atoms) and (SiO 4/2 ) units, and the ratio of (R 3 3 SiO 1/2 ) units to (SiO 4/2 ) units is 0.5.
  • :3-dimensional network organopolysiloxane in the range of 1 to 1.8:1,
  • D hydrosilylation reaction catalyst, as well as,
  • E A silicone pressure sensitive adhesive composition containing an antioxidant.
  • the present invention also provides a method for evaluating silicone pressure-sensitive adhesives, comprising: (1) a first step of preparing a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer made of a silicone pressure-sensitive adhesive on one side of a base material; (2) After the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film is crimped onto the surface of a stainless steel plate according to JIS Z 0237, the pressure-sensitive adhesive film is peeled off at a 180° angle to the stainless steel plate at a tensile speed of 300 mm/min.
  • a polyethylene terephthalate film is crimped within the range after peeling off the pressure-sensitive adhesive film on the stainless steel plate after the second step, and then the polyethylene terephthalate film is crimped at a tensile speed of 300 mm/min.
  • the silicone pressure-sensitive adhesive composition of the present invention contains the following components (A) to (E).
  • Component (A) in the silicone pressure-sensitive adhesive composition of the present invention is a straight line represented by the following average formula (1) and having an alkenyl group content bonded to a silicon atom of 0.0010 to 0.010 mol/100g. It is a linear organopolysiloxane.
  • R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, which may be the same or different from each other, and n is a number from 3,000 to 15,000. .
  • R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, which may be the same or different, and examples of the monovalent hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, Alkyl groups having 1 to 12 carbon atoms such as n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, cyclopentyl, cyclohexyl group; phenyl, naphthyl group Aryl groups with 6 to 12 carbon atoms such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl groups; alkylaryl groups with 7 to 12 carbon atoms such as benzyl,
  • Examples thereof include aralkyl groups having 7 to 12 carbon atoms, and alkenyl groups having 2 to 12 carbon atoms such as vinyl, allyl, butenyl, hexenyl, octenyl, decenyl, and dodecenyl groups.
  • alkenyl groups having 2 to 12 carbon atoms such as vinyl, allyl, butenyl, hexenyl, octenyl, decenyl, and dodecenyl groups.
  • methyl group, phenyl group, and vinyl group are preferred.
  • 0.0010 to 0.010 mol/100g of component (A) as a whole is an alkenyl group, and the amount of alkenyl groups is preferably 0.0015 to 0.005 mol/100g. If the amount of alkenyl group is less than 0.0010 mol/100 g, crosslinking with component (B) described below will be insufficient, resulting in insufficient releasability of the resulting pressure-sensitive adhesive, and Adhesive residue is likely to occur when peeled off, and on the other hand, if it exceeds 0.010 mol/100g, the adhesive force of the resulting pressure-sensitive adhesive may decrease.
  • n is a number from 3,000 to 15,000, preferably from 5,000 to 10,000.
  • the pressure-sensitive adhesive may have insufficient adhesive strength and releasability.
  • the property of component (A) may be oil-like or raw rubber-like. If it is oily, its viscosity at 25° C. is preferably 1,000 mPa ⁇ s or more, more preferably 10,000 mPa ⁇ s or more. In addition, if it is raw rubber-like, it is preferable that the viscosity of the solution when dissolved in toluene to a concentration of 30% is 5,000 to 100,000 mPa ⁇ s, and 10,000 to 50,000 mPa. - s is more preferable.
  • the viscosity is a value measured at 25°C using a B-type rotational viscometer.
  • linear organopolysiloxane of component (A) include dimethylsiloxane with dimethylvinylsiloxy groups at both ends, methylvinylsiloxane with trimethylsiloxy at both ends, dimethylsiloxane with methylphenylvinylsiloxy at both ends, Examples include diphenylsiloxane with methylphenylvinylsiloxy groups endblocked at both ends, and methylphenylsiloxane endblocked with methylphenylvinylsiloxy groups at both ends.
  • Component (A) may be used alone or in combination of two or more.
