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
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/08—Macromolecular additives
• • 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
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/22—Plastics; Metallised plastics
• • 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]

Definitions

• the present invention relates to a silicone adhesive composition, an adhesive article, and an adhesion enhancer.
• Adhesives are a type of adhesive, and are often used in the form of adhesive tapes or labels made by coating a substrate with the adhesive and letting it harden. These are typical examples of products that use adhesives that we see every day. These products have a wide range of uses, including labels for identifying items, packaging luggage, and joining multiple items together.
• Rubber-based adhesives are a general-purpose base material that has been used for a long time, and are inexpensive and used in general-purpose products such as tapes.
• Acrylic-based adhesives use polyacrylate as a base, and have better chemical properties than rubber-based adhesives, so they can be used in adhesive products with higher functionality than rubber-based adhesives.
• Silicone-based adhesives are made of high-viscosity silicone gum and silicone resin, and have many siloxane bonds in the main chain, giving them a variety of excellent characteristics, including heat resistance, cold resistance, weather resistance, chemical resistance, and electrical insulation.
• Silicone adhesives take advantage of the excellent properties mentioned above and are used in high-performance industrial tapes such as heat-resistant tapes, masking tapes for manufacturing processes, and flame-retardant mica tapes, and are used in situations where their properties can be fully utilized even under harsh operating conditions.
• the substrate used for screen protectors is a plastic film, and transparent polyester films such as PET are often used.
• plastic films are said to have poorer adhesion to adhesives than paper substrates. This is thought to be because plastic films have a flatter surface and, compared to paper, which has a large amount of unevenness, have a weaker anchoring effect, which allows the adhesive to bite into the substrate. Poor adhesion can cause problems such as offset when rolled up, or the adhesive layer transferring to the substrate when peeled off after being applied to the substrate for a certain amount of time.
• Patent documents 2 to 4 give examples of silicon-based materials that show good adhesion to the target substrate, but when added to silicone adhesives, the effect is insufficient, and further improvement is required.
• Patent Documents 5 and 6 exemplify silicone pressure-sensitive adhesive compositions that do not require a primer coating and exhibit good adhesion to substrates. However, there is still room for improvement in the adhesion to substrates, and further improvements in performance are desired.
• the objective of the present invention is to provide a silicone adhesive that has improved adhesion to plastic film substrates compared to conventional techniques.
• the present invention has been made to solve the above problems, and provides the following silicone adhesive composition, adhesive article, and adhesion enhancer.
• the present invention provides: (A) 100 to 40 parts by mass of an organopolysiloxane represented by the average composition formula (1), which has at least two alkenyl-containing organic groups in one molecule and contains 0.0002 to 0.10 moles of alkenyl groups per 100 g, (R 1 may be the same or different and is a monovalent hydrocarbon group having 1 to 10 carbon atoms, at least two of the R 1 contain an alkenyl-containing organic group having 2 to 10 carbon atoms, a is a positive number of 2 or more, b is a positive number of 1 or more, c and d are positive numbers of 0 or more, and 50 ⁇ a+b+c+d ⁇ 15000.) (B) 60 to 0 parts by mass of a polyorganosiloxane composed of R 2 3 SiO 1/2 units and SiO 4/2 units, in which the molar ratio of (R 2 3 SiO 1/2 units)/(SiO 4/2 units) is 0.6 to 1.0 (each R 2 independently
• Such a silicone adhesive composition can be made to have good adhesion to plastic film substrates even in high temperature and high humidity environments.
• component (G) which is a silicon compound containing 0.15 moles or more of alkenyl groups per 100 g, in an amount of 0.01 to 10 parts by mass relative to the total amount of components (A) to (C) above, in the silicone adhesive composition.
• silicone adhesive composition containing component (G) If such a silicone adhesive composition containing component (G) is used, it is possible to obtain an adhesive article in which the increase in adhesive strength to the adherend over time is suppressed.
• an addition reaction inhibitor (H) in the silicone adhesive composition in an amount of 0.01 to 5 parts by mass based on the total amount of components (A) to (C).
• component (H) By adding this type of component (H) to the silicone adhesive composition, it is possible to control the start of the curing reaction.
• the component (E) is preferably a compound represented by the following average composition formula (3).
• R4 represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms and no aliphatic unsaturated bonds, at least one of R4 represents an aryl group-containing organic group having 6 to 10 carbon atoms, at least three of R4 represent a Si-H group, g represents a positive number of 2 or more, h represents a positive number of 1 or more, i and j represent positive numbers of 0 or more, and 10 ⁇ g+h+i+j ⁇ 500.)
• the ratio of the total number of aryl-containing organic groups to the total number of Si-H and silicon-bonded groups in component (E) is preferably 8 to 30%.
• component (E) that has such an aryl group
• the Si-H groups in component (E) interact with the functional groups present on the substrate surface, improving the adhesive of the silicone adhesive composition and the adhesion to the plastic film substrate.
• the above component (F) preferably contains an organosilicon compound having both an epoxy group-containing organic group and a hydrolyzable alkoxy group having 1 to 10 carbon atoms.
• the component (F) is preferably a compound represented by the following formula (4) or a compound in which a portion of the hydrolyzable groups in the compound represented by the following formula (4) has been condensed.
• R5 is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms
• R6 is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms
• k is a positive number satisfying 1 ⁇ k ⁇ 3.
• component (F) By adding such component (F) to the silicone adhesive composition, the adhesiveness of the silicone adhesive composition, which is provided by component (E), to the substrate of the plastic film can be further improved.
