WO2014167898A1 - 無溶剤型シリコーン粘着剤組成物及び粘着性物品 - Google Patents
無溶剤型シリコーン粘着剤組成物及び粘着性物品 Download PDFInfo
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- WO2014167898A1 WO2014167898A1 PCT/JP2014/054144 JP2014054144W WO2014167898A1 WO 2014167898 A1 WO2014167898 A1 WO 2014167898A1 JP 2014054144 W JP2014054144 W JP 2014054144W WO 2014167898 A1 WO2014167898 A1 WO 2014167898A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- 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
- C09J2483/00—Presence of polysiloxane
Definitions
- the present invention relates to a solvent-free silicone pressure-sensitive adhesive composition and a pressure-sensitive adhesive article using the composition.
- Adhesives are used in various situations, mainly on labels and adhesive tapes attached to products. Recently, the application has been expanded with the advancement of technologies related to electronic terminals, such as adhesive films for display protection and protective films in the manufacturing process of products. In addition to surface protection, it is also used for optical members by taking advantage of the transparency of the material, and applications that are used inside products such as Optical Clear Adhesive Tape (OCA tape) are also being developed.
- OCA tape Optical Clear Adhesive Tape
- the main categories of adhesives are acrylic, rubber, silicone, etc., each with advantages and disadvantages. Silicone pressure-sensitive adhesives are more disadvantageous than acrylic and rubber materials because of the high cost of raw materials, but have two other characteristics such as heat resistance, cold resistance, weather resistance, chemical resistance, and electrical insulation. Better than the adhesive.
- One way to improve the productivity of these films is to improve the curability of the pressure-sensitive adhesive layer.
- the improved curability enables product production at a faster speed than before.
- JP 2011-012092 A Patent Document 6 also mentions low-temperature curing, which uses a large amount of solvent in the same manner as conventional silicone adhesives, and is a solvent-free silicone adhesive. There has never been a low temperature curing technique for.
- the present invention has been made in view of the above circumstances, and an object thereof is to provide a solventless silicone pressure-sensitive adhesive composition and a pressure-sensitive adhesive that are cured at a low temperature of 100 ° C. or lower.
- the present inventor has made the solvent-free by using a silicone pressure-sensitive adhesive composition containing a specific raw material, and is superior in curability at a low temperature than a conventional silicone pressure-sensitive adhesive. It discovered that it became a composition and came to make this invention.
- the present invention provides the following solventless silicone pressure-sensitive adhesive composition and pressure-sensitive adhesive article.
- A 40-100 parts by mass of an organopolysiloxane having at least two alkenyl group-containing organic groups in one molecule represented by the following average composition formula (1):
- R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be the same or different, and includes at least two alkenyl group-containing organic groups 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 100 ⁇ a + b + c + d ⁇ 2000.
- R 2 3 SiO 1/2 unit (R 2 is each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms which does not have an aliphatic unsaturated bond. ) And SiO 4/2 units, and (R 2 3 SiO 1/2 units) / (SiO 4/2 units) is a molar ratio of 0.6 to 1.0, 0 to 60 parts by mass of an organopolysiloxane , (However, the total of the components (A) and (B) is 100 parts by mass.) (C) represented by the following average composition formula (2), having at least three Si—H groups in one molecule, and having a Si—H group content of 30 mol% or less of all organic groups bonded to silicon atoms Organohydrogenpolysiloxane (A) and (B) for all alkenyl groups of component, An amount of Si—H groups in a molar ratio of 0.2 to 10, R 3 e H f SiO (4
- [6] The solvent-free silicone pressure-sensitive adhesive composition according to any one of [1] to [5], wherein the cured product has a rubber hardness of 40 or less when measured using an Asker C-type hardness meter object.
- the solventless silicone pressure-sensitive adhesive composition of the present invention can be cured under energy-saving conditions such as fast curing and low temperature curing.
- Component (A) is an organopolysiloxane having at least two alkenyl group-containing organic groups in one molecule. Specific examples include those represented by the following average composition formula (1).
- R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be the same or different, and at least two of them are alkenyl group-containing organic groups having 2 to 10 carbon atoms.
- the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and a benzyl group.
- Aralkyl groups and the like, and some or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with halogen atoms or other groups, such as trifluoromethyl group, 3,3,3-trimethyl Examples include a fluoropropyl group. Of these, a saturated aliphatic group or aromatic group is preferable, and a methyl group and a phenyl group are particularly preferable.
- alkenyl group-containing organic group examples include vinyl groups, allyl groups, hexenyl groups, octenyl groups and other alkenyl groups, acryloylpropyl groups, acryloylmethyl groups, methacryloylpropyl groups and other acryloylalkyl groups and methacryloylalkyl groups, Examples thereof include a cycloalkenylalkyl group such as a cyclohexenylethyl group and an alkenyloxyalkyl group such as a vinyloxypropyl group. Among these, a vinyl group is particularly preferable.
- the amount of alkenyl group contained in component (A) is preferably 0.005 to 0.08 mol, more preferably 0.008 to 0.06 mol, per 100 g of organopolysiloxane.
- a is an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6, and b is an integer of 1 or more, preferably 90 to 1,900, More preferably, it is 180 to 1,700, c and d are integers of 0 or more, 100 ⁇ a + b + c + d ⁇ 2,000, and preferably 200 ⁇ a + b + c + d ⁇ 1,800.
