WO2010107006A1 - Matière adhésive - Google Patents

Matière adhésive Download PDF

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Publication number
WO2010107006A1
WO2010107006A1 PCT/JP2010/054371 JP2010054371W WO2010107006A1 WO 2010107006 A1 WO2010107006 A1 WO 2010107006A1 JP 2010054371 W JP2010054371 W JP 2010054371W WO 2010107006 A1 WO2010107006 A1 WO 2010107006A1
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WO
WIPO (PCT)
Prior art keywords
silyl group
group
pressure
sensitive adhesive
containing polymer
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PCT/JP2010/054371
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English (en)
Japanese (ja)
Inventor
輝彦 安田
仁 下間
寿 佐藤
豪明 荒井
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旭硝子株式会社
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Publication of WO2010107006A1 publication Critical patent/WO2010107006A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
    • 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]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/20—Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; 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
    • C09J2475/00—Presence of polyurethane

Definitions

  • the present invention relates to a pressure-sensitive adhesive body, a silyl group-containing polymer used for the pressure-sensitive adhesive body, and a method for producing a pressure-sensitive adhesive sheet.
  • a pressure-sensitive adhesive is a solid that is tacky at room temperature and adheres to it by applying pressure to the adherend so that there is no adhesive residue from the adherend. Adhesive with removable removability. On the other hand, the adhesive other than the pressure-sensitive adhesive is required to be hard to peel off the adhesive (the adhesive after curing in the case of a curable adhesive) and the adherend.
  • an adhesive shall mean things other than an adhesive.
  • an adhesive may be abbreviated as PSA.
  • PSA As the pressure-sensitive adhesive, there is a type of pressure-sensitive adhesive that becomes a pressure-sensitive adhesive by curing the curable composition.
  • a layer of the curable composition is formed on the surface of the substrate, and then the curable composition is cured to form a layer of the adhesive on the surface of the substrate.
  • the base material and the pressure-sensitive adhesive layer are bonded to each other by the adhesive force at the time of curing the curable composition, and this adhesive force is higher than the pressure-sensitive adhesive force between the pressure-sensitive adhesive layer and the adherend.
  • the base material and the pressure-sensitive adhesive layer hardly peel off. That is, the pressure-sensitive adhesive formed from the curable composition is required to exhibit adhesiveness when the curable composition is cured and to be removable from the pressure-sensitive adhesive formed after curing.
  • the pressure-sensitive adhesive formed from the curable composition is required to have characteristics different from those of the curable adhesive.
  • the present invention relates to a pressure-sensitive adhesive formed from a curable composition.
  • this curable composition that is cured to become a pressure-sensitive adhesive is referred to as a “curable composition”, and curing of this curable composition.
  • the cured product having adhesiveness formed by the above is called “adhesive”.
  • the thickness of the pressure-sensitive adhesive layer may be reduced to suppress an increase in adhesive force.
  • the original function of the pressure-sensitive adhesive i.e., adhesion to the adherend with light pressure, tends to be impaired.
  • An object of the present invention is to provide a silyl group-containing polymer used for the pressure-sensitive adhesive body and a method for producing a pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive body of the present invention is composed of a structural unit derived from an initiator (a) having two or more active hydrogen groups per molecule and a structure derived from a dicarboxylic acid anhydride (b).
  • the silyl group-containing polymer (S) is At the molecular terminal of the polyester ether polyol (Z) obtained by ring-opening polymerization of the dicarboxylic anhydride (b) and the alkylene oxide (c) to the initiator (a) having two or more active hydrogen groups per molecule, Silyl group-containing polymer (S1) obtained by introducing a hydrolyzable silyl group, A polyester ether polyol (Z) is obtained by ring-opening polymerization of a dicarboxylic acid anhydride (b) and an alkylene oxide (c) to an initiator (a) having two or more active hydrogen groups per molecule, and the polyester ether polyol A polyol (A) containing (Z) and a polyisocyanate compound (B) are reacted to obtain a prepolymer (P), which is obtained by introducing a hydrolyzable silyl group into the molecular terminal of the prepolymer (P).
  • a polyester ether polyol (Z) is obtained by ring-opening polymerization of a dicarboxylic acid anhydride (b) and an alkylene oxide (c) to an initiator (a) having two or more active hydrogen groups per molecule, and the polyester ether polyol A polyol (A) containing (Z) and a polyisocyanate compound (B) are reacted to obtain a prepolymer (P), and a chain extender (C) is reacted with the prepolymer (P) to form a chain extended polyurethane.
  • a silyl group-containing polymer (S3) obtained by introducing a hydrolyzable silyl group into the molecular end of the chain-extended polyurethane; It is preferable that
  • the present invention is also derived from a structural unit derived from an initiator (a) having two or more active hydrogen groups per molecule, a structural unit derived from a dicarboxylic acid anhydride (b), and an alkylene oxide (c). And a silyl group-containing polymer (S) having a hydrolyzable silyl group at the molecular end.
  • the present invention also forms an uncured layer comprising a curable composition containing the silyl group-containing polymer (S) of the present invention on a substrate, and then the opposite side of the uncured layer from the substrate.
  • a method for producing a pressure-sensitive adhesive sheet wherein the uncured layer is cured in a state where the surface is exposed or in a state where a release sheet is laminated on the surface.
  • the present invention it is possible to realize a pressure-sensitive adhesive body having removability, having good heat resistance and being less likely to be re-removable even when time passes at high temperatures, and having low adhesive strength. According to the present invention, it is possible to realize a pressure-sensitive adhesive sheet that has removability, has good heat resistance, and does not easily decrease removability even when time passes at high temperatures, and has low adhesive strength.
  • the silyl group containing polymer (S) of this invention is suitable as a hardening component of the curable composition used as the adhesive body of this invention after hardening.
  • the number average molecular weight (Mn) and the mass average molecular weight (Mw) in this specification are polystyrene-converted molecular weights obtained by measuring with gel permeation chromatography using a standard curve prepared using a standard polystyrene sample with a known molecular weight. It is.
  • the molecular weight distribution (Mw / Mn) is a value obtained by dividing the mass average molecular weight (Mw) by the number average molecular weight (Mn).
  • the average hydroxyl value (OHV) in the present specification is a measured value based on JIS-K-1557-6.4.
  • the polyester ether polyol is a polyol having an ester bond and an ether bond.
  • the adhesiveness may be classified according to the peeling adhesive strength (peeling strength from the adherend). Slight adhesion when peel adhesion exceeds 0 N / 25 mm and less than 1 N / 25 mm, low adhesion when peel adhesion exceeds 1 N / 25 mm and less than 8 N / 25 mm, peel adhesion exceeds 8 N / 25 mm and 15 N / 25 mm The following cases are referred to as medium adhesion, and the case where the peel adhesive strength exceeds 15 N / 25 mm and is 50 N / 25 mm or less is called strong adhesion.
  • the peel adhesive strength conforms to the 180-degree peeling method specified in JIS-Z-0237 (1999) -8.3.1 and follows the following test method. Specifically, in a 23 ° C. environment, a 1.5 mm thick bright annealed stainless steel plate (SUS304 (JIS)) was pasted with an adhesive sheet test piece (width: 25 mm) to be measured, and a rubber roll having a mass of 2 kg. Crimp. After 30 minutes, the peel strength (180 degree peel, tensile speed 300 mm / min) is measured using a tensile tester specified in JIS-B-7721. The value of the peel strength after 30 minutes of sticking obtained in this way is defined as “peel adhesive strength” in the present invention.
  • SUS304 Japanese Industrial Standard
  • the pressure-sensitive adhesive body of the present invention is a cured product obtained by curing a curable composition containing a silyl group-containing polymer (S).