• the component (G) added to the silicone adhesive composition is preferably a silicon compound having at least one siloxane bond in one molecule.
• the crosslink density of the entire adhesive layer can be adjusted by adding a (G) component with a high vinyl group content to a silicone adhesive composition with a reduced vinyl group content.
• the silicone adhesive composition can be applied to at least one surface of a substrate and cured to obtain an adhesive article.
• silicone adhesive composition it is possible to obtain adhesive articles that have good adhesion even to plastic substrates.
• the present invention also provides an adhesion improver containing the above-mentioned components (E) and (F) for use by adding to an addition-type silicone pressure-sensitive adhesive composition.
• the present invention provides an adhesion improver for use by being added to an addition-type silicone pressure-sensitive adhesive composition, comprising: (E) a polyorganohydrogensiloxane having at least three Si-H groups in one molecule and an aryl group-containing organic group directly bonded to a silicon atom, the ratio of the total number of the aryl group-containing organic groups to the total number of the Si-H and the organic groups bonded to silicon being 5 to 40%, and (F) an organosilicon compound having at least one epoxy group in one molecule and containing at least one silicon atom;
• the adhesion improver is characterized by comprising:
• an addition-type silicone adhesive composition containing the above-mentioned components (E) and (F) as an adhesion improver it is possible to obtain an adhesion improver that has improved adhesion to the substrate.
• silicone adhesive composition of the present invention it is possible to obtain adhesive articles that have better adhesion to substrates than conventional adhesive articles, even when subjected to long-term high temperature and high humidity environments.
• the present invention will be described in detail below, but the present invention is not limited thereto.
• the present inventors have discovered a silicone pressure-sensitive adhesive composition which further improves substrate adhesion to plastic films under high temperature and high humidity conditions by using, in addition to a phenyl-containing silicon compound having a specific structure, a hydrolyzable silicon compound having an epoxy-containing organic group having a new specific structure, or a hydrolysate thereof, and have thus completed the present invention.
• the present invention provides: (A) 100 to 40 parts by mass of an organopolysiloxane represented by the average composition formula (1), which has at least two alkenyl-containing organic groups in one molecule and contains 0.0002 to 0.10 moles of alkenyl groups per 100 g, (R 1 may be the same or different and is a monovalent hydrocarbon group having 1 to 10 carbon atoms, at least two of the R 1 contain an alkenyl-containing organic group having 2 to 10 carbon atoms, a is a positive number of 2 or more, b is a positive number of 1 or more, c and d are positive numbers of 0 or more, and 50 ⁇ a+b+c+d ⁇ 15000.) (B) 60 to 0 parts by mass of a polyorganosiloxane composed of R 2 3 SiO 1/2 units and SiO 4/2 units, in which the molar ratio of (R 2 3 SiO 1/2 units)/(SiO 4/2 units) is 0.6 to 1.0 (each R 2 independently
• the present invention also provides an adhesion improver for use by being added to an addition-type silicone pressure-sensitive adhesive composition, comprising: (E) a polyorganohydrogensiloxane having at least three Si-H groups in one molecule and an aryl group-containing organic group directly bonded to a silicon atom, the ratio of the total number of the aryl group-containing organic groups to the total number of the Si-H and the organic groups bonded to silicon being 5 to 40%, and (F) an organosilicon compound having at least one epoxy group in one molecule and containing at least one silicon atom;
• the adhesion improver is characterized by comprising:
• Component (A) is an organopolysiloxane having at least two alkenyl-containing organic groups in each molecule.
• Specific structures include the following: (R 1 may be the same or different and is a monovalent hydrocarbon group having 1 to 10 carbon atoms, at least two of the R 1 contain an alkenyl-containing organic group having 2 to 10 carbon atoms.
• a is an integer of 2 or more
• b is an integer of 1 or more
• c and d are integers of 0 or more, and 50 ⁇ a+b+c+d ⁇ 15000.
• R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, of which two or more are alkenyl-containing organic groups.
• the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, and aryl groups such as phenyl groups, and further, some or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with halogen atoms or other groups, and examples include a trifluoromethyl group and a 3,3,3-trifluoropropyl group. Saturated aliphatic or aromatic groups are preferred, and a methyl group and a phenyl group are particularly preferred.
• Alkenyl-containing organic groups are preferably those having 2 to 10 carbon atoms, and examples include alkenyl groups such as vinyl, allyl, hexenyl, and octenyl groups; acryloylalkyl and methacryloylalkyl groups such as acryloylpropyl, acryloylmethyl, and methacryloylpropyl groups; cycloalkenylalkyl groups such as cyclohexenylethyl groups; and alkenyloxyalkyl groups such as vinyloxypropyl groups. When used, vinyl groups are particularly preferred.
• the amount of alkenyl groups contained in (A) is 0.0002 to 0.10 mol per 100 g of organopolysiloxane, preferably 0.0004 to 0.04 mol, and more preferably 0.0005 to 0.03 mol. If it is less than 0.0002 mol, the crosslink density will be low and cohesive failure of the adhesive layer may occur, and if it is more than 0.10 mol, the adhesive layer will be hard and appropriate adhesive strength and tack may not be obtained.
• a is a positive number of 2 or more
• b is a positive number of 1 or more
• c and d are positive numbers of 0 or more
• Component (A) is usually produced by ring-opening polymerization of a cyclic low molecular weight siloxane such as octamethylcyclotetrasiloxane using a catalyst. Since the resulting product contains the raw material cyclic low molecular weight siloxane after polymerization, it is preferable to use the reaction product after distilling it off under heating and reduced pressure while passing an inert gas through the reaction product.