- a + b + c + d is smaller than 100, the reaction is delayed due to an excessive number of crosslinking points, and when it is larger than 2,000, the viscosity of the composition becomes very high, resulting in poor handling.
- the viscosity of the component (A) is preferably 100 to 100,000 mPa ⁇ s at 25 ° C., more preferably 500 to 80,000 mPa ⁇ s.
- the viscosity of the base polymer In order to obtain a solvent-free silicone adhesive, the viscosity of the base polymer must be low to some extent, and it is difficult to apply a high-viscosity solid organopolysiloxane called gum (raw rubber) as in the past.
- the viscosity is a value measured using a rotational viscometer at 25 ° C. (hereinafter the same).
- the component (A) is usually obtained by ring-opening polymerization of a cyclic low-molecular siloxane such as octamethylcyclotetrasiloxane using a catalyst, but contains a cyclic low-molecular siloxane as a raw material after polymerization. Therefore, it is preferable to use what was distilled off, heating and reducing pressure, making an inert gas pass in the reaction product.
- Component (B) is an R 2 3 SiO 1/2 unit (wherein R 2 is each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms that does not have an aliphatic unsaturated bond). ) And SiO 4/2 units, and (R 2 3 SiO 1/2 units) / (SiO 4/2 units) in a molar ratio of 0.6 to 1.0, preferably 0.65 to An organopolysiloxane that is 0.9. When this molar ratio is less than 0.6, the adhesive strength and tackiness of the cured product may be reduced, and when it exceeds 1.0, the adhesive strength and holding power may be reduced.
- the monovalent hydrocarbon group having 1 to 10 carbon atoms in R 2 is preferably a methyl group, ethyl group, propyl group, butyl group or the like, preferably an alkyl group having 2 to 6 carbon atoms, phenyl group, tolyl group or the like.
- An aryl group having 6 to 10 carbon atoms, a benzyl group, etc., preferably an aralkyl group having 7 to 10 carbon atoms can be mentioned.
- Examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, an allyl group, and a butenyl group.
- the component (B) two or more organopolysiloxanes may be used in combination.
- the R 2 2 SiO 3/2 unit and the R 2 SiO 2/2 unit in the component (B) are contained within the range not impairing the characteristics of the present invention, particularly within 20 mol% of the component (B). It is also possible to make it contain.
- Component (B) may be subjected to a condensation reaction in the presence of a catalyst. This is an operation of reacting hydrolyzable groups present on the surface, and an effect such as improvement in adhesive strength can be expected.
- the reaction may be performed at room temperature to reflux using an alkaline catalyst, and neutralized as necessary.
- the alkaline catalyst examples 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 butyllithium; Potassium silanolates; Nitrogen compounds such as ammonia gas, aqueous ammonia, methylamine, trimethylamine, and triethylamine. Among these, ammonia gas or ammonia Water is 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 for neutralizing the alkaline catalyst may be added as necessary.
- the neutralizing agent include acidic gases such as hydrogen chloride and carbon dioxide; organic acids such as acetic acid, octylic acid and citric acid; and mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid.
- an inert gas such as nitrogen may be vented and distilled off.
- the amount of component (A) is 40 to 100 parts by mass, preferably 40 to 95 parts by mass More preferably, the content is 45 to 95 parts by mass, and the remainder (that is, 0 to 60 parts by mass, preferably 5 to 60 parts by mass, more preferably 5 to 55 parts by mass) is used as component (B).
- component (A) If a component is less than 40 mass parts, the viscosity of a composition will become high and handling will become difficult.
- Component (C) is an organohydrogenpolysiloxane having at least 3 Si—H groups in one molecule, and the content of Si—H groups is 30 mol% or less of all organic groups in the siloxane.
- Genpolysiloxane Specific examples include those represented by the following average composition formula (2). R 3 e H f SiO (4-ef) / 2 (2)
- R 3 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably having no aliphatic unsaturated bond.
- alkyl groups such as methyl group, ethyl group, propyl group and butyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, aralkyl groups such as benzyl group, etc.
- a part or all of the hydrogen atoms bonded to the carbon atom of the above group may be substituted with a halogen atom or other group, and examples thereof include a trifluoromethyl group and a 3,3,3-trifluoropropyl group. .
- e and f are numbers satisfying e> 0, f> 0 and 0 ⁇ e + f ⁇ 3, preferably 0 ⁇ e ⁇ 2, 0 ⁇ f ⁇ 2, 1 ⁇ e + f ⁇ 3. It is.
- the component (C) preferably has a structure as shown by the following general formula (3).
- R 4 and R 7 are a monovalent hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom.
- R 5 and R 6 are each a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably having no aliphatic unsaturated bond, such as a methyl group, an ethyl group, a propyl group, or a butyl group.
- An alkyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and a part or all of the hydrogen atoms bonded to the carbon atoms of these groups are halogen atoms or It may be substituted with other groups, and examples thereof include a trifluoromethyl group and a 3,3,3-trifluoropropyl group. Of these, a saturated aliphatic group or aromatic group is preferable, and a methyl group and a phenyl group are particularly preferable.
- G in the general formula (3) is an integer satisfying 1 ⁇ g ⁇ 100, preferably 3 ⁇ g ⁇ 80.
- H is an integer satisfying 3 ⁇ h ⁇ 80, preferably 4 ⁇ h ⁇ 70.