  • a curable composition containing a silyl group-containing polymer (S).
  • the cured product adheres to the substrate, and the cured product (adhesive) exhibits adhesiveness to the adherend.
  • the silyl group-containing polymer (S) includes a structural unit derived from an initiator (a) having two or more active hydrogen groups per molecule, a structural unit derived from a dicarboxylic acid anhydride (b), and an alkylene oxide.
  • the silyl group-containing polymer (S1) of the first embodiment is prepared by adding a dicarboxylic acid anhydride (b) and an alkylene oxide (c) to an initiator (a) having two or more active hydrogen groups per molecule. It is obtained by introducing a hydrolyzable silyl group into the molecular terminal of the polyester ether polyol (Z) obtained by ring-opening polymerization.
  • the silyl group-containing polymer (S2) of the second embodiment is prepared by reacting the polyol (A) containing the polyester ether polyol (Z) with the polyisocyanate compound (B) to produce a prepolymer (P). And a hydrolyzable silyl group is introduced at the molecular end of the prepolymer.
  • the silyl group-containing polymer (S3) of the third embodiment is obtained by reacting the prepolymer (P) with a chain extender (C) to obtain a chain extended polyurethane, and a molecular end of the chain extended polyurethane. It is obtained by introducing a hydrolyzable silyl group.
  • the silyl group-containing polymer (S) in the present specification is a concept including the silyl group-containing polymers (S1) to (S3) of the first to third embodiments.
  • the initiator (a) is a compound having two or more active hydrogen groups per molecule, and examples thereof include polyether polyols and polyhydric alcohols.
  • the number of active hydrogen groups per molecule of the initiator (a) is preferably 2 to 4, more preferably 2 or 3. That is, as the initiator (a), polyhydric alcohols may be used as they are, and further, alkylene oxide may be added and used as a polyether polyol.
  • the active hydrogen group in the initiator (a) is particularly preferably a hydroxyl group.
  • the structural unit derived from the initiator (a) means the remaining group obtained by removing all active hydrogen groups from the initiator (a).
  • the polyether polyol is a compound having a molecular weight of 300 to 4000 per hydroxyl group obtained by adding an alkylene oxide to a polyhydric alcohol.
  • a polyether diol as the initiator (a).
  • the polyhydric alcohols include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, and glycerin.
  • the alkylene oxide is preferably an alkylene oxide having 2 to 4 carbon atoms, and examples thereof include propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and ethylene oxide. Alkylene oxide may use only 1 type, or may use 2 or more types together.
  • the alkylene oxide is preferably ethylene oxide or propylene oxide, and more preferably only propylene oxide.
  • the molecular weight of the initiator (a) is preferably 62 to 4000, more preferably 400 to 2000. If the molecular weight is 62 or more, good flexibility can be obtained in the resulting adhesive. Moreover, if the said molecular weight is 4000 or less, it is preferable when improving the cohesion force of the adhesive body obtained.
  • the constituent unit derived from the initiator (a) is preferably contained in an amount of 1 to 60% by mass, more preferably 10 to 60% by mass. If the content of the structural unit derived from the initiator (a) is 1% by mass or more, the polyester ether polyol (Z) is easily obtained efficiently. Moreover, if content of the structural unit derived from an initiator (a) is 60 mass% or less, since content of dicarboxylic acid anhydride (b) in polyester ether polyol (Z) can be increased, the adhesive which is obtained The cohesive strength of is improved.
  • dicarboxylic anhydride (b) examples include phthalic anhydride, maleic anhydride, and succinic anhydride.
  • aromatic dicarboxylic acid anhydrides are preferable in that they have a high cohesion and polarity, and thus contribute greatly to the adhesion to the substrate and the adhesion to the adherend.
  • phthalic anhydride is more preferable.
  • the structural unit derived from the dicarboxylic acid anhydride (b) is preferably contained in an amount of 10 to 50% by mass, and more preferably 15 to 40% by mass.
  • alkylene oxide (c) examples include the same alkylene oxides used for the synthesis of the polyether polyol as the initiator (a). Among these, it is more preferable to use propylene oxide or ethylene oxide.
  • the molar ratio of the alkylene oxide (c) to the dicarboxylic acid anhydride (b) is 50/50 or more, the alkylene oxide (c) becomes excessive with respect to the dicarboxylic acid anhydride (b), and the alkylene oxide is terminated at the terminal.
  • dicarboxylic acid anhydride (b) and alkylene oxide (c) are copolymerized
  • dicarboxylic acid anhydride (b) and alkylene oxide (c) alternate. Or an alkylene oxide (c) undergoes a block addition reaction.
  • dicarboxylic acid anhydride (b) and alkylene oxide (c) dicarboxylic acid anhydride (b) is more reactive and dicarboxylic acid anhydride (c) does not undergo an addition reaction continuously.
  • the number of alkylene oxides (c) constituting the block chain in the polymer chain is as short as several.
  • the entire structure of the polyester ether polyol (Z) can be designed by adjusting the molecular weight of the initiator (a) and the addition amount of the alkylene oxide (c) at the terminal portion.
  • the alkylene oxide (c) is used in excess of the dicarboxylic acid anhydride (b), and the dicarboxylic acid is used. It is preferable to reduce the remaining amount of the unreacted acid anhydride (b) from the viewpoint of improving the reactivity between the molecular terminal of the polyester ether polyol (Z) and the isocyanate group.
  • a catalyst In the production of the polyester ether polyol (Z), it is preferable to use a catalyst from the viewpoint of a high polymerization reaction rate.
  • a ring-opening addition polymerization catalyst is suitably used, and examples thereof include alkali catalysts such as potassium hydroxide and cesium hydroxide; double metal cyanide complex catalysts; phosphazene catalysts.
  • alkali catalysts such as potassium hydroxide and cesium hydroxide
  • double metal cyanide complex catalysts phosphazene catalysts.
  • a double metal cyanide complex catalyst is more preferable.
  • the double metal cyanide complex catalyst a zinc hexacyanocobaltate complex coordinated with an organic ligand is preferable.
  • the organic ligand ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, and alcohols such as tert-butyl alcohol are preferable.
  • the polyester ether polyol (Z) has a hydroxyl value-converted molecular weight per hydroxyl group of preferably 250 to 20,000, more preferably 1000 to 10,000, and still more preferably 1,000 to 5,000.
  • a hydroxyl value-converted molecular weight per hydroxyl group preferably 250 to 20,000, more preferably 1000 to 10,000, and still more preferably 1,000 to 5,000.
  • the molecular weight in terms of hydroxyl value is 250 or more, the flexibility of the obtained pressure-sensitive adhesive is improved. If the molecular weight in terms of hydroxyl value is 20,000 or less, the cohesive force of the resulting pressure-sensitive adhesive is improved, and the viscosity of the solution tends to be low when the silyl group-containing polymer (S) is dissolved in a solvent.
  • the molecular weight in terms of hydroxyl value of the polyester ether polyol (Z) can be easily adjusted by appropriately adjusting the number of moles of the dicarboxylic acid anhydride (b) and the alkylene oxide (c) copolymerized with the initiator (a).
  • the polyester ether polyol (Z) preferably has an average molecular weight (M ′) per copolymer chain of 100 to 3000, more preferably 200 to 2000.
  • the average molecular weight (M ′) per copolymer chain means the average molecular weight per copolymer chain formed by copolymerization of dicarboxylic anhydride (b) and alkylene oxide (c). This is a value obtained by removing the molecular weight of the initiator (a) from the molecular weight in terms of hydroxyl value and dividing the molecular weight by the number of functional groups (number of active hydrogen groups) of the initiator (a).