• a cyclic low molecular weight siloxane such as octamethylcyclotetrasiloxane
• Examples of the component (A) include, but are not limited to, those represented by the following general formula: R 1-1 R 1-2 2 SiO(R 1-2 2 SiO) l SiR 1-2 2 R 1-1 R 1-1 R 1-2 2 SiO(R 1-2 2 SiO) l (R 1-1 R 1-2 SiO) m SiR 1-2 2 R 1-1 R 1-1 3 SiO(R 1-2 2 SiO) l (R 1-1 R 1-2 SiO) m SiR 1-2 2 R 1-1 3 R 1-2 3 SiO(R 1-2 2 SiO) l (R 1-1 R 1-2 SiO) m SiR 1-2 2 R 1-2 3 (In the formula, R 1-1 is the same or different alkenyl-containing organic group, R 1-2 is the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms, l ⁇ 48, and m ⁇ 1 (however, when there is no R 1-1 other than (R 1-1 R 1-2 SiO) m in the molecule, m ⁇ 2). Examples of R
• component (A) include, but are not limited to, those represented by the following general formula: In the following formula, Me, Vi, and Ph represent a methyl group, a vinyl group, and a phenyl group, respectively.
• Component (B) is a polyorganosiloxane consisting of R 2 3 SiO 1/2 units (wherein R 2 each independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms that does not have an aliphatic unsaturated bond or an alkenyl group having 2 to 10 carbon atoms) and SiO 4/2 units, with the molar ratio (R 2 3 SiO 1/2 units)/(SiO 4/2 units) being 0.6 to 1.0, preferably 0.65 to 0.9. If this molar ratio is less than 0.6, the adhesive strength and tackiness may decrease, and if it exceeds 1.0, the adhesive strength and holding power may decrease.
• Each R2 independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms having no aliphatic unsaturated bond or an alkenyl group having 2 to 10 carbon atoms
• examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms for R2 include alkyl groups preferably having 2 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, and a butyl group, and aryl groups preferably having 6 to 10 carbon atoms, such as a phenyl group and a tolyl group.
• alkenyl group having 2 to 6 carbon atoms include a vinyl group, an allyl group, and a butenyl group.
• (B) Two or more kinds of components (B) may be used in combination. It is also possible for (B) to contain R 2 SiO 3/2 units and R 2 2 SiO 2/2 units.
• (B) may undergo a condensation reaction in the presence of a catalyst.
• This is a process in which hydrolyzable groups present on the surface are reacted with each other, and is expected to have effects such as improved adhesive strength.
• An alkaline catalyst is used, and the reaction is carried out at room temperature or under reflux, and neutralized as necessary.
• Alkaline catalysts include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; metal alkoxides such as sodium methoxide and potassium butoxide; organic metals such as butyl lithium; potassium silanolate; and nitrogen compounds such as ammonia gas, aqueous ammonia, methylamine, trimethylamine, and triethylamine, with ammonia gas or aqueous ammonia being preferred.
• the temperature of the condensation reaction may be from room temperature to the reflux temperature of the organic solvent.
• the reaction time is not particularly limited, but may be 0.5 to 20 hours, preferably 1 to 16 hours.
• a neutralizing agent may be added to neutralize the alkaline catalyst, if necessary.
• neutralizing agents include acidic gases such as hydrogen chloride and carbon dioxide; organic acids such as acetic acid, octyl acid, and citric acid; and mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid.
• an inert gas such as nitrogen may be passed through to distill it off.
• the amount of component (A) is 100-40 parts by mass, and the amount of component (B) is 60-0 parts by mass.
• Component (C) is a polyorganohydrogensiloxane having at least three Si-H groups in one molecule. Specific structures include the following: R 3 e H f SiO (4-ef)/2 average composition formula (2) ( R3 represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, e>0, f>0, and further, 0 ⁇ e+f ⁇ 3.)
• R3 is a monovalent hydrocarbon group having 1 to 10 carbon atoms.
• alkyl groups such as methyl, ethyl, propyl, and butyl groups
• cycloalkyl groups such as cyclohexyl groups
• alkenyl groups such as vinyl, allyl, hexenyl, and octenyl groups
• aryl groups such as phenyl groups.
• some or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with halogen atoms or other groups, and examples include a trifluoromethyl group and a 3,3,3-trifluoropropyl group. Saturated aliphatic or aromatic groups are preferred, and a methyl group and a phenyl group are particularly preferred.
• e and f are numbers that satisfy e>0, f>0 and 0 ⁇ e+f ⁇ 3.
• the component (C) include, but are not limited to, those represented by the following general formula: R 3-1 R 3-2 2 SiO(R 3-2 2 SiO) s SiR 3-2 2 R 3-1 R 3-1 R 3-2 2 SiO(R 3-2 2 SiO) s (R 3-1 R 3-2 SiO) t SiR 3-2 2 R 3-1 R 3-2 3 SiO(R 3-2 2 SiO) s (R 3-1 R 3-2 SiO) t SiR 3-2 3 R 3-2 3 SiO(R 3-1 R 3-2 SiO) t SiR 3-2 3 (In the formula, R 3-1 is a hydrogen atom, R 3-2 are the same or different monovalent hydrocarbon groups having 1 to 10 carbon atoms, s is 8 or more, and t is 1 or more.