  • Component (B) in the silicone pressure-sensitive adhesive composition of the present invention is represented by the following average formula (2), and has a content of hydrogen atoms (SiH groups) bonded to silicon atoms of 0.0010 to 0.020 mol. /g, and is a component that crosslinks with the alkenyl group contained in component (A) through a hydrosilylation reaction.
  • R 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, which may be the same or different from each other, and m is a number from 0 to 200.
  • R 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, which may be the same or different from each other; the monovalent hydrocarbon group having 1 to 12 carbon atoms is hydrosilylated; Those containing no reactive carbon-carbon unsaturated bonds are preferred, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl.
  • n-decyl cyclopentyl, cyclohexyl, and other alkyl groups having 1 to 12 carbon atoms
  • phenyl, naphthyl, and other aryl groups having 6 to 12 carbon atoms
  • tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl Examples include alkylaryl groups having 7 to 12 carbon atoms such as pentylphenyl and hexylphenyl; aralkyl groups having 7 to 12 carbon atoms such as benzyl and phenethyl; methyl and phenyl groups are particularly preferred.
  • the amount of hydrogen atoms (SiH groups) in R 2 is 0.0010 to 0.020 mol/g, preferably 0.0020 to 0.010 mol/g, based on the entire component (B). If the amount of SiH groups is less than 0.0010 mol/g, crosslinking with the component (A) will be insufficient, resulting in insufficient releasability of the resulting pressure-sensitive adhesive, making it difficult to peel off from the adherend. On the other hand, if it exceeds 0.020 mol/g, it is difficult to synthesize due to its structure, and the adhesive force of the resulting pressure-sensitive adhesive may decrease. .
  • m is a number from 0 to 200, preferably from 50 to 100. When m exceeds 200, the pressure-sensitive adhesive may have insufficient adhesive strength and releasability.
  • linear organohydrogenpolysiloxane of component (B) include dimethylsiloxane with dimethylhydrogensiloxy groups blocked at both ends, methylhydrogensiloxane/dimethylsiloxane copolymer blocked with trimethylsiloxy groups at both ends , phenylhydrogensiloxane/dimethylsiloxane copolymer blocked with dimethylphenylsiloxy groups on both ends, methylhydrogensiloxane/diphenylsiloxane copolymer blocked with dimethylphenylsiloxy groups on both ends, diphenylpolysiloxane blocked with methylphenylhydrogensiloxy groups on both ends, Examples include a dimethylsiloxane/diphenylsiloxane/methylhydrogensiloxane copolymer blocked with methylphenylhydrogensiloxy groups at both ends, and a dimethylsiloxane/diphenylsiloxane/dipheny
  • Component (B) may be used alone or in combination of two or more.
  • the molar ratio of the hydrosilyl group in component (B) to the alkenyl group in component (A) is preferably 0.2 to 50, more preferably 1.0 to 10.
  • the blending amount of component (B) is such that the number of SiH groups in component (B) is preferably 0.2 to 50, more preferably 0.5 to 50 per alkenyl group in component (A).
  • the amount is 10.0, more preferably in the range of 1.0 to 5.0. Within this range, the resulting pressure-sensitive adhesive will have superior adhesive strength and releasability.
  • Component ( C ) in the silicone pressure-sensitive adhesive composition of the present invention has (R 3 3 SiO 1/2 ) units and (SiO 4/2 ) units; :(SiO 4/2 ) unit ratio is in the range of 0.5:1 to 1.8:1.
  • R 3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, which may be the same or different from each other; Specific examples of groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, cyclopentyl, cyclohexyl.
  • Alkyl groups having 1 to 12 carbon atoms such as groups; Aryl groups having 6 to 12 carbon atoms such as phenyl and naphthyl groups; Tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl groups, etc.
  • a part of R 3 may be a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and the content of the hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom is determined based on the total number of R 3 . It is preferably 4% or less.
  • alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy groups, and methoxy groups and ethoxy groups preferable.
  • halogen atom examples include chlorine and bromine.