  • the average molecular weight (M ′) per copolymer chain is 100 or more, the flexibility of the obtained pressure-sensitive adhesive is easily improved. Further, when the average molecular weight (M ′) per copolymer chain is 3000 or less, the viscosity of the resulting polyester ether polyol (Z) does not become too high.
  • the average molecular weight (M ′) per copolymer chain is appropriately determined by the number of moles of the dicarboxylic acid anhydride (b) and alkylene oxide (c) copolymerized with the initiator (a) as in the case of the hydroxyl value converted molecular weight. It can be easily adjusted by adjusting.
  • the acid value of the polyester ether polyol (Z) is preferably 2.0 mgKOH / g or less, more preferably 1.0 mgKOH / g or less, and may be zero. If the acid value of the polyester ether polyol (Z) is 2.0 mgKOH / g or less, the reactivity between the molecular terminal of the polyester ether polyol (Z) and the isocyanate group is improved, and the storage stability of the resulting pressure-sensitive adhesive is improved. improves.
  • silyl group-containing polymer (S1) The silyl group-containing polymer (S1) of this embodiment is obtained by introducing a hydrolyzable silyl group into the molecular terminal of the polyester ether polyol (Z) by the method described later.
  • a polyol (A) containing a polyester ether polyol (Z) and a polyisocyanate compound (B) are reacted to obtain a prepolymer (P), and hydrolysis is performed at the molecular terminals of the prepolymer (P). A functional silyl group is introduced.
  • the polyester ether polyol (Z) is the same as that of the first embodiment including the preferred mode.
  • the ratio of the polyester ether polyol (Z) in the polyol (A) is preferably 10% by mass or more and more preferably 50% by mass or more in order to increase the flexibility of the pressure-sensitive adhesive and prevent the removability from being lowered.
  • all of the polyol (A) is most preferably a polyester ether polyol (Z).
  • the polyester ether polyol (Z) may be one type or a combination of two or more types.
  • any one of polyoxytetramethylene polyol, polyoxyalkylene polyol, polyester polyol, and polycarbonate polyol is used as the balance of the polyol (A) or Two or more kinds of polyols (other polyols) are preferably used.
  • Polyisocyanate compound (B) examples include naphthalene-1,5-diisocyanate, polyphenylene polymethylene polyisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate (hereinafter referred to as 2,4-TDI).
  • aromatic polyisocyanates such as 2,6-tolylene diisocyanate (hereinafter sometimes referred to as 2,6-TDI); aralkyl such as xylylene diisocyanate and tetramethylxylylene diisocyanate Polyisocyanate; aliphatic polyisocyanate such as hexamethylene diisocyanate (hereinafter referred to as HDI); isophorone diisocyanate (hereinafter referred to as IPDI) and 4,4′-methylenebis (cyclohexyl isocyanate) Alicyclic polyisocyanates over G) or the like; and urethane modified product obtained from the polyisocyanate, biuret modified compounds, allophanate modified body, carbodiimide modified body, and isocyanurate-modified products thereof.
  • 2,6-TDI aromatic polyisocyanates
  • aralkyl such as xylylene diisocyanate and tetramethylxylylene diiso
  • polyisocyanate compound (B) those having two isocyanate groups are preferable, and 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, or isophorone diisocyanate is particularly preferable.
  • a non-yellowing polyisocyanate as the polyisocyanate compound (B).
  • aliphatic polyisocyanates such as hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, 2,4,4-trimethyl-hexamethylene diisocyanate; alicyclic rings such as isophorone diisocyanate and methylenebis (4-cyclohexylisocyanate) Formula polyisocyanate; non-yellowing aromatic diisocyanate such as xylylene diisocyanate.
  • the prepolymer (P) may be an isocyanate group-terminated prepolymer (PI) having an isocyanate group at the end of the molecular chain, or a hydroxyl group-terminated prepolymer (PH) having a hydroxyl group at the end of the molecular chain.
  • PI isocyanate group-terminated prepolymer
  • PH hydroxyl group-terminated prepolymer
  • the isocyanate group-terminated prepolymer (PI) is obtained by reacting the polyol (A) with the polyisocyanate compound (B) in an excess ratio of isocyanate groups (hereinafter, this reaction is referred to as prepolymer formation reaction).
  • a specific example of the prepolymer forming reaction is a reaction in which the polyol (A) and the polyisocyanate compound (B) are heated at 60 to 100 ° C. for 1 to 20 hours in a dry nitrogen stream.
  • a urethanization reaction catalyst can be used.
  • the urethanization reaction catalyst examples include organic tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and tin 2-ethylhexanoate; iron compounds such as iron acetylacetonate and ferric chloride; And tertiary amine catalysts such as triethylamine and triethylenediamine.
  • organotin compounds are preferred.
  • the prepolymer formation reaction it may be diluted with a solvent.
  • the solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone (hereinafter referred to as MEK), and dimethylformamide. And cyclohexanone. These may be used alone or in combination of two or more.
  • the ratio of the polyol (A) and the polyisocyanate compound (B) in the prepolymer formation reaction is defined as a value 100 times the molar ratio of “isocyanate group of the polyisocyanate compound (B) / hydroxyl group of the polyol (A)”.
  • the isocyanate index is preferably more than 100 to 200, more preferably 105 to 170.
  • the isocyanate group-terminated prepolymer (PI) obtained by the prepolymer formation reaction has an isocyanate group content of 1.5 to 10.0 mass. % Is preferred.
  • the molecular weight of the isocyanate group-terminated prepolymer (PI) is preferably 2000 to 150,000, more preferably 3000 to 80,000 in terms of number average molecular weight (Mn).
  • the hydroxyl group-terminated prepolymer (PH) is obtained by reacting the polyol (A) with the polyisocyanate compound (B) at a ratio of excess hydroxyl group.
  • the reaction between the polyol (A) and the polyisocyanate compound (B) can be carried out in the same manner as the prepolymer formation reaction for obtaining the isocyanate group-terminated prepolymer (PI). That is, in the step of performing the prepolymer forming reaction, the ratio of the polyol (A) and the isocyanate compound (B) is preferably such that the isocyanate index is 50 to less than 100, more preferably 50 to 98.
  • a urethanization reaction catalyst similar to the prepolymer formation reaction for obtaining the isocyanate group-terminated prepolymer (PI) may be used. Moreover, you may dilute with the solvent similar to the prepolymer formation reaction for obtaining isocyanate group terminal prepolymer (PI).
  • the hydroxyl group content in the hydroxyl group-terminated prepolymer (PH) thus obtained is preferably 0.03 to 1.00% by mass.
  • the molecular weight of the hydroxyl-terminated prepolymer (PH) is preferably 2000 to 100,000, more preferably 3000 to 80,000 in terms of number average molecular weight (Mn).
  • silyl group-containing polymer (S2) The silyl group-containing polymer (S2) of this embodiment is obtained by introducing a hydrolyzable silyl group into the molecular terminal of the isocyanate group-terminated prepolymer (PI) or the hydroxyl group-terminated prepolymer (PH) by the method described later. It is done.
  • the polyol (A) containing the polyester ether polyol (Z) and the polyisocyanate compound (B) are reacted to obtain a prepolymer (P), and a chain extender is added to the isocyanate group-terminated prepolymer (P).
  • (C) is reacted to obtain a chain-extended polyurethane, and a hydrolyzable silyl group is introduced into the molecular end of the chain-extended polyurethane.
  • the polyester ether polyol (Z), polyol (A), polyisocyanate compound (B), and prepolymer (P) are the same as in the second embodiment, including preferred aspects.
  • Chain extender (C) When the isocyanate group-terminated prepolymer (PI) is used as the prepolymer (P), low-molecular diols or low-molecular diamines are preferable as the chain extender.