• R 3-1 and R 3-2 include those exemplified above for R 3.
• the amount of component (C) used should be such that the molar ratio of Si-H groups in component (C) to alkenyl groups in component (A) is 0.2 to 20, and preferably in the range of 0.5 to 15. If it is less than 0.2, the crosslink density will be low, which may result in low cohesive strength and holding power. If it exceeds 20, the crosslink density will be high, and appropriate adhesive strength and tack may not be obtained.
• Component (C) is usually produced by ring-opening polymerization of cyclic low molecular weight siloxanes such as octamethylcyclotetrasiloxane and siloxanes containing Si-H such as tetramethylcyclotetrasiloxane using an acid catalyst. Since the raw material cyclic low molecular weight siloxane is still contained after polymerization, it is preferable to use the product that has been distilled off while passing an inert gas through the reaction product under heating and reduced pressure.
• cyclic low molecular weight siloxanes such as octamethylcyclotetrasiloxane and siloxanes containing Si-H such as tetramethylcyclotetrasiloxane using an acid catalyst. Since the raw material cyclic low molecular weight siloxane is still contained after polymerization, it is preferable to use the product that has been distilled off while passing an inert gas through the reaction product under heating and reduced pressure.
• Me represents a methyl group.
• Component (D) is a platinum group metal catalyst for curing by hydrosilylation addition of alkenyl groups in components (A) to (C) and Si-H groups in component (C), and examples of central metals include platinum, palladium, iridium, rhodium, osmium, and ruthenium, with platinum being preferred among them.
• platinum catalysts include chloroplatinic acid, alcohol solutions of chloroplatinic acid, reaction products of chloroplatinic acid and alcohols, platinum complexes obtained by reaction of chloroplatinic acid and olefin compounds, complexes of platinum and vinyl group-containing siloxanes, and complexes of platinum and vinyl group-containing polysiloxanes.
• the content of component (D) is preferably such that the metal content is 1 to 500 ppm, and more preferably 2 to 450 ppm, relative to the total amount of components (A) to (C). If it is less than 1 ppm, the reaction will be slow and curing will be insufficient, which may prevent the adhesive strength and holding power from being fully exerted. If it exceeds 500 ppm, the flexibility of the cured product may be poor.
• Component (E) has three or more hydrogen atoms bonded to silicon atoms different from component (C) in each molecule, and has an aryl group directly bonded to a silicon atom, and the ratio of the total number of the aryl groups to the total number of the hydrogen atoms bonded to the silicon atom and the organic groups bonded to the silicon atom is 5 to 40%. It is preferably an organohydrogenpolysiloxane represented by the following average composition formula (3). As described above, the aryl group is at least one of an aryl group bonded to a silicon atom and an aryl group possessed by an aralkyl group bonded to a silicon atom.
• R4 represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms and no aliphatic unsaturated bonds, at least one of R4 represents an aryl group-containing organic group having 6 to 10 carbon atoms, at least three of R4 represent a Si-H group, g represents a positive number of 2 or more, h represents a positive number of 1 or more, i and j represent positive numbers of 0 or more, and 10 ⁇ g+h+i+j ⁇ 500.
• the organohydrogenpolysiloxane may be used alone or in combination of two or more types.
• the amount of component (E) used is 0.01 to 10 parts by mass, preferably 0.03 to 5 parts by mass, and more preferably 0.05 to 1 part by mass, based on the total amount of components (A) to (C). If the amount is less than 0.01 parts by mass, the composition may not be able to provide sufficient adhesion to the substrate, whereas if the amount is more than 10 parts by mass, the adhesive strength of the laminate may increase over time, resulting in poor reworkability.
• Component (E) has an amount of aryl group-containing organic groups such that the ratio (%) of the number of aryl group-containing organic groups to the total number of organic groups bonded to silicon atoms and hydrogen atoms bonded to silicon atoms is 5 to 40%, preferably 8 to 30%, and more preferably 10 to 25%.
• [the proportion (%) of the aryl groups in component (E)] - [the proportion (%) of the total number of aryl groups to the total number of groups bonded to silicon atoms in component (A)] is ⁇ 5.0%. More preferably, the difference is 7.0% or more, and even more preferably 9.0% or more. There is no particular upper limit to the difference, but it is preferably 40% or less, even more preferably 30% or less, and even more preferably 25% or less. This improves the adhesion of the resulting cured coating to the substrate.
• component (E) having aryl groups in the above range reduces compatibility with components (A) and (B), and as the crosslinking reaction occurs, component (E) localizes near the substrate. This causes the Si-H groups in component (E) to interact with functional groups present on the substrate surface, and when the substrate is a plastic film in particular, the aryl groups in component (E) interact with the ⁇ electrons of the aromatic rings in the plastic, resulting in a stacking effect that improves adhesion. Furthermore, because of the low compatibility with adherends such as glass, it is possible to suppress an increase in adhesive strength over time.
• the cured coating can be given good adhesion to the substrate.
• the number of aryl groups includes the number of aryl groups contained in the aralkyl group as described above.
• Examples of the group bonded to the silicon atom include a hydroxyl group, an alkyl group, an aryl group, an aralkyl group, and an alkyl group substituted with a halogen atom. More specifically, examples include the group represented by R11 described later.
• Component (E) preferably has an average degree of polymerization of 500 or less, more preferably an average degree of polymerization of 5 to 500, and even more preferably an average degree of polymerization of 15 to 450. If the average degree of polymerization is 500 or less, the adhesion to the substrate is not reduced.
