WO2006134997A1 - Agent pour stratifies de type agent contenu dans un emballage unique - Google Patents

Agent pour stratifies de type agent contenu dans un emballage unique Download PDF

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Publication number
WO2006134997A1
WO2006134997A1 PCT/JP2006/312010 JP2006312010W WO2006134997A1 WO 2006134997 A1 WO2006134997 A1 WO 2006134997A1 JP 2006312010 W JP2006312010 W JP 2006312010W WO 2006134997 A1 WO2006134997 A1 WO 2006134997A1
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Prior art keywords
curable composition
group
adherend
weight
polymer
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PCT/JP2006/312010
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English (en)
Japanese (ja)
Inventor
Toyohisa Fujimoto
Katsuhiro Ando
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Kaneka Corporation
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Priority to JP2007521336A priority Critical patent/JP5021471B2/ja
Publication of WO2006134997A1 publication Critical patent/WO2006134997A1/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
    • C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
    • C09J143/04—Homopolymers or copolymers of monomers containing silicon

Definitions

  • the present invention relates to a method for forming a releasable pressure-sensitive adhesive that can be widely used in construction sites and the like, and a method for bonding adherends.
  • An object of the present invention is to simplify the handling of the pressure-sensitive adhesive by directly forming a pressure-sensitive adhesive that does not require a solvent drying process at a construction site such as a building, and to adhere to an object such as a reform after use. It is to provide a method for facilitating peeling.
  • the present invention comprises (A) 20 to 100 parts by weight of (B) a tackifying resin with respect to 100 parts by weight of a bulle polymer having at least one crosslinkable silyl group capable of forming a siloxane bond. And (C) a one-component bonding agent comprising a curable composition containing 0.05 to 10 parts by weight of a curing catalyst with respect to 100 parts by weight of the total amount of components (A) and (B),
  • the present invention relates to a one-component bonding agent characterized in that a curable composition is filled in an airtight container.
  • the viscosity of the curable composition is preferably 3 to 50 Pa's / 80 ° C.
  • the curable composition after coating is preferably a curable composition that can be cured within 90 minutes after coating to form an adhesive layer.
  • the main chain of the bull polymer (A) is selected from the group consisting of a (meth) acrylic monomer, an acrylonitrile monomer, an aromatic bull monomer, a fluorine-containing bull monomer, and a silicon-containing bull monomer. It is preferable that the monomer to be polymerized by the living radical polymerization method.
  • crosslinkable silyl group of the bull polymer (A) is at the molecular end of the polymer.
  • crosslinkable silyl group of the bull polymer (A) is present only at the molecular end of the polymer.
  • the molecular weight distribution of the bull polymer (A) is less than 1.8.
  • the curable composition preferably contains 0.:! To 50 parts by weight of (D) a solvent with respect to 100 parts by weight of the bull polymer (A).
  • the total weight of the sealed container filled with the curable composition is preferably 10 kg or less.
  • the one-component bonding agent of the present invention for on-site coating.
  • the present invention is a method for laminating a pair of adherends, the step of applying the curable composition filled in the sealed container to one adherend, and the curing proceeded.
  • the present invention also relates to a method for bonding an adherend including a step of bonding the other adherend to a semi-cured or cured curable composition.
  • the curable composition is discharged from the sealed container onto the adherend, and a coating film of the curable composition having a thickness of 30 xm to 3 mm is directly formed on the adherend.
  • the closed container filled with the curable composition is heated to control the temperature of the curable composition at the time of discharge.
  • 40- It is preferable to set it as 140 degreeC.
  • the sealed container is a cartridge can, and the cartridge can filled with the curable composition is heated in a heating cylinder having a hollow cylindrical heater member in a state where the cartridge can is accommodated in an extrusion gun.
  • the adherend is preferably an interior material.
  • the sealed container used in the present invention can be used without particular limitation as long as it can coat the filling agent filled with low moisture permeability from the coating outlet.
  • cartridges and tubes are preferred from the standpoints of availability and workability. Since the content of the sealed container tends to be difficult if it is too large, 10 kg or less is preferred when filled with the curable composition, 5 kg or less is more preferred, and 3 kg or less is more preferred. 1 kg or less is particularly preferable. On the other hand, if the amount is too small, work efficiency tends to decrease, so 0.1 kg or more is preferable. If it is less than that, for example about lg, it is practical enough for DIY.