  • Preferred examples of the low molecular diols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like.
  • Low molecular diamines include aliphatic diamines such as ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine and 2,2,4-trimethylhexamethylene diamine; piperazine, isophorone diamine, dicyclohexyl And alicyclic diamines such as methane-4,4′-diamine; and aromatic diamines such as tolylenediamine, phenylenediamine, and xylylenediamine.
  • aliphatic diamines such as ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine and 2,2,4-trimethylhexamethylene diamine
  • piperazine isophorone diamine
  • dicyclohexyl And alicyclic diamines such as methane-4,4′-diamine
  • aromatic diamines such as
  • a diisocyanate compound is preferred as the chain extender.
  • a preferred diisocyanate compound is the same as the polyisocyanate compound (B) having two isocyanate groups.
  • the chain extension polyurethane according to the present invention is obtained by subjecting the prepolymer (P) to a chain extension reaction.
  • the end of the chain extended polyurethane may be any of an isocyanate group, a hydroxyl group, or an amino group.
  • the method for introducing a hydrolyzable silyl group differs depending on the terminal group.
  • the method of chain extension reaction is not particularly limited.
  • the method 1) or 3) is preferable because it is easy to obtain a uniform chain-extended polyurethane.
  • the solvent the same solvents as those exemplified in the prepolymer formation reaction can be used.
  • the ratio of the prepolymer (PI) and the low molecular diamine is “NCO group / low molecule of the prepolymer (PI)”.
  • the isocyanate index defined by a value 100 times the molar ratio of “NH2 group of diamine” is preferably 50 to less than 100, more preferably 50 to 98. Within this range, an amino group-terminated chain-extended polyurethane can be obtained.
  • the isocyanate index defined by a value 100 times the molar ratio of “group / OH group of prepolymer (PH)” is preferably more than 100 to 200, more preferably 101 to 150.
  • the isocyanate index is preferably 50 to less than 100, more preferably 50 to 98.
  • the reaction temperature in the chain extension reaction is preferably 80 ° C. or lower. When the reaction temperature exceeds 80 ° C., the reaction rate becomes too fast and it becomes difficult to control the reaction, so that it tends to be difficult to obtain a chain-extended polyurethane having a desired molecular weight and a desired structure.
  • the reaction temperature is preferably set to be equal to or lower than the boiling point of the solvent. In particular, 40-60 ° C. is preferable in the presence of MEK and / or ethyl acetate.
  • the molecular weight of the chain extended polyurethane is preferably 4,000 to 500,000 in terms of number average molecular weight. More preferably, it is 8,000 to 250,000.
  • silyl group-containing polymer (S3) The silyl group-containing polymer (S3) of the present embodiment is obtained by introducing a hydrolyzable silyl group into the molecular end of the chain-extended polyurethane by the method described later.
  • the hydrolyzable silyl group is a silyl group having a hydrolyzable group.
  • a silyl group represented by —SiX a R 3 (3-a) is preferable.
  • a represents an integer of 1 to 3.
  • a is preferably 2 to 3, and 3 is most preferred.
  • R 3 is a monovalent organic group having 1 to 20 carbon atoms, preferably a monovalent organic group having 1 to 6 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.
  • R 3 may have a substituent.
  • substituents examples include a methyl group and a phenyl group. If the hydrolyzable silyl group has a plurality of R 3, R 3 of the plurality of it may be the same or different from each other. That is, when a is 1, two R 3 bonded to one silicon atom (Si) are each independently a monovalent monovalent group having 1 to 20 carbon atoms that may have a substituent. An organic group is shown.
  • X represents a hydroxyl group (—OH) or a hydrolyzable group.
  • the hydrolyzable group include an —OR group (R is a hydrocarbon group having 4 or less carbon atoms).
  • R is a hydrocarbon group having 4 or less carbon atoms.
  • Such —OR group is preferably an alkoxy group or an alkenyloxy group, and particularly preferably an alkoxy group.
  • the alkoxy group or alkenyloxy group has 4 or less carbon atoms.
  • Specific examples include a methoxy group, an ethoxy group, a propoxy group, and a propenyloxy group.
  • a methoxy group or an ethoxy group is more preferable in that the curing rate of the curable composition can be further increased.
  • the plurality of X may be the same as or different from each other. That is, when a is 2 or 3, each X independently represents a hydroxyl group or a hydrolyzable group.
  • a trialkoxysilyl group is preferable, a trimethoxysilyl group or a triethoxysilyl group is more preferable, and a trimethoxysilyl group is particularly preferable. This is because the storage stability of the silyl group-containing polymer (S) is good and the curing rate of the curable composition is fast.
  • hydrolyzable silyl group introduction ratio As a method for introducing a hydrolyzable silyl group, a method using an isocyanate silane (Q1), a method using an aminosilane (Q2), a method using a mercaptosilane (Q3), a method using an epoxysilane (Q4), And a method (Q5) using hydrosilanes.
  • the ratio of introducing hydrolyzable silyl groups (hereinafter sometimes referred to as hydrolyzable silyl group introduction ratio) is 50 to 100 mol%, assuming that all the terminals capable of reacting theoretically are 100 mol%. It is preferably introduced, more preferably 80 to 100 mol%.
  • the terminal functional group of the polyol (Z), prepolymer (P) or chain-extended polyurethane to be introduced with the hydrolyzable silyl group is a group capable of reacting with an isocyanate group
  • the terminal functional group A hydrolyzable silyl group can be introduced by reacting silane with isocyanate silanes.
  • the group capable of reacting with an isocyanate group is, for example, a hydroxyl group or an amino group.
  • Isocyanate silanes include isocyanate methyltrimethoxysilane, 2-isocyanatoethyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 4-isocyanatobutyltrimethoxysilane, 5-isocyanatepentyltrimethoxysilane, isocyanatemethyltriethoxysilane, 2-isocyanatoethyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, 4-isocyanatobutyltriethoxysilane, 5-isocyanatepentyltriethoxysilane, isocyanatemethylmethyldimethoxysilane, 2-isocyanatoethylethyldimethoxysilane, 3-isocyanatepropyl Examples include trimethoxysilane or 3-isocyanatopropyltriethoxysilane. That. Among these, isocyanate
  • a catalyst may be used for this reaction.
  • a known urethanization reaction catalyst is used as the catalyst.
  • organic acid salts / organometallic compounds, tertiary amines and the like include organic acid salts / organometallic compounds, tertiary amines and the like.
  • Specific organic acid salts and organometallic compounds include tin catalysts such as dibutyltin dilaurate (DBTDL), bismuth catalysts such as bismuth 2-ethylhexanoate [bismuth tris (2-ethylhexanoate)], zinc naphthenate
  • zinc catalysts such as cobalt catalysts such as cobalt naphthenate and copper catalysts such as copper 2-ethylhexanoate.
  • Tertiary amines include triethylamine, triethylenediamine, N-methylmorpholine and the like.
  • Examples of the group capable of reacting with an amino group are an isocyanate group, an acryloyl group, and a methacryloyl group. If necessary, these groups may be introduced at the terminal before introducing the hydrolyzable silyl group.
  • the functional group at the end of the polyol (Z), prepolymer (P) or chain-extended polyurethane to be introduced with a hydrolyzable silyl group is a hydroxyl group, by reacting the hydroxyl group with acrylic acid or methacrylic acid , An acryloyl group or a methacryloyl group can be introduced at the molecular end.
  • an acryloyl group or a methacryloyl group can be introduced at the molecular terminal by reacting with hydroxyalkyl acrylates or hydroxyalkyl methacrylates.
  • hydroxyalkyl acrylates include 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate.