• the organohydrogenpolysiloxane of component (E) is represented, for example, by the following average composition formula (5).
• R 11 y H z SiO (4-y-z)/2 average composition formula (5) R 11 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 11 in a number that is 5 to 40% of the total number of R 11 and the total number of hydrogen atoms bonded to silicon atoms is an aryl group, y>0, z>0, and 0 ⁇ y+z ⁇ 3.
• R 11 is a monovalent hydrocarbon group having 1 to 10 carbon atoms.
• alkyl groups such as methyl, ethyl, propyl, and butyl groups
• cycloalkyl groups such as cyclohexyl groups
• alkenyl groups such as vinyl, allyl, hexenyl, and octenyl groups
• aryl groups such as phenyl groups.
• some or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with halogen atoms or other groups, and examples include a trifluoromethyl group and a 3,3,3-trifluoropropyl group. Saturated aliphatic or aromatic groups are preferred, and a methyl group and a phenyl group are particularly preferred.
• y and z are numbers that satisfy y>0, z>0 and 0 ⁇ y+z ⁇ 3.
• Examples of the component (E) include, but are not limited to, those represented by the following general formula: R 11-1 R 11-2 2 SiO (R 11-2 2 SiO) aa SiR 11-2 2 R 11-1 R 11-1 R 11-2 2 SiO(R 11-2 2 SiO) aa (R 11-1 R 11-2 SiO) ab SiR 11-2 2 R 11-1 R 11-2 3 SiO(R 11-2 2 SiO) aa (R 11-1 R 11-2 SiO) ab SiR 11-2 3 R 11-2 3 SiO(R 11-1 R 11-2 SiO) ab SiR 11-2 3 (In the formula, R 11-1 is a hydrogen atom, R 11-2 are the same or different monovalent hydrocarbon groups having 1 to 10 carbon atoms, aa ⁇ 8, and ab ⁇ 1.
• R 11-1 when there is no R 11-1 other than (R 11-1 R 11-2 SiO) ab in the molecule, ab ⁇ 3. At least one of R 11-2 has an aryl group.
• R 11-1 and R 11-2 include those exemplified above for R 11. Preferably, 8 ⁇ aa ⁇ 498, more preferably, 1 ⁇ ab ⁇ 498, and more preferably, 3 ⁇ ab ⁇ 498.
• Aryl groups include phenyl, tolyl, naphthyl, styryl, and oxyaryl groups, with phenyl being particularly preferred.
• Aralkyl groups include phenylmethyl and phenylethyl groups, with phenylmethyl being preferred.
• Component (E) is usually produced by ring-opening polymerization of a cyclic low molecular weight siloxane such as octamethylcyclotetrasiloxane, a siloxane containing Si-H such as tetramethylcyclotetrasiloxane, and a silicon compound having diaryldialkoxysilane or diarylsiloxy units using an acid catalyst. Since the product contains the cyclic low molecular weight siloxane raw material after polymerization, it is preferable to use the product that has been distilled off by passing an inert gas through the reaction product under heating and reduced pressure.
• a cyclic low molecular weight siloxane such as octamethylcyclotetrasiloxane
• a siloxane containing Si-H such as tetramethylcyclotetrasiloxane
• a silicon compound having diaryldialkoxysilane or diarylsiloxy units using an acid catalyst. Since the product contains the
• Me and Ph represent a methyl group and a phenyl group, respectively.
• M 2 D ac D H ad D Ph ae (0 ⁇ ac ⁇ 498, 3 ⁇ ad ⁇ 498, 1 ⁇ ae ⁇ 200)
• M 2 D H ad D Ph ae (3 ⁇ ad ⁇ 498, 1 ⁇ ae ⁇ 200)
• M H 2 D H ad D Ph ae (3 ⁇ ad ⁇ 498, 1 ⁇ ae ⁇ 200)
• D ac D H ad D Ph ae T af (0 ⁇ ac ⁇ 492, 3 ⁇ ad ⁇ 495, 1 ⁇ ae ⁇ 200, 1 ⁇ af ⁇ 10) M (af+2ag+2)
• D ac D H ad D Ph ae T af Q ag (0 ⁇ ac ⁇ 491, 3 ⁇ ad ⁇ 494, 1 ⁇ ae ⁇ 200, 0 ⁇ af ⁇ 10, 1 ⁇ ag ⁇ 10)
• Component (F) is an organosilicon compound having at least one epoxy group and at least one silicon atom in one molecule, and is preferably an organosilicon compound having both an epoxy group-containing organic group and a hydrolyzable alkoxy group having 1 to 10 carbon atoms.
• component (E) is the main component for improving the substrate adhesion of the silicone pressure-sensitive adhesive composition to plastic films, but the addition of component (F) can further improve the substrate adhesion.
• Specific examples of epoxy group-containing organic groups include, but are not limited to, those having the structures shown below.
• An example of an organosilicon compound having both an epoxy group-containing organic group and a hydrolyzable alkoxy group having 1 to 10 carbon atoms is a compound represented by the following formula (4).
• R5 is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms
• R6 is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms
• k is a positive number satisfying 1 ⁇ k ⁇ 3.
• the component (F) may be not only the compound of formula (4) but also a compound in which a part of the hydrolyzable group in the compound represented by formula (4) is condensed, and is represented by the following average composition formula (6).