  • the viscosity of the curable composition used in the present invention is preferably 3 to 50 Pa′sZ80 ° C. 5 to 30 Pa ′s / 80. Force C is more preferable than S, 5 to 20 Pa′sZ80. More preferably, it is C.
  • the temperature of the curable composition is preferably in the above range from the viewpoint of ensuring workability. The viscosity was measured at 80 ° C using an E-type viscometer (3 ° X R14 cone).
  • the curable composition used in the present invention is gradually cured by the hydrolysis and condensation of the polymer having reactive cage groups by moisture in the air.
  • Adhesive strength begins to develop when curing progresses to some extent, and when the adherend is bonded and cured at this point, the cured product functions as an adhesive or permanent adhesive, and both the base material and the adherend are bonded. Good adhesion.
  • the stage at which this adhesive strength began to develop is that the composition has not yet fully cured.
  • the state in which the composition is attached to the finger by finger touch or the like is defined as “semi-cured state” in the claims and the specification of the present application.
  • the composition functions as a peelable adhesive, and the adherend is bonded together. Even after this, the adherend can be easily peeled off and the position can be adjusted again.
  • the stage where the composition no longer adhered to the finger was defined as “cured state” in the claims and specification of the present application. Note that the adhesive generally exhibits peelability, but in the present invention, in order to clarify the difference between the adhesive and the permanent adhesive that does not exhibit cohesive failure after use and the permanent adhesive, Was used.
  • the curable composition used in the present invention is preferably cured within 90 minutes after coating to form an adhesive layer, more preferably within 60 minutes, and even more preferably 30 minutes. If the curing is faster than 3 minutes, the base material tends to be insufficiently wet and sufficient adhesiveness tends not to be secured. If the pressure-sensitive adhesive layer is formed after 90 minutes, it is not preferable from the viewpoint of workability.
  • the bull monomers constituting the main chain of the bull polymer (A) used in the present invention are not particularly limited, and various monomers can be used.
  • —Aromatic vinyl monomers such as methylstyrene, chlorostyrene, styrenesulfonic acid and their salts; Fluorine-containing butyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; butyltrimethoxysilane, Silicon-containing butyl monomers such as butyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid, and diolenoquinesthenoles; maleimide, methyl Males such as Nore maleimide, Ethenore maleimide, Propyl maleimide, Butyl maleimide, Hexyl maleimide, Octyl maleimide, Dodecyl maleimide, Stearyl maleimide, Phenyl maleimide, Cyclohexyl maleimide Amide monomers; Ac
  • Main chain strength of bull polymer (A) selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic bull monomers, fluorine-containing bull monomers and kale-containing bull monomers It is preferable that it is produced mainly by polymerizing at least one monomer.
  • "mainly” is 50 mole 0/0 or more of the monomer units constituting Bulle based polymer (A) is meant to be the monomer, more is possible 70 or more Monore% is the monomer preferable.
  • acrylic ester monomers and methacrylic ester monomers which are preferred to styrene monomers and (meth) atanolic acid monomers, from the physical properties of the product, etc.
  • Particularly preferred is butyl acrylate, which is more preferred by acrylate monomers, which are more preferred by mer.
  • these preferable monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, these preferable monomers are preferably contained in a weight ratio of 40% or more.
  • (meth) acrylic acid represents acrylic acid and / or methacrylic acid.
  • the glass transition temperature of the bull polymer (A) is lower than room temperature or use temperature in order to develop excellent adhesive properties.
  • the molecular weight distribution of the vinyl polymer (A) used in the present invention that is, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) ( Mw / Mn) is not particularly limited, but is preferably less than 1.8, 1.6 or less, and more preferably 1.3 or less.
  • GPC gel permeation chromatography
  • the measurement is performed with a polystyrene gel column, and the number average molecular weight can be determined in terms of polystyrene.
  • the number average molecular weight of the vinyl polymer (A) used in the present invention is not particularly limited. However, when measured by GPC, the range force S is preferably 500 to 1,000,000, preferably 5,000 to 50, 000 power is better than S.
  • the number average molecular weight being in the above range is preferable from the viewpoint of ensuring workability and exhibiting adhesive properties.