  • hydroxyalkyl methacrylates include 2-hydroxyethyl methacrylate and 4-hydroxybutyl methacrylate.
  • aminosilanes include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriisopropoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3- ( 2-aminoethyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2- Aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltriisopropoxysilane, N- (N- (2-aminoethyl) -2-aminoethyl) -3-a
  • the reaction between an amino group and an isocyanate group is a urea bond formation reaction.
  • the above-mentioned urethanization catalyst may be used.
  • the reaction between an amino group and an acryloyl group is a Michael addition reaction.
  • Examples of the group capable of reacting with a mercapto group are an isocyanate group, an acryloyl group, and an allyl group. If necessary, these groups may be introduced at the terminal before introducing the hydrolyzable silyl group.
  • the isocyanate group and acryloyl group are the same as in the method (Q2) using aminosilanes.
  • an allyl group is formed at the molecular end by reacting with allyl alcohol. Can be introduced.
  • Mercaptosilanes include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane Etc. Among these, 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane is preferable.
  • the reaction between the mercapto group and the isocyanate group is the same as the urethanization reaction, and a urethanization reaction catalyst may be used.
  • the reaction between the mercapto group and the acryloyl group or allyl group is preferably performed using a radical initiator.
  • the radical initiator include azobisisobutyronitrile (AIBN).
  • Epoxysilanes include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and the like are preferable. Among these, 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane is preferable.
  • amines and acid anhydrides are used as the catalyst in the reaction with the epoxy group.
  • examples include chain aliphatic polyamines, alicyclic polyamines, aromatic polyamines, modified aliphatic polyamines, imidazole compounds, and the like.
  • tertiary amines such as N, N-dimethylpiperazine, triethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30) and benzyldimethylamine (BDMA) are preferable.
  • the terminal functional group of the polyol (Z), prepolymer (P) or chain-extended polyurethane to be introduced with a hydrolyzable silyl group is a group capable of hydrosilylation reaction
  • the terminal functional group and the hydrosilane A hydrolyzable silyl group can be introduced by reacting with a group.
  • the group capable of hydrosilylation reaction is, for example, an acryloyl group or an allyl group, and these groups are introduced into the terminal of the polyol (Z), prepolymer (P) or chain-extended polyurethane.
  • the method for introducing an acryloyl group or an allyl group is the same as the method (Q3) using mercaptosilanes.
  • hydrosilanes examples include trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldi Examples thereof include siloxane. It is preferable to use a hydrosilylation catalyst for this reaction. Examples of the hydrosilylation catalyst include chloroplatinic acid.
  • the curable composition in this invention contains a silyl group containing polymer (S).
  • the curable composition contains at least one additive other than the silyl group-containing polymer (S), and the additive is preferably at least a curing catalyst.
  • the curing catalyst it is preferable to include water as a curing agent.
  • a preferred curable composition is a curable composition comprising a curing catalyst and at least two additives of water. The curable composition containing water can be cured in an atmosphere containing moisture.
  • the curable composition containing water is used. Since the curing reaction starts when the silyl group-containing polymer (S) is brought into contact with water, it is preferable to add water immediately before curing the curable composition.
  • this curable composition is exposed to the atmosphere containing a water
  • the curing rate can be adjusted by adjusting the amount of moisture, temperature, etc. in the atmosphere containing moisture.
  • the curable composition in this invention may contain the other polymer which has a hydrolysable silyl group other than a silyl group containing polymer (S). 30 mass% or less of the whole curable composition is preferable, and, as for the content rate of the other polymer which has a hydrolyzable silyl group, 10 mass% or less is more preferable.
  • the curable composition in the present invention may contain various additives.
  • the curable composition in this invention does not contain a plasticizer.
  • an ester plasticizer such as dioctyl phthalate.
  • the curable composition in the present invention is cured by contact with water. Therefore, it reacts with water in the atmosphere and is cured by moisture. Also, just prior to curing, water (H 2 O) may be added as a curing agent.
  • the amount of water added is 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the silyl group-containing polymer (S) and other polymers having hydrolyzable silyl groups.
  • 0.01 to 1 part by mass is more preferable, and 0.05 to 0.5 part by mass is particularly preferable. Curing can be effectively promoted by setting the content of the curing agent to 0.01 parts by mass or more, and the pot life during use can be ensured by setting the content of the curing agent to 5 parts by mass or less.
  • the curable composition in the present invention preferably contains a curing catalyst (curing accelerator) for accelerating the hydrolysis and / or crosslinking reaction of the hydrolyzable silyl group.
  • a curing catalyst a known catalyst can be appropriately used as a component for promoting the reaction of the hydrolyzable silyl group.
  • curing catalyst examples include divalent tin carboxylates such as tin 2-ethylhexanoate, tin n-octylate, tin naphthenate or tin stearate; octyl acid, oleic acid, naphthenic acid or stearin.
  • divalent tin carboxylates such as tin 2-ethylhexanoate, tin n-octylate, tin naphthenate or tin stearate; octyl acid, oleic acid, naphthenic acid or stearin.
  • Metal salts other than tin of organic carboxylic acid such as acid; bismuth carboxylate such as calcium carboxylate, zirconium carboxylate, iron carboxylate, vanadium carboxylate, bismuth tris-2-ethylhexanoate, lead carboxylate, carboxylic acid Titanium or nickel carboxylate; titanium alkoxides such as tetraisopropyl titanate, tetrabutyl titanate, tetramethyl titanate, tetra (2-ethylhexyl titanate); aluminum isopropylate, mono-sec-butoxyaluminum diisopropylate Zirconium alkoxides such as zirconium-n-propylate and zirconium-n-butyrate; Titanium chelates such as titanium tetraacetylacetonate, titanium ethylacetoacetate, titanium octylene glycolate and titanium lactate; Aluminum tris Aluminum chelates such as acetylace
  • curing catalysts may be used alone or in combination of two or more.
  • the above-mentioned metal-containing compound such as a reaction product of the divalent tin carboxylate, organotin carboxylate or organotin oxide and an ester compound, an aliphatic monoamine or other amine compound It is preferable to combine these because excellent curability can be obtained.
  • the content of the curing catalyst is preferably 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the silyl group-containing polymer (S) and other polymers. Is more preferable.
  • the curable composition in the present invention may be used after adding a solvent in order to improve the coating property and the like.
  • the solvent is not particularly limited.
  • the alcohol is preferably an alkyl alcohol having 1 to 10 carbon atoms, more preferably methanol, ethanol, isopropyl alcohol, isopentyl alcohol or hexyl alcohol, and further preferably methanol or ethanol.
  • the curing time of the curable composition can be increased by increasing the amount of addition. This is an effective technique for prolonging the so-called pot life of the curable composition until it reaches a predetermined viscosity after preparation.
  • the addition amount should be 500 mass parts or less with respect to 100 mass parts of total amounts of a silyl group containing polymer (S) and another polymer. The amount is preferably 1 to 100 parts by mass. When the addition amount exceeds 500 parts by mass, the cured product (adhesive) may shrink as the solvent volatilizes.
  • the curable composition in the present invention may contain a small amount of a dehydrating agent as long as the effects of the present invention are not impaired.
  • dehydrating agents include alkyl orthoformate such as methyl orthoformate and ethyl orthoformate; alkyl orthoacetate such as methyl orthoacetate and ethyl orthoacetate; methyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane or tetra Examples include hydrolyzable organic silicone compounds such as ethoxysilane; hydrolyzable organic titanium compounds and the like.
  • vinyltrimethoxysilane or tetraethoxysilane is preferable from the viewpoints of cost and dehydration ability.
  • the content thereof is 0.001 to 30 parts by mass with respect to 100 parts by mass of the total amount of the silyl group-containing polymer (S) and other polymers. Is more preferable, and 0.01 to 10 parts by mass is more preferable.