• R 12 ah SiO (4-ah)/2 average composition formula (6) R 12 is a group selected from the group consisting of an epoxy group-containing organic group, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, at least one of R 12 is an epoxy group-containing organic group, and ah is 1 ⁇ ah ⁇ 4.
• Ep The structure of the epoxy group-containing organic group is shown below and is designated as Ep.
• monovalent hydrocarbon groups having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl; alkenyl groups such as vinyl, allyl, hexenyl, and octenyl; and aryl groups such as phenyl.
• alkyl groups such as methyl, ethyl, propyl, and butyl
• cycloalkyl groups such as cyclohexyl
• alkenyl groups such as vinyl, allyl, hexenyl, and octenyl
• aryl groups such as phenyl.
• some or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with halogen atoms or other groups, and examples include trifluoromethyl and 3,3,3-trifluoropropyl groups.
• Saturated aliphatic or aromatic groups are preferred,
• alkoxy groups having 1 to 5 carbon atoms include methoxy, ethoxy, normal propoxy, isopropoxy, normal butoxy, and isobutoxy groups. From the standpoint of cost and availability, methoxy, ethoxy, normal propoxy, and isopropoxy groups are preferred, and methoxy and ethoxy groups are more preferred.
• the degree of polymerization of the partial hydrolysis condensate of the hydrolyzable organosilicon compound containing an epoxy group-containing organic group is not particularly limited, but is preferably 1 to 100, more preferably 1 to 80, and even more preferably 3 to 60. If it is 100 or less, it has good compatibility with other components and can be mixed well.
• the epoxy equivalent of the hydrolyzable organosilicon compound containing an epoxy group-containing organic group is not particularly limited, but is preferably 150 to 5,000 g/mol, more preferably 180 to 4,500 g/mol, and even more preferably 200 to 4,000 g/mol. If it is 150 g/mol or more, the adhesive strength of the adhesive tape made from the silicone adhesive as the main component does not increase over time and reworkability is good, and if it is 5,000 g/mol or less, sufficient adhesion to the substrate is obtained.
• the amount of component (F) added is preferably 0.005 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, and even more preferably 0.02 to 1 part by mass, based on the total amount of components (A) to (C). If the amount is less than 0.005 parts by mass, sufficient adhesion to the substrate may not be obtained, and if the amount is more than 5 parts by mass, the adhesive strength of the adhesive tape made from the silicone adhesive as the main component may increase over time, resulting in poor reworkability.
• the (G) component is a silicon compound containing 0.15 moles or more of alkenyl groups per 100 g, and preferably has at least one siloxane bond per molecule.
• the (G) component is a component for suppressing the increase in adhesive strength to the adherend over time.
• the adhesive strength to the adherend increases over time when the silicone curable composition is used as an adhesive article, so the (G) component is effective in suppressing this.
• the crosslink density of the entire adhesive layer increases by adding a small amount of additive with a large amount of vinyl groups to the base material with a small amount of vinyl groups of the silicone adhesive, which increases the hardness of the adhesive layer and makes it difficult to bite into the adherend.
• the component (G) is a compound represented by the following average composition formula (8).
• R 13 may be the same or different and is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and at least one of R 13 contains an alkenyl-containing organic group having 2 to 10 carbon atoms. ar, as, at, and au are positive numbers of 0 or more, and 2 ⁇ ar+as+at+au ⁇ 100.
• the alkenyl-containing organic group is preferably one having 2 to 10 carbon atoms, and examples include alkenyl groups such as vinyl, allyl, hexenyl, and octenyl groups, acryloylalkyl and methacryloylalkyl groups such as acryloylpropyl, acryloylmethyl, and methacryloylpropyl groups, cycloalkenylalkyl groups such as cyclohexenylethyl groups, and alkenyloxyalkyl groups such as vinyloxypropyl groups.
• vinyl groups are particularly preferred.
• the amount of alkenyl groups contained in component (G) is 0.15 mol or more per 100 g, preferably 0.18 mol or more, and more preferably 0.20 mol or more. If it is 0.15 mol or more, the effect of suppressing the increase in adhesive strength will not be weakened.
• ar, as, at, and au are positive numbers of 0 or more, and 2 ⁇ ar+as+at+au ⁇ 100, and preferably 3 ⁇ ar+as+at+au ⁇ 80. If ar+as+at+au is 2 or more, the effect of suppressing the increase in adhesive strength will not be weakened, and if ar+as+at+au is 100 or less, the reaction will be slowed down so that unreacted components remain and there is no possibility of the hardened adhesive transferring to the adherend and leaving adhesive residue.
• the amount of component (G) added is 0.01 to 10 parts by mass relative to the total amount of components (A) to (C), more preferably 0.03 to 5 parts by mass, and even more preferably 0.05 to 1 part by mass. If it is 0.01 part by mass or more, the effect of suppressing the increase in adhesive strength is not weakened, and if it is 10 parts by mass or less, the amount of alkenyl groups relative to Si-H groups does not become excessive, and the reaction proceeds smoothly and the adhesive hardens.
• Me and Vi represent a methyl group and a vinyl group, respectively.
• Component (H) is a regulator, which is added to prevent thickening or gelling of the treatment liquid caused by the addition reaction starting before heat curing when the silicone pressure-sensitive adhesive composition is prepared or applied to a substrate.
• the reaction regulator coordinates with the platinum group metal, which is an addition reaction catalyst, to suppress the addition reaction, and when heat curing is performed, the coordination is released and catalytic activity is expressed.
• Any reaction regulator that has been conventionally used in addition reaction curing silicone compositions can be used.