- the amount of (C) added is such that the molar ratio of Si—H groups in component (C) to the total alkenyl groups in components (A) and (B) (Si—H / alkenyl groups) is 0.2 to 10. Preferably, it is blended so as to be in the range of 0.5-8. When the molar ratio is less than 0.2, the crosslink density is low, thereby reducing the cohesive strength and holding power of the cured product. When the molar ratio exceeds 10, the crosslink density is high and appropriate adhesive strength and tackiness cannot be obtained.
- the component (C) is usually produced by ring-opening polymerization of a cyclic low molecular siloxane such as octamethylcyclotetrasiloxane and a siloxane containing a Si—H group such as tetramethylcyclotetrasiloxane using an acid catalyst. Since the cyclic low-molecular siloxane that is a raw material is contained after the polymerization, it is preferable to use a material obtained by distilling off the inert gas through the reaction product under heating and reduced pressure.
- Si—H modification rate Component Si—H group content (hereinafter referred to as Si—H modification rate) is 30 mol% or less, preferably 28 mol% or less, based on the total organic groups of the organopolysiloxane.
- the lower limit is preferably 0.5 mol% or more, particularly 1 mol% or more.
- the Si—H group is a functional group used for the hydrosilylation reaction with the alkenyl group such as the vinyl group of the component (A), but as the proportion of the Si—H group contained in the structure decreases (Si—H modification rate) It has been clarified through various studies that the lower the value, the better the curability.
- the higher the Si—H modification rate the shorter the physical distance between Si—H groups, and the first reaction causes steric hindrance to the next reacting Si—H group. It is presumed that the reaction becomes slow and the curability is poor.
- the component (C) is produced by the above method, it can be obtained as an average structure. However, it is considered that the smaller the Si—H group-containing siloxane, the more the Si—H groups are separated from each other. If the Si—H modification rate is less than 0.5 mol%, the crosslinking density is lowered and the cohesive force may be impaired.
- the viscosity of the component (C) is not particularly limited, but the viscosity at 25 ° C. is 1 to 1,000 mPa ⁇ s, preferably 2 to 500 mPa ⁇ s.
- the component (D) is a platinum group metal catalyst for hydrosilylation addition and curing of the alkenyl group in the component (A) and the Si—H group in the component (C).
- the central metals are platinum and palladium. Examples thereof include iridium, rhodium, osmium, ruthenium, etc. Among them, platinum is preferable.
- Platinum catalysts include chloroplatinic acid, alcohol solution of chloroplatinic acid, reaction product of chloroplatinic acid and alcohol, reaction product of chloroplatinic acid and olefin compound, reaction product of chloroplatinic acid and vinyl group-containing siloxane, etc. Is mentioned.
- the content of component (D) is such that the amount of metal is 1 to 500 ppm, preferably 2 to 450 ppm, relative to 100 parts by mass of components (A), (B), and (C). . If the content is less than 1 ppm, the reaction is slow and curing is insufficient, whereby various properties such as adhesive strength and holding power are not exhibited. If the content exceeds 500 ppm, the cured product becomes less flexible.
- a reaction control agent can be further blended as the component (E) as necessary. This is added to prevent the treatment liquid from thickening or gelling when the silicone pressure-sensitive adhesive composition is prepared or applied to the substrate, so that the addition reaction starts before heat curing. is there.
- the reaction control agent coordinates to the platinum group metal which is an addition reaction catalyst to suppress the addition reaction, and when heated and cured, the coordination is lost and the catalytic activity is exhibited.
- any of the reaction control agents conventionally used in addition reaction curable silicone compositions can be used.
- Specific examples include 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-tetramethyl 1,3-divinyldisiloxane, maleic acid ester, adipic acid ester and the like.
- the blending amount of component (E) is 0.005 to 2 parts by mass, preferably 0.01 to 1 part by mass, where the total total amount of components (A), (B), and (C) is 100 parts by mass. is there.
- amount is less than 0.005 parts by mass, a sufficient reaction control effect cannot be obtained, and unexpected curing may occur before use. If it exceeds 2 parts by mass, the reaction control effect becomes strong and sufficient curability may not be obtained.
- various additives may be added as long as the properties are not impaired.
- examples thereof include pigments made of organic or inorganic compounds, fillers, antistatic agents, and antioxidants.
- the solvent-free silicone pressure-sensitive adhesive composition of the present invention is characterized in that the cured product is soft and the rubber hardness is low, in addition to faster curing than conventional pressure-sensitive adhesive compositions. As a result, it is possible to follow a fine step that could not be followed by an adhesive tape or an adhesive film.
- the rubber hardness when the cured product of the solvent-free silicone pressure-sensitive adhesive composition of the present invention is measured using an Asker C-type hardness meter conforming to JIS S 6050 is 40 or less.
- the lower limit of the hardness is preferably 1 or more.
- the solvent-free silicone pressure-sensitive adhesive composition of the present invention can be used to obtain a pressure-sensitive adhesive article by coating it on various substrates and then heat-curing, heat-pressing, or the like.
- Paper, plastic film, or glass is selected as the substrate.
- the paper include high-quality 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, polystyrene film, ethylene-vinyl acetate copolymer film, ethylene-vinyl alcohol.
- Examples thereof include a copolymer film and a triacetyl cellulose film.
- the substrate is not limited to those shown here.
- a base material that has been previously subjected to primer treatment, corona treatment, etching treatment, plasma treatment, sandblast treatment, or the like may be used.
- the coating method may be applied using a 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, Examples include dip coating and cast coating.