  • the ratio of (R 3 3 SiO 1/2 ) units to (SiO 4/2 ) units is 0.5 to 1.8:1, preferably 0.7 to 1.2:1. If the constituent unit ratio of component (C) does not satisfy the above conditions, the pressure-sensitive adhesive may have insufficient adhesive strength or releasability.
  • Component (C) may contain R 3 SiO 3/2 units and/or R 3 2 SiO 2/2 units depending on the purpose.
  • Component (C) may be used alone or in combination of two or more.
  • the weight average molecular weight (Mw) of component (C) is not particularly limited, but is preferably in the range of 1,000 to 20,000, more preferably 2,000 to 10,000. Note that the weight average molecular weight is a polystyrene equivalent value determined by gel permeation chromatography (GPC) using toluene as a developing solvent.
  • the blending amount of component (C) is preferably 50 to 300 parts by mass, more preferably 100 to 200 parts by mass, per 100 parts by mass of component (A). Within this range, the resulting pressure-sensitive adhesive will have superior adhesive strength and releasability.
  • Component (D) in the silicone pressure-sensitive adhesive composition of the present invention is a hydrosilylation reaction catalyst, and examples thereof include platinum-based, rhodium-based, palladium-based, iron-based, ruthenium-based, iron/cobalt-based catalysts, and the like.
  • platinum-based catalysts are preferred because of their high ability to promote hydrosilylation.
  • platinum-based catalysts include chloroplatinic acid, alcoholic solutions of chloroplatinic acid, reaction products of chloroplatinic acid and alcohol, reaction products of chloroplatinic acid and olefin compounds, and chloroplatinic acid and vinyl group-containing siloxanes.
  • reaction product of chloroplatinic acid and a vinyl group-containing siloxane is preferred, and for example, a commercially available product such as the product name CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) may be used. I can do it.
  • the blending amount of component (D) may be a catalytic amount, and is not particularly limited, but is from 0.01 to 0.01 in terms of the metal in component (D) based on the total mass of the silicone pressure-sensitive adhesive composition of the present invention.
  • a range of 500 mass ppm is preferred, and a range of 0.05 to 100 mass ppm is more preferred.
  • Component (E) in the silicone pressure-sensitive adhesive composition of the present invention is an antioxidant used for the purpose of preventing transparency from being impaired due to coloring of the composition, and includes phenolic antioxidants, thioether Antioxidants such as antioxidants, amine antioxidants, phosphite antioxidants, and the like can be appropriately selected and used.
  • phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis-(4-methyl-6-t-butylphenol), 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]- 1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 4,4'-butylidenebis-(6-t-butyl-3-methylphenol), 4,4' -thiobis(6-t-butyl-3-methylphenol), tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 2,2-thio-diethylenebis[ 3-(3,5-di-t-butyl-4
  • phenolic antioxidants in addition to the phenol hydroxyl group, compounds containing at least one of a phosphorus atom, a sulfur atom, and an amine in the same molecule are also listed, although this overlaps with the examples below.
  • thioether antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and pentaerythyl.
  • Lythyltetrakis (3-laurylthiopropionate), ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole, 4,4'-thiobis(6-t-butyl-3-methylphenol), 2 , 2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 4,6-bis(dodecylthiomethyl)-o-cresol, 2,4-1bis [(octylthio)methyl]-o-cresol, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, etc. Can be mentioned.
  • amine antioxidants include N,N'-diallyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, octylated diphenylamine, and 2,4-bis-( Examples include n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine.
  • phosphite-based antioxidants include trisnonylphenyl phosphite, triphenyl phosphite, bis(3,5-di-t-butyl-4-hydroxybenzyl ethylphosphonate) calcium, tris(2,4 -di-t-butylphenyl) phosphite, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, and the like.
  • antioxidants can be used as the antioxidant, and examples of such commercially available products include ADEKA STAB AO-60, ADEKA STAB AO-50, ADEKA STAB AO-80, and ADEKA STAB AO manufactured by ADEKA Corporation.