  • the curable composition may contain the following fillers, reinforcing agents, stabilizers, flame retardants, antistatic agents, mold release agents, antifungal agents, and the like.
  • the filler or reinforcing agent include carbon black, aluminum hydroxide, calcium carbonate, titanium oxide, silica, glass, bone powder, wood powder, and fiber flakes.
  • the stabilizer include an antioxidant, an ultraviolet absorber, and a light stabilizer.
  • the flame retardant include chloroalkyl phosphate, dimethyl methyl phosphonate, ammonium polyphosphate, or an organic bromine compound.
  • the mold release agent include wax, soaps, or silicone oil.
  • the antifungal agent examples include pentachlorophenol, pentachlorophenol laurate, bis (tri-n-butyltin) oxide, and the like.
  • the curable composition may contain an adhesion-imparting agent for the purpose of improving the adhesion to the substrate.
  • the pressure-sensitive adhesive body of the present invention is suitably used as a pressure-sensitive adhesive layer for pressure-sensitive adhesive sheets.
  • the pressure-sensitive adhesive sheet is provided with a pressure-sensitive adhesive layer on a base material, and the surface of the pressure-sensitive adhesive layer opposite to the base material is used as a pressure-sensitive adhesive surface having removability.
  • the peeling sheet is laminated
  • the base material consists of a peeling sheet, and the double-sided adhesive sheet by which the peeling sheet was laminated
  • the thickness of an adhesive sheet is not ask
  • the thickness of the pressure-sensitive adhesive layer is preferably 10 to 200 ⁇ m, more preferably 30 to 80 ⁇ m.
  • the thickness of the substrate is preferably 1 ⁇ m to 500 ⁇ m, more preferably 5 ⁇ m to 100 ⁇ m, although it depends on the type of substrate.
  • an uncured layer comprising a curable composition containing a silyl group-containing polymer (S) is formed on a substrate, and the surface of the uncured layer on the opposite side of the substrate.
  • the curable composition containing the silyl group-containing polymer (S) has excellent curability, and when it comes into contact with moisture, it cures rapidly and firmly (moisture curing) to obtain a cured product.
  • the wet air curing hydrolyzable silyl group (-SiX a R 3 (3- a)) contributes. It can also be formed by cutting, die cutting or the like after curing of the curable composition.
  • the curing conditions for the curable composition are set as necessary.
  • a curable composition containing a silyl group-containing polymer (S) and a curing catalyst is prepared.
  • a predetermined amount of water is added to this as a curing agent and mixed well.
  • This is coated on a base material to form an uncured layer.
  • it can be cured by heating in an oven or the like and curing at room temperature with the surface of the uncured layer exposed or with a release sheet laminated on the surface. It is also effective to leave it in a humidified environment when curing at room temperature or after curing.
  • the heating by the oven or the like is appropriately set depending on the heat resistance temperature of the base material and the release sheet.
  • the uncured layer When the uncured layer is cured, good adhesion between the cured product (adhesive) and the substrate is obtained, and the exposed surface of the cured product layer or the surface that is in close contact with the release sheet is removable. It becomes the adhesive surface which has.
  • the material of the substrate is not particularly limited.
  • Preferred examples include polyesters such as polyethylene terephthalate (PET); polyolefins such as polyethylene, polypropylene and ethylene-propylene copolymers (block copolymers and random copolymers); halogenated polyolefins such as polyvinyl chloride; Examples include paper such as cardboard; cloth such as woven fabric and nonwoven fabric; metal foil such as aluminum foil.
  • PET polyethylene terephthalate
  • polyolefins such as polyethylene, polypropylene and ethylene-propylene copolymers (block copolymers and random copolymers); halogenated polyolefins such as polyvinyl chloride
  • Examples include paper such as cardboard; cloth such as woven fabric and nonwoven fabric; metal foil such as aluminum foil.
  • These base materials may be used in combination. For example, you may use the laminated body which laminated
  • the bonding surface with the pressure-sensitive adhesive layer of polyesters or papers is difficult to peel off due to the adhesive effect accompanying the curing of the curable composition without performing prior processing.
  • the surface which coats a curable composition when using polyolefin for a base material, it is preferable to process beforehand the surface which coats a curable composition. This is because the peel adhesive strength may be low for an untreated surface.
  • examples of the prior treatment for the surface of the substrate on which the curable composition of the substrate using polyolefins is applied include corona treatment (corona discharge treatment) and primer treatment.
  • the corona treatment is preferable because the treatment is simple and the process can be simplified.
  • ⁇ Peeling sheet> papers that have been surface-treated with a general release agent; the above-mentioned untreated polyolefins: such as those obtained by laminating polyolefins on a base material such as papers, etc., have weak adhesion to the pressure-sensitive adhesive layer. Anything is acceptable.
  • a release sheet is used as the substrate, a pressure-sensitive adhesive body having removability on both front and back surfaces is obtained.
  • the pressure-sensitive adhesive body of the present invention has a low peel strength after curing and good re-peelability as shown in the examples described later. Specifically, the peel adhesive strength is more than 0 N / 25 mm and not more than 8 N / 25 mm, preferably more than 0 N / 25 mm and not more than 1 N / 25 mm, more preferably 0.005 to 0.8 N / 25 mm. A pressure sensitive adhesive body is obtained. It is preferable that the curable composition in the present invention does not contain an additive that increases the tackiness.
  • tan ⁇ In the temperature characteristic of loss tangent (tan ⁇ ) expressed by the ratio of loss elastic modulus to storage elastic modulus (loss elastic modulus / storage elastic modulus), tan ⁇ is 0.1 or more in the temperature range of 0 to 40 ° C. , Have preferable physical properties as a damping material. Damping material converts vibration energy into thermal energy and absorbs vibration. The vibration absorbing capacity of the damping material is generally the ratio of loss elastic modulus to storage elastic modulus (loss elastic modulus / storage elastic modulus). The loss tangent (tan ⁇ ) expressed is an index. As tan ⁇ is larger, vibration energy is more easily converted into heat energy and consumed, and vibration damping by vibration absorption is more likely to be exhibited.
  • tan ⁇ When tan ⁇ is large in a wide temperature range as described above, good vibration damping properties are easily obtained stably even when the vibration damping material is used in various indoor or outdoor temperature conditions.
  • the value of loss tangent (tan ⁇ ) in this specification is obtained by cutting each cured film (thickness: 100 ⁇ m) into a rectangular shape having a length of 20 mm and a width of 10 mm to prepare an evaluation sample, and measuring dynamic viscoelasticity Tan ⁇ was measured in a tensile mode with an apparatus (manufactured by SII, product name: EXSTAR DMS6100). Tan ⁇ was measured at a frequency of 10 Hz in the range of ⁇ 100 to 150 ° C., and the temperature dependency was evaluated.
  • a hydrolyzable silyl group (—SiX a R 3 (3 -A) ), the structural unit derived from the dicarboxylic anhydride (b), the urethane bond, and the urea bond are considered to contribute.
  • the urethane bond is formed by the reaction of an isocyanate group and a hydroxyl group
  • the urea bond is formed by the reaction of an isocyanate group and an amino group.
  • the polyol (Z) has a structural unit derived from the dicarboxylic acid anhydride (b), and the prepolymer (P) and the chain extended polyurethane further have a urethane bond. Further, when a hydrolyzable silyl group is introduced into the polyol (Z), the prepolymer (P) or the chain extended polyurethane, a urethane bond or a urea bond can be introduced into the silyl group-containing polymer (S).