- the curing temperature is preferably 40 ° C. or higher and 100 ° C. or lower, more preferably 50 ° C. or higher and 80 ° C. or lower. If the curing temperature is less than 40 ° C, the composition may not be completely cured, and if it exceeds 100 ° C, a substrate having poor heat resistance may not be used.
- the curing time may be 20 seconds to 30 minutes, but is not limited thereto.
- the composition of the present invention is solvent-free, not only the same coating as a normal silicone adhesive but also press molding is effective for forming a thick film.
- the pressing condition may be that the temperature of the pressed metal member is 80 to 100 ° C. and the pressing time is 20 seconds to 60 minutes, but is not limited thereto.
- Such press molding has a structure in which both sides of the base material / adhesive layer / base material adhesive layer are sandwiched with the base material.
- Potting is also possible as a method for producing a cured product of the solventless silicone pressure-sensitive adhesive composition.
- the existing solvent-type silicone pressure-sensitive adhesive composition it is considered that potting is difficult because bubbles remain due to solvent volatilization, but this is made possible by using a solvent-free type.
- it may involve a bubble when pouring into a container it can deaerate by pressure reduction.
- fluorine-based or silicone-based ones can be used as the release agent.
- the solvent-free silicone pressure-sensitive adhesive composition in the present invention is usually used as it is, and when improvement in use conditions such as poor handling properties is required, it is organic within the range that does not impair the characteristics of the present invention. It is acceptable to add a solvent.
- Me represents a methyl group
- Vi represents a vinyl group
- Example 1 95 parts by mass of dimethylpolysiloxane (A-1) having vinyl groups at both ends represented by the following average composition formula (4): 60 mass% toluene of organopolysiloxane (B) containing Me 3 SiO 1/2 units and SiO 2 units and having a (Me 3 SiO 1/2 units) / (SiO 2 unit) molar ratio of 0.85 5 parts by mass of the above-mentioned two components as a non-volatile component were mixed in a container, heated at 150 ° C. to distill off toluene, and then further distilled off at 130 ° C. under reduced pressure.
- A-1 dimethylpolysiloxane having vinyl groups at both ends represented by the following average composition formula (4): 60 mass% toluene of organopolysiloxane (B) containing Me 3 SiO 1/2 units and SiO 2 units and having a (Me 3 SiO 1/2 units) / (SiO 2 unit) molar ratio of 0.85 5
- organohydrogenpolysiloxane (C-1) represented by the following average composition formula (5) with respect to 100 parts by mass of the composition:
- a control agent 0.1 part by mass of 1-ethynyl-1-cyclohexanol was added and mixed and stirred to obtain a solventless silicone pressure-sensitive adhesive composition.
- Example 2 In Example 1, instead of the component (C-1), Example 1 was used except that 3.35 parts by mass of the organohydrogenpolysiloxane (C-2) represented by the following average composition formula (6) was used. In the same manner as above, a solventless silicone pressure-sensitive adhesive composition was obtained.
- Example 3 Example 1 except that 1.61 parts by mass of the organohydrogenpolysiloxane (C-3) represented by the following average composition formula (7) was used in place of the component (C-1) in Example 1. In the same manner as above, a solventless silicone pressure-sensitive adhesive composition was obtained.
- Example 1 is the same as Example 1 except that 0.83 parts by mass of organohydrogenpolysiloxane (C-4) represented by the following average composition formula (8) is used in place of the component (C-1). Similarly, a solvent-free silicone pressure-sensitive adhesive composition was obtained.
- C-4 organohydrogenpolysiloxane represented by the following average composition formula (8)
- Example 1 is the same as Example 1 except that 0.56 parts by mass of organohydrogenpolysiloxane (C-5) represented by the following average composition formula (9) is used instead of (C-1). Similarly, a solvent-free silicone pressure-sensitive adhesive composition was obtained.
- C-5 organohydrogenpolysiloxane represented by the following average composition formula (9)
- Example 2 Solvent-free silicone pressure-sensitive adhesive in the same manner as in Example 1 except that 0.40 part by mass of the organohydrogenpolysiloxane (C-6) represented by the following average composition formula (10) was used in Example 1. A composition was obtained.
- Example 5 60 parts by mass of dimethylpolysiloxane (A-2) having vinyl groups at both ends represented by the following average composition formula (11): 60 mass% toluene of organopolysiloxane (B) containing Me 3 SiO 1/2 units and SiO 2 units and having a (Me 3 SiO 1/2 units) / (SiO 2 unit) molar ratio of 0.85 40 parts by mass of the above two components as a non-volatile component were mixed in a container, heated at 150 ° C. to distill off toluene, and then further distilled off at 130 ° C. under reduced pressure.
- A-1 60 mass% toluene of organopolysiloxane (B) containing Me 3 SiO 1/2 units and SiO 2 units and having a (Me 3 SiO 1/2 units) / (SiO 2 unit) molar ratio of 0.85 40 parts by mass of the above two components as a non-volatile component were mixed in a container, heated at 150 ° C
- organohydrogenpolysiloxane (C-1) represented by the following average composition formula (5) with respect to 100 parts by mass of the composition:
- a control agent 0.1 part by mass of 1-ethynyl-1-cyclohexanol was added and mixed and stirred to obtain a solventless silicone pressure-sensitive adhesive composition.
- Example 6 In Example 5, instead of the component (C-1), Example 5 was used except that 3.27 parts by mass of an organohydrogenpolysiloxane (C-2) represented by the following average composition formula (6) was used. In the same manner as above, a solventless silicone pressure-sensitive adhesive composition was obtained.