  • ADK STAB AO-412S ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-81, ADK STAB LA -82, ADK STAB LA-87, ADK STAB LA-402AF, ADK STAB LA-502XP, ADK STAB 2112, ADK STAB PEP-36; Irganox 1010, Irganox 1010FF, Irganox 1035, Irga manufactured by BASF Japan Co., Ltd.
  • Nox 1035FF Irganox 1076, Irganox 1076FF, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1726, Irganox 1425WL, Irganox 1520L, Irganox 245, Irganox 245FF, Irganox 259, Irganox 3114 , Irganox 5057, Irganox 565, Irgafoss 168; manufactured by Sumitomo Chemical Co., Ltd.
  • Sumilizer GA-80 Sumilizer MDP-S, Sumilizer WX-R, Sumilizer WX-RC, Sumilizer TP-D; manufactured by Sumika Chemtex Co., Ltd. Examples include Sumilizer BBM-S.
  • Each of the antioxidants shown above may be used alone or in combination of two or more types, and it is preferable to use two or more types in combination because it can improve the coloring prevention effect. Among these, it is more preferable to use a phenolic antioxidant and a thioether antioxidant in combination. Although the upper limit of the number of types of antioxidants is not particularly limited, for example, three or less types of antioxidants can be used in combination.
  • the blending amount of component (E) is preferably 0.01 to 1 part by mass, more preferably 0.1 to 0.5 part by mass, per 100 parts by mass of component (A). Within this range, a better coloring prevention effect can be obtained.
  • reaction control agent In the silicone pressure-sensitive adhesive composition of the present invention, a known reaction control agent having a reaction control effect on the hydrosilylation reaction catalyst of component (D) may be used.
  • a reaction control agent 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclohexanol, 3-Methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxycyclohexane , bis(2,2-dimethyl-3-butynoxy)dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,1,3,3-tetra Examples include methyl-1,
  • the silicone pressure-sensitive adhesive composition of the present invention may be used for the purpose of mixing components (A) to (E) and other components added as necessary, and/or for controlling the viscosity of the silicone pressure-sensitive adhesive composition.
  • An organic solvent may be added for the purpose of adjustment.
  • organic solvents include aromatic solvents such as toluene and xylene, aliphatic solvents such as heptane, octane, and isoparaffin, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and ester solvents such as ethyl acetate and isobutyl acetate.
  • Examples include solvents, ether solvents such as diisopropyl ether and 1,4-dioxane, and mixed solvents thereof.
  • Components other than (A) to (E) may be added to the silicone pressure-sensitive adhesive composition of the present invention, if necessary.
  • non-reactive polyorganosiloxanes such as polydimethylsiloxane and polydimethyldiphenylsiloxane
  • heat-resistant aids such as hindered amine compounds
  • light stabilizers such as triazoles and benzophenones
  • phosphoric acid esters and halogens.
  • antimony-based flame retardants and antistatic agents such as cationic activators, anionic activators, and nonionic activators.
  • the silicone pressure-sensitive adhesive composition of the present invention can be made into a silicone pressure-sensitive adhesive by curing.
  • the curing conditions for the silicone pressure-sensitive adhesive composition are appropriately adjusted depending on the coating amount, etc., but are typically 80 to 130° C. and 30 seconds to 3 minutes.
  • the adherend of the silicone pressure-sensitive adhesive of the present invention is not particularly limited.
  • metals such as stainless steel, copper, and iron, metals whose surfaces have been plated or rust-proofed, glass, ceramics, ceramics, resins such as polytetrafluoroethylene, polyimide, epoxy, and novolac resins, and these materials.
  • resins such as polytetrafluoroethylene, polyimide, epoxy, and novolac resins
  • the silicone pressure-sensitive adhesive of the present invention preferably has an adhesive force of 5.0 N/25 mm or more at a room temperature of 23° C. and a pulling speed of 300 mm/min in a 180° peel test specified in JIS Z 0237. .
  • Such a silicone pressure sensitive adhesive has sufficient adhesive strength.
  • the silicone pressure-sensitive adhesive of the present invention preferably has an adhesive force of 5.0 N/25 mm or more and 15 N/25 mm or less at a room temperature of 23° C. and a tensile speed of 300 mm/min in the above tensile test.