  • the ester bond, urethane bond, and urea bond of the structural unit derived from the dicarboxylic acid anhydride (b) are polar bonds, these are cohesive forces in the silyl group-containing polymer (S), It is considered to act in the direction of increasing the adhesiveness and the adhesion to the adherend.
  • the hydrolyzable silyl group is considered to act in the direction of lowering the adhesiveness of the adhesive to the adherend. And it is thought that slight adhesiveness or low adhesiveness is expressed by these interactions. Further, since the position at which the hydrolyzable silyl group is introduced is the molecular end, the cohesive force can be increased without hindering the molecular motion, and the adhesive force can be stably exhibited.
  • the ratio (MEU / MS molar ratio) of the total amount (MEU) of ester bond, urethane bond and urea bond (MEU) and the amount of hydrolyzable silyl group (MS) in the silyl group-containing polymer (S) is controlled.
  • the MEU / MS molar ratio is preferably in the range of 2/1 to 100/1, and is preferably 2/1 to 90/1. It is more preferable.
  • the MEU / MS molar ratio can be controlled, for example, by adjusting the molecular weight of the polyol (Z), prepolymer (P), or chain extended polyurethane.
  • the cured product (adhesive) obtained by curing the curable composition containing the silyl group-containing polymer (S) exhibits high tan ⁇ is not clear, but has a bent chain derived from dicarboxylic acid anhydride. It is considered that vibration absorption due to heat generation is expressed due to the influence of the substituent derived from the dicarboxylic acid compound.
  • the thickness of the pressure-sensitive adhesive body of the present invention is not particularly limited, but is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and more preferably 30 ⁇ m or more for obtaining good vibration damping properties. Further, from the viewpoint of stability of adhesive strength and economical efficiency, it is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, and further preferably 80 ⁇ m or less.
  • the pressure-sensitive adhesive body of the present invention has good heat resistance and removability, has good vibration damping properties, and provides impact resistance.
  • protective sheets for electronic materials such as electronic substrates and IC chips
  • protective sheets for optical members such as polarizing plates, light diffusing plates, light diffusing sheets, prism sheets
  • protective sheets for various displays protective sheets for automobiles
  • Surface protective film for plate material such as metal plate, coated steel plate, synthetic resin plate, decorative plywood, heat reflection glass.
  • the vibration damping property can be imparted to these protective sheet, protective tape, and surface protective material, impact resistance can be obtained.
  • Zinc hexacyanocobaltate (hereinafter referred to as TBA-DMC catalyst) having tert-butyl alcohol as an organic ligand was produced by the following method.
  • the polyol X in this example is a polyol having a number average molecular weight (Mn) of 1000 obtained by addition polymerization of propylene oxide to dipropylene glycol.
  • an aqueous solution consisting of 10.2 g of zinc chloride and 10 g of water was placed in a 500 ml flask, and while maintaining the aqueous solution at 40 ° C., stirring at 300 rpm (300 rpm), 4.2 g An aqueous solution composed of potassium hexacyanocobaltate (K 3 [Co (CN)] 6 ) and 75 g of water was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred for 30 minutes.
  • K 3 [Co (CN)] 6 potassium hexacyanocobaltate
  • EGMTBE ethylene glycol mono-tert-butyl ether
  • TBA tert-butyl alcohol
  • polyol X polyol X
  • Example 1 A silyl group-containing polymer (S3-1) of the third embodiment was prepared under the production conditions shown in Table 1.
  • the initiator (a1) is a polyoxypropylene having a hydroxyl value of 160.3 mgKOH / g and a molecular weight of 700 produced by reacting propylene glycol with propylene oxide (hereinafter sometimes referred to as PO) using a KOH catalyst. Diol was used.
  • a mixture having a molar ratio of propylene oxide and phthalic anhydride (PO / phthalic anhydride) of 75/25 as an initiator (a1) is subjected to ring-opening polymerization in the presence of the TBA-DMC catalyst obtained in Reference Production Example 1.
  • a polyester ether polyol (Z1) having a content of 36% by mass and a content of structural units derived from phthalic anhydride of 30% by mass was obtained.
  • polyester ether polyol (Z1) obtained above in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, and 2,4 as the polyisocyanate (B).
  • TDI-100 tolylene diisocyanate
  • DBTDL dibutyltin dilaurate
  • polyester ether polyol (Z1) And TDI-100 were charged in an amount corresponding to 25 ppm.
  • the isocyanate index in the charged amount was 150. Subsequently, the temperature was gradually raised to 85 ° C., and a prepolymer formation reaction was performed for 3 hours to obtain an isocyanate group-terminated prepolymer (PI-1).
  • PI-1 the isocyanate group content
  • NCO% the isocyanate group content
  • the obtained curable composition was applied onto a PET film (base material) having a thickness of 100 ⁇ m so that the film thickness after drying was 5 ⁇ m, 15 ⁇ m, 25 ⁇ m, and 50 ⁇ m, respectively, and 100 ° C. in a circulation oven. For 3 minutes. And it cured for one week at 23 degreeC and 50% of relative humidity, and formed the adhesion body layer.
  • four types of pressure-sensitive adhesive sheets having different pressure-sensitive adhesive layer thicknesses were obtained.
  • Table 1 also shows the measurement results of peel strength when the thickness of the pressure-sensitive adhesive layer is 15 ⁇ m. The smaller this value, the lower the adhesive strength, the easier it is to peel off, and the better the removability.
  • the value of the peel strength after 30 minutes at room temperature corresponds to the “peel strength” in the present invention.
  • Table 2 also shows the ratio of the peel strength after 3 weeks at 60 ° C. (after 3 weeks / 30 minutes), based on the peel strength after 30 minutes. A larger value indicates a greater increase in adhesive strength with time.
  • Tan ⁇ was measured at a frequency of 10 Hz in the range of ⁇ 100 to 150 ° C., and the temperature dependency was evaluated. The result is shown in FIG.
  • the left vertical axis represents storage elastic modulus (E ′, unit: Pa) and loss elastic modulus (E ′′, unit: Pa)
  • the right vertical axis represents loss tangent (tan ⁇ )
  • the horizontal axis Represents the measured temperature (unit: ° C).
  • the pressure-sensitive adhesive obtained by curing the silyl group-containing polymer (S3-1) of Example 1 has a large tan ⁇ value around room temperature, and is good at around room temperature. It can be seen that it has excellent damping properties.
  • the peak temperature and peak value of tan ⁇ are shown in Table 1.
  • Example 2 In Example 1, the production conditions were changed as shown in Table 1 to synthesize a silyl group-containing polymer, and a curable composition and a pressure-sensitive adhesive were produced using the same (hereinafter the same). In this example, the silyl group-containing polymer (S2-1) of the second embodiment is used.
  • the other polyol used in combination with the polyester ether polyol (Z1) was produced by reacting propylene oxide with propylene glycol as an initiator and using a KOH catalyst, having a hydroxyl value of 56.2 mgKOH / g, a molecular weight of 2, 000 polyoxypropylene diol is used.
  • the temperature was gradually raised to 85 ° C., and a prepolymer formation reaction was performed for 3 hours to obtain an isocyanate group-terminated prepolymer (PI-2).
  • PI-2 isocyanate group-terminated prepolymer
  • the NCO% was 1.14% by mass.
  • Example 3 [Production of isocyanate group-terminated prepolymer (P2-2)]
  • the other polyol used in combination with the polyester ether polyol (Z1) was produced by reacting propylene oxide using propylene glycol as an initiator and a KOH catalyst, and having a hydroxyl value of 16.3 mgKOH / g and a molecular weight of 7000. Polyoxypropylene diol is used.
  • the temperature was gradually raised to 85 ° C., and a prepolymer formation reaction was performed for 3 hours to obtain an isocyanate group-terminated prepolymer (PI-2).