- Example 7 In Example 5, Example 5 was used except that 1.57 parts by mass of organohydrogenpolysiloxane (C-3) represented by the following composition formula (7) was used instead of the component (C-1). Similarly, a solvent-free silicone pressure-sensitive adhesive composition was obtained.
- organohydrogenpolysiloxane (C-3) represented by the following composition formula (7) was used instead of the component (C-1).
- Example 8 Example 5 except that 0.81 part by mass of the organohydrogenpolysiloxane (C-4) represented by the following average composition formula (8) was used in place of the component (C-1) in Example 5. In the same manner as above, a solventless silicone pressure-sensitive adhesive composition was obtained.
- Example 5 instead of the component (C-1), Example 5 was used except that 0.55 parts by mass of the organohydrogenpolysiloxane (C-5) represented by the following average composition formula (9) was used. In the same manner as above, a solventless silicone pressure-sensitive adhesive composition was obtained.
- Example 5 Example 5 was used except that 0.39 parts by mass of organohydrogenpolysiloxane (C-6) represented by the following average composition formula (10) was used instead of the component (C-1). In the same manner as above, a solventless silicone pressure-sensitive adhesive composition was obtained.
- C-6 organohydrogenpolysiloxane represented by the following average composition formula (10)
- the silicone pressure-sensitive adhesive composition obtained as described above was evaluated according to the following items. ⁇ Si-H modification rate> The Si—H group content (mol%) relative to the total organic groups of the organohydrogenpolysiloxane of component (C) was determined.
- ⁇ Curing property> A silicone solution containing 0.5% by mass of platinum content of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex with respect to 100 parts by mass of the obtained silicone pressure-sensitive adhesive composition. 0.2 parts by mass mixed, coated on a PET film having a thickness of 23 ⁇ m and a width of 25 mm using an applicator so that the thickness of the pressure-sensitive adhesive layer after curing is 30 ⁇ m, and drying at 75 ° C. or 85 ° C. And air-dried for 1 minute to produce an adhesive article. The adhesive layer of this article was touched with the tip of a finger to evaluate curability as shown below. ⁇ : Hardened and no finger marks are left. (Triangle
- ⁇ Rubber hardness> A silicone solution containing 0.5% by mass of platinum content of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex with respect to 100 parts by mass of the obtained silicone pressure-sensitive adhesive composition. After 0.2 parts by mass was mixed and poured into an aluminum container that had been subjected to a mold release treatment, it was defoamed and dried for 1 hour in a 75 ° C. dryer to obtain a cured product. The cured product was taken out of the container, and the rubber hardness was measured with an Asker C-type rubber hardness meter (conforming to JIS S 6050).