• acetylenic alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, and 2-phenyl-3-butyn-2-ol
• acetylenic compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne
• vinyl siloxanes such as tetramethylvinylsiloxane cyclic compounds
• organic nitrogen compounds such as benzotriazole and other organic phosphorus compounds
• oxime compounds such as benzotriazole and other organic phosphorus compounds
• organic chloro compounds such as benzotriazole and other organic phosphorus compounds.
• the content of component (H) is 0.01 to 5 parts by mass, preferably 0.02 to 4 parts by mass, and more preferably 0.03 to 3 parts by mass, based on the total amount of components (A) to (C). If it is 0.01 part by mass or more, a sufficient pot life can be obtained, and if it is 5 parts by mass or less, the control ability is too strong and reactivity is not deteriorated.
• solvent examples include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane, and isoparaffin, hydrocarbon solvents such as industrial gasoline, petroleum benzine, and solvent naphtha, ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonylacetone, and cyclohexanone, ester solvents such as eth
• suitable solvents include ether-based solvents such as ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane, and 1,4-dioxane; solvents having an ester and an ether moiety, such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, and 2-butoxyethyl acetate; siloxane-based solvents, such as hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tris(trimethylsiloxy)methylsilane, and tetrakis(trimethylsiloxy)silane; and mixed solvents thereof.
• ether-based solvents such as ethyl ether, dipropyl
• the present invention provides an adhesion improver for use by adding to an addition-type silicone pressure-sensitive adhesive composition, comprising: (E) a polyorganohydrogensiloxane having at least three Si-H groups in one molecule and an aryl group-containing organic group directly bonded to a silicon atom, the ratio of the total number of the aryl group-containing organic groups to the total number of the Si-H and the organic groups bonded to silicon being 5 to 40%, and (F) an organosilicon compound having at least one epoxy group in one molecule and containing at least one silicon atom;
• the adhesion improver is characterized by comprising:
• Components (E) and (F) are as described above.
• an adhesion improver containing components E and F to an addition-type silicone adhesive composition, the adhesion to the substrate is improved, and an adhesive article having good adhesion to the substrate even when exposed to high temperature and high humidity for long periods of time can be obtained.
• silicone adhesives do not contain a catalyst.
• the catalyst is mixed uniformly before use.
• the curing conditions are 80-150°C for 20 seconds to 10 minutes, but are not limited to these.
• Paper, plastic film, glass, and metal are selected as substrates for coating with silicone adhesives.
• Examples of paper include fine paper, coated paper, art paper, glassine paper, polyethylene laminated paper, and craft paper.
• plastic films include polyethylene film, polypropylene film, polyester film, polyimide film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, polycarbonate film, polytetrafluoroethylene film, polystyrene film, ethylene-vinyl acetate copolymer film, ethylene-vinyl alcohol copolymer film, triacetyl cellulose film, polyether ether ketone film, and polyphenylene sulfide film.
• Glass fiber can also be used, and it may be used alone or in combination with other resins.
• metals include aluminum foil, copper foil, gold foil, silver foil, and nickel foil.
• silicone adhesives are often used on plastic films.
• silicone adhesives are often used with plastic film as substrate.
• Adhesive tapes and adhesive sheets made with various plastic films as substrates are used for various purposes, such as protective films for various displays, electrical insulating tapes, masking tapes, splicing tapes, and skin attachment.
• Displays include television receivers, computer monitors, monitors for mobile information terminals, surveillance monitors, video cameras, digital cameras, mobile phones, mobile information terminals, dashboard displays for automobiles, dashboard displays for various equipment, devices, and devices, liquid crystal displays, organic EL displays, automatic ticket vending machines, automatic teller machines, and various touch panels and flat panel displays (FPDs) for displaying characters, symbols, and images.
• FPDs flat panel displays
• the coating method may be any known coating method, such as a comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater, gravure coater, screen coating, dip coating, cast coating, etc.
• the coating amount can be 0.1-300 ⁇ m, preferably 0.5-200 ⁇ m.
• Me represents a methyl group
• Vi represents a vinyl group
• Ph represents a phenyl group.
• the silicone adhesive containing the components (A), (B), and (C) is added with the curing catalyst (D) and the components (E), (F), (G), and (H) described above, and mixed and stirred quickly to prepare a treatment bath, which is then applied to a polyethylene terephthalate (PET) film having a thickness of 23 ⁇ m and a width of 25 mm, using an applicator to set the thickness of the adhesive layer after curing to 30 ⁇ m.
• PET polyethylene terephthalate
• the adhesive article is left to stand under three conditions: 1 day at 60° C./90% RH, 7 days at 60° C./90% RH, and 28 days at 60° C./90% RH.
• ⁇ The adhesive layer does not peel off from the substrate.
• ⁇ The adhesive layer is completely peeled off from the substrate.
• Adhesive strength The adhesive tape prepared in the same manner as described in the above [Adhesion] was applied to a glass plate and pressed by rolling a 2 kg rubber-coated roller back and forth twice.
• the glass plate to which the adhesive tape was applied was placed in a thermostatic chamber with a constant humidity and temperature for a predetermined number of days, and then removed.
• the force (N/25 mm) required to peel the tape from the glass plate at an angle of 180° at a speed of 300 mm/min was measured using a tensile tester.
• ethynylcyclohexanol (0.20 parts by mass) was mixed, and toluene was added to obtain silicone pressure-sensitive adhesive base composition I containing approximately 60% by mass of the active ingredient.