  • the method for synthesizing the bulle polymer (A) used in the present invention is more preferably an atom transfer radical polymerization method, which is preferably a living radical polymerization method among the controlled radical polymerization methods. These are described below.
  • the radical polymerization method is a “general radical polymerization method (free radical polymerization) in which a monomer having a specific functional group and a bure monomer are simply copolymerized using an azo compound or peroxide as a polymerization initiator. Polymerization method) ”and“ controlled radical polymerization method ”in which a specific functional group can be introduced at a controlled position such as a terminal.
  • the "general radical polymerization method” is a simple method, but in this method, a monomer having a specific functional group is introduced into the polymer only in a probabilistic manner, so that the functionalization rate is high. When trying to obtain polymer, it is necessary to use a very large amount of this monomer. In use, there is a problem S that the proportion of the polymer in which this specific functional group is not introduced increases. In addition, since it is a free radical polymerization method, only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.
  • Controlled radical polymerization method is a "chain transfer agent method” in which a vinyl polymer having a functional group at the terminal is obtained by polymerization using a chain transfer agent having a specific functional group. It can be classified as “living radical polymerization method” in which a polymer with a molecular weight almost as designed can be obtained by growing the polymerization growth terminal without causing a termination reaction.
  • the "chain transfer agent method” is capable of obtaining a polymer with a high functionalization rate, but requires a considerably large amount of a chain transfer agent having a specific functional group with respect to the initiator. There are also economic problems including Further, like the above-mentioned “general radical polymerization method”, there is a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained because it is a free radical polymerization method.
  • the "living radical polymerization method” is a radical polymerization that is difficult to control because it tends to cause a termination reaction due to coupling between the radicals where the polymerization rate is high.
  • a polymer with a narrow molecular weight distribution (Mw / Mn is about 1.:! To 1.5), which is difficult to cause a termination reaction, can be obtained, and the molecular weight can be controlled freely according to the monomer to initiator charge ratio. Can do.
  • the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and introduces a monomer having a specific functional group at almost any position of the polymer. Therefore, it is more preferable as a method for producing a bulle polymer having the specific functional group.
  • living polymerization refers to polymerization where the terminal always has activity and the molecular chain grows, but generally, the terminal is inactive and inactive. This includes quasi-living polymerization that grows while the product is in an equilibrium state.
  • the definition in the present invention is also the latter.
  • Examples include, for example, Journal of American Chemical Society, J. Am. Chem. So, 1994, 116 ⁇ , p. 7943 (cononole-ponofilin complex as shown here).
  • a radical scavenger such as a nitroxide compound as shown in Macromolecules, 1994, pages 27, 7228
  • transition metal complexes using organic halogenated compounds as initiators And "Atom Transfer Radical Polymerization (ATRP) ATRP
  • the "atom transfer radical polymerization method” for polymerizing bulle monomers using an organic halide or a halogenated sulfone dirich compound as an initiator and a transition metal complex as a catalyst is the above-mentioned
  • it has a halogen atom, which is relatively advantageous for functional group conversion reactions, and has a large degree of freedom in designing initiators and catalysts.
  • a method for producing a vinyl-based polymer it is more preferable.
  • the living radical polymerization method will be described in detail below. Before that, one of the controlled radical polymerizations that can be used for the production of vinyl polymers described later, a chain transfer agent is used. The polymerization used will be described.
  • the radical polymerization using a chain transfer agent (telomer) is not particularly limited, but the following two methods are exemplified as methods for obtaining a vinyl polymer having a terminal structure suitable for the present invention.
  • a radical cabbing agent such as a nitroxide compound
  • examples of such compounds include, but are not limited to, 2, 2, 6, 6-substituted 1-piperidinylone xylazy, and 2, 2, 5, 5-substituted 1-pyridinyloxy radicals.
  • Nitroxy free radicals from cyclic hydroxyamines are preferred.
  • an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable.
  • nitroxy free radical compounds include, but are not limited to, 2, 2, 6, 6 tetramethyl mono 1-piperidinyloxy radical (TEMPO), 2, 2, 6, 6 — tetraethyl mono 1-piperidinyloxy radical, 2, 2, 6, 6-tetramethyl-1-4-oxo 1-piperidinyloxy radical, 2, 2, 5, 5-tetramethyl _ 1 _pyrrolidinyloxy radical, 1, 1, 3, 3-tetramethyl-2-isoindolinyloxy radical, N, N tert-butylamineoxy radical and the like.