- ⁇ Step following capability> A silicone solution containing 0.5% by mass of platinum content of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex with respect to 100 parts by mass of the obtained silicone pressure-sensitive adhesive composition. 0.2 parts by mass is mixed and applied to a PET film having a thickness of 23 ⁇ m and a width of 25 mm using an applicator so that the thickness of the pressure-sensitive adhesive layer after curing is set to 60 ⁇ m, and a 75 ° C. drier for 3 minutes. Air-dried to produce an adhesive article.
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Abstract
Description
〔1〕 (A)下記平均組成式(1)で表される、1分子中に少なくとも2つのアルケニル基含有有機基を有するオルガノポリシロキサン
40~100質量部、
(B)R2 3SiO1/2単位(R2はそれぞれ独立に脂肪族不飽和結合を有さない炭素数1~10の一価炭化水素基又は炭素数2~6のアルケニル基である。)とSiO4/2単位とからなり、(R2 3SiO1/2単位)/(SiO4/2単位)がモル比で0.6~1.0であるオルガノポリシロキサン
0~60質量部、
(但し、(A),(B)成分の合計は100質量部である。)
(C)下記平均組成式(2)で表され、1分子中に少なくとも3個のSi-H基を有し、Si-H基含有量がケイ素原子に結合する全有機基の30モル%以下であるオルガノハイドロジェンポリシロキサン
(A)成分及び(B)成分の全アルケニル基に対し、
Si-H基がモル比で0.2~10となる量、
R3 eHfSiO(4-e-f)/2 (2)
(R3は非置換又は置換の炭素数1~10の一価炭化水素基であり、e>0、f>0であり、更に0<e+f≦3である。)
(D)(A)成分のアルケニル基と(C)成分のSi-H基とをヒドロシリル化付加反応させて硬化させるための白金族金属系触媒
上記(A)~(C)成分の合計100質量部に対し、
金属量が1~500ppmとなる量
を含むことを特徴とする無溶剤型シリコーン粘着剤組成物。
〔2〕 (A)成分が40~95質量部、(B)成分が5~60質量部である〔1〕記載の無溶剤型シリコーン粘着剤組成物。
〔3〕 (C)成分が下記一般式(3)で表される〔1〕又は〔2〕記載の無溶剤型シリコーン粘着剤組成物。
R4 3Si-O-(SiR5 2-O)g-(SiR6H-O)h-O-SiR7 3
(3)
(R4、R7は炭素数1~10の一価炭化水素基又は水素原子、R5、R6は炭素数1~10の一価炭化水素基であり、1≦g≦100、3≦h≦80である。)
〔4〕 硬化温度を100℃以下とすることを特徴とする〔1〕、〔2〕又は〔3〕記載の無溶剤型シリコーン粘着剤組成物。
〔5〕 硬化温度を80℃以下とすることを特徴とする〔4〕記載の無溶剤型シリコーン粘着剤組成物。
〔6〕 硬化物をアスカーC型硬度計を用いて測定したときのゴム硬度が40以下であることを特徴とする〔1〕~〔5〕のいずれかに記載の無溶剤型シリコーン粘着剤組成物。
〔7〕 更に、(E)反応制御剤を(A)~(C)成分の合計100質量部に対し、0.005~2質量部含有する〔1〕~〔6〕のいずれかに記載の無溶剤型シリコーン粘着剤組成物。
〔8〕 〔1〕~〔7〕のいずれかに記載の無溶剤型シリコーン粘着剤組成物を基材上に塗布し、該組成物を硬化させて得られる粘着性物品。
(A)成分は、1分子中に少なくとも2つのアルケニル基含有有機基を有するオルガノポリシロキサンである。具体的な構造としては下記平均組成式(1)で表されるものが挙げられる。
なお、(A)成分に含まれるアルケニル基の量は、オルガノポリシロキサン100gあたり0.005~0.08モルが好ましく、0.008~0.06モルがより好ましい。
ここで、粘度は25℃において回転粘度計を用いて測定した値である(以下、同じ)。
(B)成分は、R2 3SiO1/2単位(R2はそれぞれ独立に脂肪族不飽和結合を有さない炭素数1~10の一価炭化水素基又は炭素数2~6のアルケニル基である。)とSiO4/2単位とからなり、(R2 3SiO1/2単位)/(SiO4/2単位)がモル比で0.6~1.0、好ましくは0.65~0.9であるオルガノポリシロキサンである。このモル比が0.6未満では硬化物として粘着力やタック性が低下することがあり、1.0を超える場合には粘着力や保持力が低下することがある。
(C)成分は1分子中に少なくとも3個のSi-H基を有するオルガノハイドロジェンポリシロキサンであり、Si-H基含有量が当該シロキサン中において全有機基の30モル%以下であるオルガノハイドロジェンポリシロキサンである。具体的な構造としては下記平均組成式(2)で表されるものが挙げられる。
R3 eHfSiO(4-e-f)/2 (2)
また、式(2)におけるe及びfは、e>0、f>0かつ0<e+f≦3を満たす数であり、好ましくは0≦e≦2、0≦f≦2、1≦e+f≦3である。
R4 3Si-O-(SiR5 2-O)g-(SiR6H-O)h-O-SiR7 3
(3)
(D)成分は、(A)成分中のアルケニル基と(C)成分中のSi-H基をヒドロシリル化付加して硬化させるための白金族金属系触媒であり、中心金属としては白金、パラジウム、イリジウム、ロジウム、オスミウム、ルテニウム等が例として挙げられ、中でも白金が好適である。白金触媒としては、塩化白金酸、塩化白金酸のアルコール溶液、塩化白金酸とアルコールとの反応物、塩化白金酸とオレフィン化合物との反応物、塩化白金酸とビニル基含有シロキサンとの反応物等が挙げられる。
本発明における無溶剤型シリコーン粘着剤組成物には、更に必要により(E)成分として反応制御剤を配合することができる。これは、シリコーン粘着剤組成物を調合ないし基材に塗工する際に加熱硬化の以前に付加反応が開始して処理液が増粘やゲル化を起こさないようにするために添加するものである。反応制御剤は付加反応触媒である白金族金属に配位して付加反応を抑制し、加熱硬化させるときには配位がはずれて触媒活性が発現する。ここで、付加反応硬化型シリコーン組成物に従来使用されている反応制御剤はいずれも使用することができる。具体例としては、3-メチル-1-ブチン-3-オール、3-メチル-1-ペンチン-3-オール、3,5-ジメチル-1-ヘキシン-3-オール、1-エチニルシクロヘキサノール、3-メチル-3-トリメチルシロキシ-1-ブチン、3-メチル-3-トリメチルシロキシ-1-ペンチン、3,5-ジメチル-3-トリメチルシロキシ-1-ヘキシン、1-エチニル-1-トリメチルシロキシシクロヘキサン、ビス(2,2-ジメチル-3-ブチノキシ)ジメチルシラン、1,3,5,7-テトラメチル-1,3,5,7-テトラビニルシクロテトラシロキサン、1,1,3,3-テトラメチル-1,3-ジビニルジシロキサン、マレイン酸エステル、アジピン酸エステル等が挙げられる。