  • PI-2 isocyanate group-terminated prepolymer
  • the NCO% was 0.46% by mass.
  • Example 4 the silyl group-containing polymer (S1-1) of the first embodiment is used.
  • the initiator (a2) polyoxypropylene diol having a hydroxyl value of 112 mgKOH / g and a molecular weight of 1000, produced by reacting propylene glycol with PO using a KOH catalyst, was used.
  • a mixture having a molar ratio of propylene oxide and phthalic anhydride (PO / phthalic anhydride) of 79/21 as an initiator (a2) is subjected to ring-opening polymerization in the presence of the TBA-DMC catalyst obtained in Reference Production Example 1.
  • a mixture of propylene oxide and phthalic anhydride in a molar ratio (PO / phthalic anhydride) 91/9 was subjected to ring-opening polymerization in the presence of the TBA-DMC catalyst obtained in Reference Production Example 1, and a hydroxyl value of 17.3 mgKOH / G, (hydroxyl value converted molecular weight 6474), average molecular weight per copolymer chain (M ′) 2737, acid value 0.11 mg KOH / g, polyester ether polyol having a structural unit content of 20% by mass derived from phthalic anhydride ( Z2) was obtained.
  • a silyl group-containing polymer having no ester bond, urethane bond, or urea bond was used.
  • a mixture of 200 g of 5000 polyoxypropylene triol (hereinafter referred to as triol B) was used as an initiator, and in the presence of 1.2 g of zinc hexacyanocobaltate-glyme complex catalyst, 2480 g of PO was gradually added to the reaction vessel.
  • the polymerization reaction was carried out under the condition of 120 ° C., and after the total amount of PO was added, the reaction was continued until the internal pressure of the reaction vessel was not lowered.
  • the zinc hexacyanocobaltate-glyme complex catalyst can be produced using glyme in place of EGMTBE and TBA in Reference Production Example 1. Subsequently, 120 g of diol A and 200 g of triol B were charged into the reaction vessel, and after 1680 g of PO was added little by little in the same manner as described above, the reaction was continued until the internal pressure of the reaction vessel did not decrease.
  • the pressure-sensitive adhesive body of the present invention is useful for producing a pressure-sensitive adhesive sheet having a low pressure-sensitive adhesive force.
  • the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2009-0665106 filed on March 17, 2009 are cited here as disclosure of the specification of the present invention. Incorporated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyethers (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesive Tapes (AREA)

Abstract

L'invention porte sur une matière adhésive qui a une excellente aptitude au retrait et une bonne résistance à la chaleur, et dont l'aptitude au retrait est moins susceptible d'être réduite au cours du temps aux températures supérieures. La matière adhésive est caractérisée par le fait qu'elle est obtenue par durcissement d'une composition durcissable contenant un polymère (S) à teneur en groupes silyle qui a une unité constitutive provenant d'un amorceur (a) qui a au moins deux groupes à hydrogène actif par molécule, une unité constitutive provenant d'un acide dicarboxylique anhydre (b) et une unité constitutive provenant d'un oxyde d'alkylène (c) et qui a également un groupe silyle hydrolysable à l'extrémité terminale de sa molécule.
PCT/JP2010/054371 2009-03-17 2010-03-15 Matière adhésive WO2010107006A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010242070A (ja) * 2009-03-17 2010-10-28 Asahi Glass Co Ltd 硬化性組成物
JP2016203533A (ja) * 2015-04-24 2016-12-08 マツダ株式会社 樹脂部材およびこの部材を備えた車体構造
CN111684034A (zh) * 2018-02-07 2020-09-18 3M创新有限公司 用于光投影的可热拉伸的装饰性膜和其所粘结的制品

Families Citing this family (1)

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KR102442964B1 (ko) * 2016-08-09 2022-09-14 코베스트로 도이칠란트 아게 실란-관능성 중합체성 폴리우레탄

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WO2007040232A1 (fr) * 2005-10-05 2007-04-12 Asahi Glass Company, Limited Polymère contenant un groupe silyle et son procédé de production
JP2008143994A (ja) * 2006-12-08 2008-06-26 Toyo Ink Mfg Co Ltd 感圧式接着剤組成物
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JP2008202014A (ja) * 2007-02-23 2008-09-04 Toyo Ink Mfg Co Ltd 感圧式接着剤組成物
WO2010013653A1 (fr) * 2008-07-28 2010-02-04 旭硝子株式会社 Matière adhésive, feuille adhésive sensible à la pression et leur utilisation
WO2010026995A1 (fr) * 2008-09-05 2010-03-11 旭硝子株式会社 Matériau adhésif, feuille adhésive et utilisation associée
WO2010041667A1 (fr) * 2008-10-08 2010-04-15 旭硝子株式会社 Stratifié adhésif
JP2010100836A (ja) * 2008-09-26 2010-05-06 Asahi Glass Co Ltd 粘着体および粘着シート
JP2010100835A (ja) * 2008-09-26 2010-05-06 Asahi Glass Co Ltd 粘着体および粘着シート

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JPS53139695A (en) * 1977-05-12 1978-12-06 Kanegafuchi Chem Ind Co Ltd Production of cold curable silicon-containing polymer
JPS546096A (en) * 1977-06-15 1979-01-17 Kanegafuchi Chem Ind Co Ltd Preparation of silyl-terminated polymer
JPS54156099A (en) * 1978-05-31 1979-12-08 Kanegafuchi Chem Ind Co Ltd New curable polyester oligomer and its preparation
JP2000169759A (ja) * 1998-12-11 2000-06-20 Kanegafuchi Chem Ind Co Ltd 新規なポリエステル系粉体塗料用樹脂組成物
WO2007040232A1 (fr) * 2005-10-05 2007-04-12 Asahi Glass Company, Limited Polymère contenant un groupe silyle et son procédé de production
JP2008143995A (ja) * 2006-12-08 2008-06-26 Toyo Ink Mfg Co Ltd 感圧式接着剤組成物
JP2008143994A (ja) * 2006-12-08 2008-06-26 Toyo Ink Mfg Co Ltd 感圧式接着剤組成物
WO2008102576A1 (fr) * 2007-02-22 2008-08-28 Mitsui Chemicals, Inc. Résine contenant de l'alcoxysilane, résine contenant de l'alcoxysilane modifiée, leurs procédés de fabrication, adhésif thermofusible et produit durci à base de résine
JP2008202015A (ja) * 2007-02-23 2008-09-04 Toyo Ink Mfg Co Ltd 感圧式接着剤組成物
JP2008202014A (ja) * 2007-02-23 2008-09-04 Toyo Ink Mfg Co Ltd 感圧式接着剤組成物
WO2010013653A1 (fr) * 2008-07-28 2010-02-04 旭硝子株式会社 Matière adhésive, feuille adhésive sensible à la pression et leur utilisation
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JP2010100836A (ja) * 2008-09-26 2010-05-06 Asahi Glass Co Ltd 粘着体および粘着シート
JP2010100835A (ja) * 2008-09-26 2010-05-06 Asahi Glass Co Ltd 粘着体および粘着シート
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010242070A (ja) * 2009-03-17 2010-10-28 Asahi Glass Co Ltd 硬化性組成物
JP2016203533A (ja) * 2015-04-24 2016-12-08 マツダ株式会社 樹脂部材およびこの部材を備えた車体構造
CN111684034A (zh) * 2018-02-07 2020-09-18 3M创新有限公司 用于光投影的可热拉伸的装饰性膜和其所粘结的制品
CN111684034B (zh) * 2018-02-07 2022-06-14 3M创新有限公司 用于光投影的可热拉伸的装饰性膜和其所粘结的制品

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