• ethynylcyclohexanol (0.20 parts by mass) was mixed, and toluene was added to obtain silicone pressure-sensitive adhesive base composition II containing approximately 60% by mass of the active ingredient.
• component (C) polyorganohydrogensiloxane having 1.561 mol/100 g of Si-H groups represented by the above formula (C-1) (1.28 parts by mass, the molar ratio of Si-H groups to alkenyl groups in (A-2) is 10.0) and as component (H) ethynylcyclohexanol (0.20 parts by mass) were mixed, and toluene was added to obtain silicone adhesive base composition III with an active ingredient of approximately 30% by mass.
• component (C) polyorganohydrogensiloxane having 1.561 mol/100 g of Si-H groups represented by the above formula (C-1) (0.46 parts by mass, the molar ratio of Si-H groups to alkenyl groups in (A-1) is 2.0) was mixed with ethynylcyclohexanol (0.10 parts by mass) as component (H) to obtain silicone adhesive base composition IV.
• the components (D) to (G) used in the preparation of the silicone pressure-sensitive adhesive composition are as follows: Component (D) (D-1): Toluene solution containing 0.5% by mass of platinum in 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex (D-2): Silicone solution containing 0.5% by mass of platinum in 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex
• E-1 Methylhydrogenpolysiloxane represented by the following formula (aryl group ratio: 9.6%)
• E-2) Methylhydrogenpolysiloxane represented by the following formula (aryl group ratio: 19.7%)
• E-3) Methylhydrogenpolysiloxane represented by the following formula (aryl group ratio: 19.9%)
• e2-1 Methylhydrogenpolysiloxane represented by the following formula (aryl group ratio: 0.0%) (for comparison)
• Component (F) (F-1) An organosilicon compound represented by the following formula (Ep has the following structure): (F-2) Organosilicon compound represented by the following average composition formula: [Ep-Si-O 3/2 ] 4.0 [-O 1/2 Me] 6.0 (F-2) (F-3) Organosilicon compound represented by the following average composition formula: [Ep-Si-O 3/2 ] 2.0 [Si-O 4/2 ] 2.0 [-O 1/2 Me] 8.0 (F-3)
• Component (G) (G-1) Organopolysiloxane represented by the following average composition formula (alkenyl group amount: 0.53 mol/100 g): (G-2) Organopolysiloxane represented by the following formula (alkenyl group amount: 0.22 mol/100 g)
• Examples 1 to 11 it was confirmed that good adhesion to the substrate was obtained with a single coating, and the adhesion to the substrate was good under the above conditions in all cases. This is believed to be due to an interaction at the interface between the component (E) having an aryl group and the substrate due to the stacking effect of ⁇ electrons.
• the component (E) of the present invention is not contained, and therefore sufficient substrate adhesion is not obtained.
• the component (E) is contained, but the component (F) is not contained, and therefore it is understood that the substrate adhesion deteriorates under high temperature and high humidity conditions for a long time.
• a silicone pressure-sensitive adhesive composition comprising: [2]: The silicone pressure-sensitive adhesive composition according to [1], further comprising (G) 0.01 to 10 parts by mass of a silicon compound containing 0.15 mol or more of alkenyl groups per 100 g, based on the total amount of components (A) to (C). [3]: The silicone pressure-sensitive adhesive composition according to [1] or [2], further comprising an addition reaction inhibitor (H) in an amount of 0.01 to 5 parts by mass based on the total amount of components (A) to (C).
• [4] The silicone pressure-sensitive adhesive composition according to any one of [1] to [3], wherein the component (E) is represented by the following average composition formula (3): ( R4 represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms and no aliphatic unsaturated bonds, at least one of R4 represents an aryl group-containing organic group having 6 to 10 carbon atoms, at least three of R4 have a Si-H group, g represents a positive number of 2 or more, h represents a positive number of 1 or more, i and j represent positive numbers of 0 or more, and 10 ⁇ g+h+i+j ⁇ 500.) [5]: The silicone pressure-sensitive adhesive composition according to any one of [1] to [4], characterized in that the ratio of the total number of aryl group-containing organic groups to the total number of Si-H and silicon-bonded groups in component (E) is 8 to 30%.
• [7] The silicone pressure-sensitive adhesive composition according to any one of [1] to [6], wherein the component (F) is at least one of a compound represented by the following formula (4) or a compound in which a portion of a hydrolyzable group in a compound represented by the following formula (4) is condensed: ( R5 is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, R6 is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and k is a positive number satisfying 1 ⁇ k ⁇ 3.) [8]: The silicone pressure-sensitive adhesive composition according to [2], wherein the component (G) is a silicon compound having at least one siloxane bond per molecule.
• a pressure-sensitive adhesive article comprising the silicone pressure-sensitive adhesive composition according to any one of [1] to [8] coated on at least one surface of a substrate and cured.
• An adhesion improver for use as an additive in an addition-type silicone pressure-sensitive adhesive composition (E) a polyorganohydrogensiloxane having at least three Si-H groups in one molecule and an aryl group-containing organic group directly bonded to a silicon atom, the ratio of the total number of the aryl group-containing organic groups to the total number of the Si-H and the organic groups bonded to silicon being 5 to 40%, and (F) an organosilicon compound having at least one epoxy group in one molecule and containing at least one silicon atom;
• An adhesion improver comprising:
• the present invention is not limited to the above-described embodiments.
• the above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included within the technical scope of the present invention.

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