基材としては、紙やプラスチックフィルム、ガラスが選択される。紙としては、上質紙、コート紙、アート紙、グラシン紙、ポリエチレンラミネート紙、クラフト紙等が挙げられる。プラスチックフィルムとしては、ポリエチレンフィルム、ポリプロピレンフィルム、ポリエステルフィルム、ポリイミドフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリビニルアルコールフィルム、ポリカーボネートフィルム、ポリスチレンフィルム、エチレン-酢酸ビニル共重合体フィルム、エチレン-ビニルアルコール共重合体フィルム、トリアセチルセルロースフィルム等が挙げられる。ガラスについても、厚みや種類などについて特に制限はなく、化学強化処理などをしたものでもよい。基材について、こちらに示したものだけに制限されるものではない。
下記平均組成式(4)で表される両末端にビニル基を有するジメチルポリシロキサン(A-1)95質量部、
実施例1において、(C-1)成分に代えて、下記平均組成式(6)で表されるオルガノハイドロジェンポリシロキサン(C-2)3.35質量部を用いた以外は、実施例1と同様にして無溶剤型シリコーン粘着剤組成物を得た。
実施例1において、(C-1)成分に代えて、下記平均組成式(7)で表されるオルガノハイドロジェンポリシロキサン(C-3)1.61質量部を用いた以外は、実施例1と同様にして無溶剤型シリコーン粘着剤組成物を得た。
実施例1において、(C-1)成分に代えて下記平均組成式(8)で表されるオルガノハイドロジェンポリシロキサン(C-4)0.83質量部を用いた以外は、実施例1と同様にして無溶剤型シリコーン粘着剤組成物を得た。
実施例1において、(C-1)に代えて、下記平均組成式(9)で表されるオルガノハイドロジェンポリシロキサン(C-5)0.56質量部を用いた以外は、実施例1と同様にして無溶剤型シリコーン粘着剤組成物を得た。
下記平均組成式(11)で表される両末端にビニル基を有するジメチルポリシロキサン(A-2)60質量部、
実施例5において、(C-1)成分に代えて、下記平均組成式(6)で表されるオルガノハイドロジェンポリシロキサン(C-2)3.27質量部を用いた以外は、実施例5と同様にして無溶剤型シリコーン粘着剤組成物を得た。
実施例5において、(C-1)成分に代えて、下記組成式(7)で表されるオルガノハイドロジェンポリシロキサン(C-3)1.57質量部を用いた以外は、実施例5と同様にして無溶剤型シリコーン粘着剤組成物を得た。
実施例5において、(C-1)成分に代えて、下記平均組成式(8)で表されるオルガノハイドロジェンポリシロキサン(C-4)0.81質量部を用いた以外は、実施例5と同様にして無溶剤型シリコーン粘着剤組成物を得た。
実施例5において、(C-1)成分に代えて、下記平均組成式(9)で表されるオルガノハイドロジェンポリシロキサン(C-5)0.55質量部を用いた以外は、実施例5と同様にして無溶剤型シリコーン粘着剤組成物を得た。
実施例5において、(C-1)成分に代えて、下記平均組成式(10)で表されるオルガノハイドロジェンポリシロキサン(C-6)0.39質量部を用いた以外は、実施例5と同様にして無溶剤型シリコーン粘着剤組成物を得た。
<Si-H変性率>
(C)成分のオルガノハイドロジェンポリシロキサンの全有機基に対するSi-H基含有量(モル%)を求めた。
(C)成分のSi-H基同士がどれだけ平均的に離れているかということを計算した。即ち、末端のMe3SiO1/2単位を除き、分子の両末端にMeHSiO2/2がひとつずつ存在すると仮定したときのSi-H基間に存在するMe2SiO2/2の数を示した。
得られたシリコーン粘着剤組成物100質量部に対し、1,3-ジビニル-1,1,3,3-テトラメチルジシロキサン白金(0)錯体の白金分を0.5質量%含むシリコーン溶液を0.2質量部混合し、厚み23μm、幅25mmのPETフィルムに、アプリケーターを用いて硬化後の粘着剤層の厚みが30μmとなるよう設定して塗工し、75℃又は85℃の乾燥機で1分間風乾させて粘着性物品を作製した。この物品の粘着剤層を指の先で触れて下記に示すように硬化性を評価した。
○:硬化しており、指の跡が残らない。
△:硬化不十分で指の跡が残る。
×:未硬化で糸引きをする。
得られたシリコーン粘着剤組成物100質量部に対し、1,3-ジビニル-1,1,3,3-テトラメチルジシロキサン白金(0)錯体の白金分を0.5質量%含むシリコーン溶液を0.2質量部混合し、離型処理をしたアルミ製の容器に流し込んだ後に脱泡し、75℃の乾燥機で1時間乾燥させて硬化物を得た。この硬化物を容器から取り出し、アスカーC型ゴム硬度計(JIS S 6050に準拠)にてゴム硬度を測定した。
得られたシリコーン粘着剤組成物100質量部に対し、1,3-ジビニル-1,1,3,3-テトラメチルジシロキサン白金(0)錯体の白金分を0.5質量%含むシリコーン溶液を0.2質量部混合し、厚み23μm、幅25mmのPETフィルムに、アプリケーターを用いて硬化後の粘着剤層の厚みが60μmとなるよう設定して塗工し、75℃の乾燥機で3分間風乾させて粘着性物品を作製した。次に、平坦なガラス上に粘着剤層を向けて厚み23μmのPETフィルムを置き、ガラスと当該フィルムとを貼り合わせたときの外観を下記に示すように評価した。
○:ガラスとフィルムとの間にフィルムの浮きが認められない。
×:ガラスとフィルムとの間にフィルムが部分的に浮いた隙間が認められる。
以上の評価結果を表1に示す。
Claims (8)
- (A)下記平均組成式(1)で表される、1分子中に少なくとも2つのアルケニル基含有有機基を有するオルガノポリシロキサン
40~100質量部、
(B)R2 3SiO1/2単位(R2はそれぞれ独立に脂肪族不飽和結合を有さない炭素数1~10の一価炭化水素基又は炭素数2~6のアルケニル基である。)とSiO4/2単位とからなり、(R2 3SiO1/2単位)/(SiO4/2単位)がモル比で0.6~1.0であるオルガノポリシロキサン 0~60質量部、
(但し、(A),(B)成分の合計は100質量部である。)
(C)下記平均組成式(2)で表され、1分子中に少なくとも3個のSi-H基を有し、Si-H基含有量がケイ素原子に結合する全有機基の30モル%以下であるオルガノハイドロジェンポリシロキサン
(A)成分及び(B)成分の全アルケニル基に対し、
Si-H基がモル比で0.2~10となる量、
R3 eHfSiO(4-e-f)/2 (2)
(R3は非置換又は置換の炭素数1~10の一価炭化水素基であり、e>0、f>0であり、更に0<e+f≦3である。)
(D)(A)成分のアルケニル基と(C)成分のSi-H基とをヒドロシリル化付加反応させて硬化させるための白金族金属系触媒
上記(A)~(C)成分の合計100質量部に対し、