  • TEMPO 2, 2, 6, 6 tetramethyl mono 1-piperidinyloxy radical
  • 2, 6, 6 — tetraethyl mono 1-piperidinyloxy radical 2, 2, 6, 6-tetramethyl-1-4-oxo 1-piperidinyloxy radical
  • 2, 2, 5, 5-tetramethyl _ 1 _pyrrolidinyloxy radical 1, 1, 3, 3-tetramethyl-2-isoindolinyloxy radical
  • the radical cabbing agent is used in combination with a radical generator. It is considered that the polymerization product of the addition polymerizable monomer proceeds with the reaction product of the radical cabbing agent and the radical generator as a polymerization initiator.
  • the combination ratio of both is not particularly limited, but is preferably 0 to! To 10 mol of the radical generator with respect to 1 mol of the radical cabbing agent.
  • a peroxide capable of generating a radical under the polymerization temperature condition is preferable.
  • the peroxide includes, but is not limited to, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide, di_t_butyl peroxide, and diisopropyl peroxide dicarbonate.
  • Peroxycarbonates such as bis (4_t-butylcyclohexyl) peroxydicarbonate, and alkyl peresters such as t-butyl benzoate and t_butylperoxybenzoate.
  • benzoyl peroxide is particularly preferable.
  • a radical generator such as a radical-generating azo compound such as azobisisobutyronitrile can be used in place of the oxide.
  • an alkoxyamine such as Use the compound as an initiator.
  • an alkoxyamine compound When used as an initiator, if it has a functional group such as a hydroxyl group as shown in the above formula, a polymer having a functional group at the terminal can be obtained. When this is used in the method of the present invention, a polymer having a functional group at the terminal can be obtained. Moreover, the polymer which has a functional group only at the terminal is obtained.
  • the polymerization conditions such as the monomer, the solvent, and the polymerization temperature used in the polymerization using a radical scavenger such as the above nitroxide compound are not limited, but are the same as those used for the atom transfer radical polymerization method described below. It's okay.
  • an organic halide particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the ⁇ -position or a compound having a halogen at the benzyl-position).
  • a sulfonyl halide compound or the like can be used as an initiator.
  • R 2 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryleno group, or an aralkyl group, and X is a chlorine atom, a bromine atom, or an iodine atom
  • R 1 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group
  • X is a chlorine atom, a bromine atom, or an iodine atom
  • an initiator for the atom transfer radical polymerization method an organic halide or a halogenated sulfone compound having a functional group other than the functional group for initiating polymerization can also be used.
  • a vinyl polymer having a functional group at one end of the main chain and a growth terminal structure of atom transfer radical polymerization at the other main chain end is produced.
  • a functional group include an alkenyl group, a crosslinkable silyl group, a hydroxyl group, an epoxy group, an amino group, and an amide group.
  • the organic halide having an alkenyl group is not limited, and examples thereof include those having a structure represented by the general formula (1).
  • R 3 is a hydrogen atom or a methyl group
  • R 4 and R 5 are a hydrogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms, an aryleno group, or an aralkyl group, or Concatenated
  • R 6 is — C ( ⁇ ) ⁇ — (ester group), — C ( ⁇ ) — (keto group), or o—, m—, p-phenylene group
  • R 7 is a direct bond, or It is a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds.
  • X is a chlorine atom, bromine atom or iodine atom
  • R 4 and R 5 include a hydrogen atom, a methyl group, an ethyl group, an n_propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexynole group.
  • R 4 and R 5 are other
  • X is a chlorine atom, bromine atom, or iodine atom
  • n is an integer from 0 to 20
  • m is an integer from:! To 20
  • H -O- (CH) -CH CH, o, m, p-CH CH C (H) (X) _C H _0_ (CH
  • X is a chlorine atom, bromine atom, or iodine atom
  • n is an integer of 0 to 20
  • X is a chlorine atom, bromine atom, or iodine atom
  • n is an integer from 1 to 20
  • m is an integer from:! To 20
  • Examples of the organic halide having an alkenyl group further include compounds represented by the general formula (2).