  • the silicone pressure-sensitive adhesive of the present invention was tested in a 180° peel test specified in JIS Z 0237 of a polyethylene terephthalate film on the adhered surface after the above-mentioned peel test at a room temperature of 23°C and a tensile speed of 300 mm/min. It is preferable that the adhesive force is 0.1 N/25 mm or less. Such a silicone pressure-sensitive adhesive has excellent releasability.
  • the silicone pressure-sensitive adhesive of the present invention has an adhesion strength of 0 N/25 mm or more at a room temperature of 23°C and a pulling speed of 300 mm/min in the above 180° peel test of a polyethylene terephthalate film on the adhered surface after the above peel test. More preferably, it is 0.1 N/25 mm or less.
  • the silicone pressure-sensitive adhesive of the present invention preferably has a b * value of 0.15 or less at a thickness of 300 ⁇ m in the L * a * b * color system defined in JIS Z 8781-4.
  • a b * value of 0.15 or less indicates that the cured layer is not colored yellow, and meets the required characteristics when used as a pressure-sensitive adhesive for display applications, etc. Note that the b * value of 0.15 or less also indicates that the cured layer is substantially transparent.
  • the silicone pressure-sensitive adhesive of the present invention more preferably has a b * value of -0.15 or more and 0.15 or less.
  • the silicone pressure-sensitive adhesive composition of the present invention can be applied to various film substrates and cured to produce a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer.
  • Base materials include plastic films such as polyethylene terephthalate, polyimide, polyester, polytetrafluoroethylene, polyimide, polyphenylene sulfide, polyamide, polycarbonate, polystyrene, polypropylene, polyethylene, and polyvinyl chloride; metal foils such as aluminum foil and copper foil; Examples include paper such as Japanese paper, synthetic paper, and polyethylene laminate paper, cloth, glass fiber, and composite substrates formed by laminating multiple of these materials.
  • a base material that has been subjected to primer treatment, corona treatment, etching treatment, or plasma treatment may be used, but from the viewpoint of simplifying the work process, these It is preferable not to use this method.
  • Coating may be performed using any known coating method, including comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater, gravure coater, screen coating, and dipping. Examples include coating, cast coating, etc.
  • the coating amount is set depending on the application, but typically the thickness of the silicone pressure-sensitive adhesive layer after curing is 1 to 500 ⁇ m, for display device members 100 to 300 ⁇ m, and for masking tape applications. The thickness is preferably 5 to 50 ⁇ m.
  • a pressure-sensitive adhesive film may be produced by applying the silicone pressure-sensitive adhesive composition directly to a substrate as described above, or a silicone pressure-sensitive adhesive composition may be applied to a release film or release paper with a release coating and cured. After this, a pressure sensitive adhesive film may be produced by laminating the substrates together and transferring the silicone pressure sensitive adhesive layer.
  • the silicone pressure-sensitive adhesive composition of the present invention can be cured to form a pressure-sensitive adhesive layer, and an image display device including the same can be manufactured.
  • Such an image display device has excellent reliability and visibility.
  • the silicone composition of the present invention has excellent releasability (less adhesive residue).
  • the releasability can be evaluated by an evaluation method comprising the following steps (1) to (4). With this method of evaluating silicone pressure-sensitive adhesives, it is possible to quantitatively evaluate the releasability without relying on visual observation, finger touch, or other sensations.
  • a polyethylene terephthalate film is crimped within the range after peeling off the pressure-sensitive adhesive film on the stainless steel plate after the second step, and then the polyethylene terephthalate film is crimped at a tensile speed of 300 mm/min.
  • Step (1) is a step of preparing a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer made of a silicone pressure-sensitive adhesive on one side of a base material, and the method for producing the pressure-sensitive adhesive film is particularly limited.
  • pressure-sensitive adhesive films can be prepared, for example, by the production methods listed above.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably about 30 ⁇ m.
  • Step (2) is a step in which the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film is pressure-bonded to the surface of the stainless steel plate, and then peeled off at 180° to the stainless steel plate at a tensile speed of 300 mm/min.