金属量が1~500ppmとなる量
を含むことを特徴とする無溶剤型シリコーン粘着剤組成物。 - (A)成分が40~95質量部、(B)成分が5~60質量部である請求項1記載の無溶剤型シリコーン粘着剤組成物。
- (C)成分が下記一般式(3)で表される請求項1又は2記載の無溶剤型シリコーン粘着剤組成物。
R4 3Si-O-(SiR5 2-O)g-(SiR6H-O)h-O-SiR7 3
(3)
(R4、R7は炭素数1~10の一価炭化水素基又は水素原子、R5、R6は炭素数1~10の一価炭化水素基であり、1≦g≦100、3≦h≦80である。) - 硬化温度を100℃以下とすることを特徴とする請求項1、2又は3記載の無溶剤型シリコーン粘着剤組成物。
- 硬化温度を80℃以下とすることを特徴とする請求項4記載の無溶剤型シリコーン粘着剤組成物。
- 硬化物をアスカーC型硬度計を用いて測定したときのゴム硬度が40以下であることを特徴とする請求項1~5のいずれか1項記載の無溶剤型シリコーン粘着剤組成物。
- 更に、(E)反応制御剤を(A)~(C)成分の合計100質量部に対し、0.005~2質量部含有する請求項1~6のいずれか1項記載の無溶剤型シリコーン粘着剤組成物。
- 請求項1~7のいずれか1項記載の無溶剤型シリコーン粘着剤組成物を基材上に塗布し、該組成物を硬化させて得られる粘着性物品。
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WO2017065131A1 (ja) * | 2015-10-14 | 2017-04-20 | 信越化学工業株式会社 | 衝撃吸収性画面保護フィルム |
US20180037013A1 (en) * | 2015-03-05 | 2018-02-08 | Dow Corning Toray Co., Ltd. | Curable organopolysiloxane composition, a use thereof, and a laminate prepared from the composition |
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CN104470398B (zh) * | 2012-07-09 | 2016-12-14 | Ykk株式会社 | 链带、具有该链带的拉链以及链带的制造方法 |
TWI767036B (zh) * | 2017-08-25 | 2022-06-11 | 美商陶氏有機矽公司 | 壓敏性聚矽氧黏著劑組成物 |
US20210246337A1 (en) | 2018-06-29 | 2021-08-12 | Dow Silicones Corporation | Solventless silicone pressure sensitive adhesive and methods for making and using same |
WO2020000387A1 (en) | 2018-06-29 | 2020-01-02 | Dow Silicones Corporation | Anchorage additive and methods for its preparation and use |
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CN113840670B (zh) * | 2019-05-22 | 2024-05-10 | 信越化学工业株式会社 | 清洗剂组合物、基板的清洗方法和支承体或基板的清洗方法 |
EP3874004B1 (en) * | 2020-01-15 | 2023-10-11 | Dow Silicones Corporation | Silicone pressure sensitive adhesive composition and methods for the preparation and use thereof |
JP7321954B2 (ja) * | 2020-02-25 | 2023-08-07 | 信越化学工業株式会社 | シリコーン粘着剤組成物 |
JP7343714B2 (ja) | 2021-07-21 | 2023-09-12 | ダウ グローバル テクノロジーズ エルエルシー | シリコーン感圧接着剤ベースの水性分散液及び分散液の調製及び使用方法 |
WO2023195390A1 (ja) * | 2022-04-04 | 2023-10-12 | 信越化学工業株式会社 | シリコーン粘着剤組成物、粘着テープおよび粘着フィルム |
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- 2014-02-21 KR KR1020157030729A patent/KR20150143530A/ko not_active Application Discontinuation
- 2014-02-21 CN CN201480020326.9A patent/CN105102576A/zh active Pending
- 2014-02-21 WO PCT/JP2014/054144 patent/WO2014167898A1/ja active Application Filing
- 2014-04-11 TW TW103113400A patent/TW201510151A/zh unknown
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US20180037013A1 (en) * | 2015-03-05 | 2018-02-08 | Dow Corning Toray Co., Ltd. | Curable organopolysiloxane composition, a use thereof, and a laminate prepared from the composition |
WO2017065131A1 (ja) * | 2015-10-14 | 2017-04-20 | 信越化学工業株式会社 | 衝撃吸収性画面保護フィルム |
JPWO2017065131A1 (ja) * | 2015-10-14 | 2018-08-09 | 信越化学工業株式会社 | 衝撃吸収性画面保護フィルム |
Also Published As
Publication number | Publication date |
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KR20150143530A (ko) | 2015-12-23 |
US20160053148A1 (en) | 2016-02-25 |
JP2014205762A (ja) | 2014-10-30 |
CN105102576A (zh) | 2015-11-25 |
TW201510151A (zh) | 2015-03-16 |
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