  • R 8 is a direct bond, C (0) 0— (ester group), C (O) ( Keto group) or o-, m-, p-phenylene groups)
  • R 7 is a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds.
  • R 7 is a carbon to which a halogen is bonded.
  • a bully group is bonded to the element, which is a halogenated compound.
  • R 8 may be one C (O) O (ester group), one C (O) (keto group), a phenyl group. Is preferred.
  • H CH (CH) C (H) (X)-COR 9
  • CH CH (CH) C (H) (X)-COR 9
  • CH CH (CH) C (H) (X)-COR 9
  • CH CHCH C (H) (X) _CH
  • CH CH (CH) C (H) (X) _C H
  • CH CH (C
  • X is a chlorine atom, bromine atom, or iodine atom
  • R 9 is an arolequinol group, an aryl group, an aralkyl group having 1 to 20 carbon atoms
  • X is a chlorine atom, bromine atom, or iodine atom
  • n is an integer of 0 to 20
  • the organic halide having a crosslinkable silyl group is not particularly limited, and examples thereof include those having a structure represented by the general formula (3).
  • R 1Q and R 11 are all an alkenoquinole group having 1 to 20 carbon atoms, carbon number A 6-20 aralkyl group, a 7-20 carbon aralkyl group, or (R ') Si0_ (R' is a monovalent hydrocarbon group having 1-20 carbon atoms, and three R ' They may be the same or different), and when two or more R 1Q or R 11 are present, they may be the same or different.
  • Y represents a hydroxyl group or a hydrolyzable group, and when there are more than three groups, they may be the same or different, a is 1, 2 or 3, and b Indicates 0, 1 or 2. 1 indicates It is an integer from 0 to 19. However, it shall be satisfied that a + lb ⁇ l. ) If the compound of the general formula (3) is specifically exemplified,
  • X is a chlorine atom, bromine atom, iodine atom, and n is an integer of 0 to 20) XCH C (O) O (CH) O (CH) Si (OCH), H CC (H) ( X) C (O) O (CH) O (CH)
  • X is a chlorine atom, bromine atom, iodine atom, n is an integer of 1-20, m is an integer of:!-20
  • X is a chlorine atom, a bromine atom, or an iodine atom
  • Examples of the organic halide having the crosslinkable silyl group further include those having a structure represented by the general formula (4).
  • R 3 , R 4 , R 5 , R 7 , X are the same as in general formula (1), R 8 is the same as in general formula (2), R 10 , R u , a, b, 1, Y Is the same as in general formula (3))
  • X is a chlorine atom, bromine atom, or iodine atom
  • R 9 is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group
  • the organic halide having a hydroxyl group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
  • X is a chlorine atom, bromine atom, or iodine atom
  • R 1 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group
  • m is an integer of:!
  • the organic halide having an amino group or the halogenosulfonyl compound is not particularly limited, and examples thereof include the following.
  • X is a chlorine atom, bromine atom, or iodine atom
  • R 1 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group
  • m is an integer of:!
  • the organic halide having the epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
  • X is a chlorine atom, bromine atom, or iodine atom
  • R is a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group
  • n is an integer of 1 to 20
  • Growth terminal structure In order to obtain a polymer having two or more in one molecule, it is preferable to use an organic halide having two or more starting points or a sulfonyl halide compound as an initiator.
  • an organic halide having two or more starting points or a sulfonyl halide compound as an initiator.
  • R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and n is 0 to 2 (An integer of 0, X is a chlorine, bromine, or iodine atom)
  • the transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably a transition metal complex having a central metal of Group 7, 8, 9, 10, or 11 of the periodic table. is there. Further preferred are complexes having a central metal of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel. Of these, copper complexes are preferred. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide and cuprous perchlorate. is there.
  • a ligand is added.
  • a preferred ligand is a nitrogen-containing compound, a more preferred ligand is a chelate-type nitrogen-containing compound, and a more preferred ligand is N, N, ⁇ ', ⁇ ", ⁇ " —pentamethyl Tylenetriamine.
  • a tristriphenylphosphine complex of divalent ruthenium chloride (RuCl (PPh)) is also suitable as a catalyst.
  • RuCl (PPh) divalent ruthenium chloride
  • aluminum alkoxides are added as an activator.