  • the crimping and peeling conditions in this step are in accordance with the 180° peeling test specified in JIS Z 0237, but a curing step may be provided after crimping if necessary.
  • Step (3) is to pressure-bond a polyethylene terephthalate film within the range after peeling off the pressure-sensitive adhesive film on the stainless steel plate after step (2), and then apply the polyethylene terephthalate film at a tensile speed of 300 mm/min. This is a process of measuring the adhesive force when peeled off at 180° to a stainless steel plate.
  • step (3) adhesive force will be generated when the polyethylene terephthalate film is peeled off in step (3).
  • the crimping and peeling conditions in this step are based on the 180° peeling test specified in JIS Z 0237, but if necessary, a curing step may be provided after the polyethylene terephthalate film is crimped.
  • Step (4) is a step of determining the quality of the silicone pressure-sensitive adhesive based on the adhesive force in step (3), and depending on whether the adhesive force satisfies 0.1 N/25 mm or less, the silicone pressure-sensitive adhesive Preferably, this is a step of determining the quality of the pressure-sensitive adhesive. With such an evaluation method, it is possible to perform a more practical evaluation of the releasability of silicone pressure-sensitive adhesives.
  • the viscosity is a value measured at 25°C using a B-type rotational viscometer
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • Examples 1 to 13 Comparative Examples 1 to 5
  • the following components were mixed in the formulations (parts by mass) shown in Tables 1 and 2 to prepare a silicone pressure-sensitive adhesive composition.
  • Linear organopolysiloxane (A-2)
  • R 2 is a methyl group and a hydrogen atom (B-3)
  • (C) Component (C-1) A three-dimensional network organopolysiloxane having a constituent unit ratio expressed as ((CH 3 ) 3 SiO 1/2 ) 0.67 (SiO 4/2 ) 1.00 and an Mw of 3,400. 60% by mass toluene solution (C-2) ((CH 3 ) 3 SiO 1/2 ) 1.75 (SiO 4/2 ) A three-dimensional network having a constituent unit ratio expressed as 1.00 and having an Mw of 7,400. 60% by mass toluene solution of organopolysiloxane
  • E Component: (E-1) Phenolic antioxidant: Irganox 1010 (manufactured by BASF Japan Ltd.) (E-2) Thioether antioxidant: ADEKA STAB AO-412S (manufactured by ADEKA Co., Ltd.) (E-3) Phosphite antioxidant: ADEKA STAB PEP-36 (manufactured by ADEKA Co., Ltd.)
  • the resulting silicone pressure-sensitive adhesive composition was evaluated for adhesive strength, peelability, and b * value by the following methods, and the results are shown in Tables 3 and 4.
  • the silicone pressure-sensitive adhesive composition was applied onto a polyethylene terephthalate film having a width of 25 mm so that the thickness after curing would be 30 ⁇ m, and then heated at 130° C. for 1 minute to produce a pressure-sensitive adhesive film.
  • This pressure-sensitive adhesive film was pressure-bonded to a stainless steel plate using a roller weighing 2 kg according to JIS Z 0237, and then cured at 25° C. for 24 hours.
  • the force (N/25 mm) required to peel the cured pressure-sensitive adhesive film from the stainless steel plate was measured by a 180° peel test at a room temperature of 23° C. and a pulling speed of 300 mm/min.
  • Examples 1 to 13 using the silicone pressure-sensitive adhesive compositions of the present invention exhibited excellent adhesive strength and peelability (little adhesive residue), and had a low b * It had a value. Furthermore, compared to Examples 1 and 2 in which one antioxidant was used alone, Examples 3 to 13 in which two antioxidants were used in combination had lower b * values.
  • Examples 3 and 5 to 13 in which phenol-based and thioether-based antioxidants were used in combination, had particularly low b * values, indicating that there was very little coloration.
  • Comparative Example 1 Comparative Example 2, and Comparative Example 3 containing a hydrosilyl group in which the amount of hydrosilyl group is less than 0.0010 mol/g in place of component (B), the amount required for peeling off in the peelability test was It can be seen that the strength was high and adhesive residue was generated.