  • divalent iron bistriphenylphosphine complex FeCl (PPh)
  • divalent nickel bistriphenylphosphine complex NiCl (PPh)
  • NiBr (PBu) divalent nickel pistribyl phosphine complex.
  • solvents include hydrocarbon solvents such as benzene and toluene, ether solvents such as jetyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform, aceton and methyl ethyl ketone.
  • Ketone solvents such as methyl isobutyl ketone, methanol solvents, alcohol solvents such as ethanol, propanol, isopropanol, n butyl alcohol, t butyl alcohol, nitrile solvents such as acetonitrile, propionitryl, benzonitrile, ethyl acetate, acetic acid
  • ester solvents such as butyl
  • carbonate solvents such as ethylene carbonate and propylene carbonate.
  • the polymerization can be carried out in the range of 0 to 200 ° C, preferably 50 to 150 ° C.
  • the atom transfer radical polymerization method of the present invention includes a so-called reverse atom transfer radical polymerization method.
  • the reverse atom transfer radical polymerization method is a high oxidation state when a normal atom transfer radical polymerization catalyst generates a radical, for example, Cu (II ') when Cu (I) is used as a catalyst.
  • This is a method in which a general radical initiator such as an oxide is allowed to act, and as a result, an equilibrium state similar to that of the atom transfer radical polymerization method is created (see Macromolecules, 1999, 32 ⁇ , pages 2872). .
  • the vinyl polymer (A) has at least one crosslinkable silyl group. Also, From the viewpoint of curability and adhesive properties of the composition, the number of crosslinkable silyl groups is preferably 1. 1 or more and 4.0 or less, more preferably 1. 2 or more and 3.0 or less.
  • the cured product obtained by curing the curable composition used in the present invention is particularly required to have rubber-like properties, the molecular weight between crosslinking points that greatly affects the adhesive properties can be increased.
  • At least one silyl group is preferably at the end of the main chain (molecular chain). More preferably, it has all the crosslinkable functional groups at the end of the main chain.
  • a method for producing a vinyl polymer (A) having at least one crosslinkable silyl group at its molecular end, and among them a (meth) acrylic polymer is disclosed in Japanese Patent Publication No. 3-14068, 4_55444, JP-A-6-211922, and the like.
  • these methods are free radical polymerization methods using the above “chain transfer agent method”
  • the resulting polymer has a relatively high proportion of crosslinkable functional groups at the molecular chain ends.
  • the molecular weight distribution expressed by M w / Mn is generally larger than 2 and the viscosity is high.
  • the above “living radical polymerization method” is used. I prefer it.
  • the crosslinkable silyl group of the bull polymer (A) used in the present invention is represented by the general formula (5):-[Si (R 10 ) (Y) 0] l-Si (R n ) (Y) ( Five)
  • hydrolyzable group examples include commonly used groups such as a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. can give. Among these, an alkoxy group, an amide group, and an aminooxy group are preferable, but among these, an alkoxy group is particularly preferable because of its mild hydrolyzability and easy handling.
  • a hydrolyzable group or a hydroxyl group can be bonded to one key atom in a range of! To 3; (a + ⁇ b) is preferably in a range of 1 to 5.
  • crosslinkable silinore group When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silinore group, they may be the same or different.
  • the number of key atoms forming a crosslinkable silyl group is one or more. In the case of key atoms linked by a siloxane bond or the like, the number is preferably 20 or less.
  • the general formula (6) is one or more. In the case of key atoms linked by a siloxane bond or the like.
  • the crosslinkable silyl group is preferable because it is easily available.
  • a is preferably 2 or more in consideration of curability. Further, it is preferable to use a compound having a force S3 (for example, a trimethoxy functional group) and two compounds (for example, a dimethoxy functional group) in view of excellent storage stability, curability and adhesive properties.
  • a force S3 for example, a trimethoxy functional group
  • two compounds for example, a dimethoxy functional group
  • the ability to explain the method for introducing a silyl group into the vinyl polymer (A) used in the present invention is not limited to the following.
  • (C) a method of reacting a compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule when a vinyl polymer is synthesized by radical polymerization.