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Abstract

La présente invention est une composition adhésive sensible à la pression de silicone qui contient : (A) un organopolysiloxane qui est représenté par la formule moyenne (1) et dans lequel la teneur en groupes alcényle liés à un atome de silicium est de 0,0010 à 0,010 mol/100 g ; (B) un organohydrogénopolysiloxane qui est représenté par la formule moyenne (2) et dans lequel la teneur en atomes d'hydrogène liés à un atome de silicium est de 0,0010 à 0,020 mol/g ; (C) un organopolysiloxane ayant (R3 3SiO1/2) unités et (SiO4/2) unités ; (D) un catalyseur de réaction d'hydrosilylation ; et (E) un antioxydant. Grâce à la présente configuration, il est possible de fournir un adhésif sensible à la pression qui présente à la fois une force d'adhérence élevée et d'excellentes propriétés de libération, subit peu de coloration, et présente une transparence élevée. (Dans la formule, R1 est un groupe hydrocarboné monovalent, et n est un nombre compris entre 3 000 et 15 000) (Dans la formule, R2 est un groupe hydrocarboné monovalent ou un atome d'hydrogène, et m est un nombre compris entre 0 et 200)
PCT/JP2023/007158 2022-04-07 2023-02-27 Composition adhésive sensible à la pression de silicone, adhésif sensible à la pression de silicone, film adhésif sensible à la pression, dispositif d'affichage d'image et procédé d'évaluation d'adhésif sensible à la pression de silicone Ceased WO2023195268A1 (fr)

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JP2022-064145 2022-04-07
JP2022164689A JP2023155125A (ja) 2022-04-07 2022-10-13 シリコーン感圧接着剤組成物、シリコーン感圧接着剤、感圧接着フィルム、画像表示装置及びシリコーン感圧接着剤の評価方法
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006016555A (ja) * 2004-07-02 2006-01-19 Dow Corning Toray Co Ltd シリコーン系感圧接着剤および粘着テープ
JP2008024777A (ja) * 2006-07-19 2008-02-07 Shin Etsu Chem Co Ltd シリコーンゴム用付加硬化型シリコーン粘着剤組成物及び該組成物から得られる粘着テープ
JP2011102336A (ja) * 2009-11-10 2011-05-26 Shin-Etsu Chemical Co Ltd シリコーン粘着剤組成物及び粘着フィルム
CN109306259A (zh) * 2018-09-07 2019-02-05 东莞市贝特利新材料有限公司 一种光固化有机硅胶粘剂及其在贴合触摸屏中的应用
JP2019089913A (ja) * 2017-11-14 2019-06-13 信越化学工業株式会社 付加硬化型シリコーン接着剤組成物
JP2021123628A (ja) * 2020-02-04 2021-08-30 アイカ工業株式会社 粘着性シリコーン樹脂組成物及びこれを塗布した粘着フィルム

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006016555A (ja) * 2004-07-02 2006-01-19 Dow Corning Toray Co Ltd シリコーン系感圧接着剤および粘着テープ
JP2008024777A (ja) * 2006-07-19 2008-02-07 Shin Etsu Chem Co Ltd シリコーンゴム用付加硬化型シリコーン粘着剤組成物及び該組成物から得られる粘着テープ
JP2011102336A (ja) * 2009-11-10 2011-05-26 Shin-Etsu Chemical Co Ltd シリコーン粘着剤組成物及び粘着フィルム
JP2019089913A (ja) * 2017-11-14 2019-06-13 信越化学工業株式会社 付加硬化型シリコーン接着剤組成物
CN109306259A (zh) * 2018-09-07 2019-02-05 东莞市贝特利新材料有限公司 一种光固化有机硅胶粘剂及其在贴合触摸屏中的应用
JP2021123628A (ja) * 2020-02-04 2021-08-30 アイカ工業株式会社 粘着性シリコーン樹脂組成物及びこれを塗布した粘着フィルム

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