  • the bur polymer having at least one alkenyl group used in the method (A) can be obtained by various methods. Examples of synthesis methods are shown below, but are not limited thereto. [0087] (AA) When synthesizing a bull polymer by radical polymerization, for example, a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule as shown in the following general formula (7): A method in which a compound having a dil group is reacted as a second monomer.
  • R 14 represents a hydrogen atom or a methyl group
  • R 15 represents —C ( ⁇ ) 0— (ester group), or o—, m—, p-phenylene group
  • R 16 represents a direct bond, Or a divalent organic group having 1 to 20 carbon atoms, which may contain one or more ether bonds
  • R 17 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms; A aralkyl group or a C 7-20 aralkyl group
  • the timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule, but the polymerization reaction is particularly desired when a rubber-like property is expected in the living radical polymerization method. It is preferable to react as the second monomer at the end of the reaction or after completion of the reaction of the predetermined monomer.
  • (Ab) When a bulle polymer is synthesized by the living radical polymerization method, for example, 1, 5-hexagen, 1, 7-octadiene, 1 after completion of the polymerization reaction or after completion of the reaction of a predetermined monomer. , A method of reacting a compound having at least two alkenyl groups having low polymerizability such as 9-decadiene.
  • (AC) Various types of vinyl polymers having at least one highly reactive carbon-halogen bond having an alkenyl group such as organotin such as allyltributyltin and allyltrioctyltin. A method of replacing halogen by reacting an organometallic compound.
  • a vinyl polymer having at least one carbon-halogen bond having high reactivity is reacted with a stabilized carbanion having an alkenyl group as shown in the general formula (8) to substitute the halogen.
  • R 17 is the same as in general formula (7), R 18 and R 19 are both electron-withdrawing groups that stabilize carbanion C—, or one is the electron-withdrawing group and the other is hydrogen or carbon number.
  • 1 to 10 represents an alkyl group or a phenyl group, R 2 ° represents a direct bond, or 2 to 10 carbon atoms.
  • M + represents alkali metal ion or quaternary ammonium ion
  • R 18 and R 19 those having a structure of —CO 2 R, —C ( ⁇ ) R and —CN are particularly preferable.
  • An enolate cation is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with, for example, a metal alone or an organometallic compound such as zinc. Reaction with an electrophilic compound having an alkenyl group, such as an alkenyl group-containing compound having a leaving group such as a cetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, an acid halide having an alkenyl group How to make.
  • an electrophilic compound having an alkenyl group such as an alkenyl group-containing compound having a leaving group such as a cetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, an acid halide having an alkenyl group How to make.
  • a vinyl polymer having at least one highly reactive carbon-halogen bond for example, an oxydione or carboxylate having an alkenyl group as represented by the general formula (9) or (10) A method of replacing halogen by reacting anion.
  • HC C (R 17 ) — R 21 — ⁇ — M + (9)
  • R 17 is the same as in general formula (7), M + is the same as in general formula (8).
  • R 21 is a divalent organic group having 1 to 20 carbon atoms and containing one or more ether bonds. You may go out)
  • R 17 is the same as in general formula (7)
  • M + is the same as in general formula (8).
  • R 22 is a direct bond or a divalent organic group having 1 to 20 carbon atoms and one or more ethers. And may contain a bond).
  • the above-described method for synthesizing a bulle polymer having at least one carbon-halogen bond having high reactivity is an atom transfer using an organic halide as described above as an initiator and a transition metal complex as a catalyst.
  • a radical polymerization method is exemplified, but the method is not limited to these.
  • the bull polymer having at least one alkenyl group can also be obtained from a vinyl polymer having at least one hydroxyl group, and is capable of using the method exemplified below. Do not mean.
  • a base such as sodium methoxide is allowed to act, and an alkenyl group such as valyl chloride.
  • a method of reacting with a halogenated material is allowed to act, and an alkenyl group such as valyl chloride.
  • (Ah) a method of reacting an alkenyl group-containing isocyanate compound such as aryl isocyanate.
  • a method of reacting an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst is
  • a bull polymer when halogen is not directly involved in the method of introducing an alkenyl group such as (A_a) and (A_b), a bull polymer can be synthesized using a living radical polymerization method. preferable.
  • the method (A_b) is more preferable because it is easier to control.
  • an alkenyl group by converting a halogen of a vinyl polymer having at least one highly reactive carbon monohalogen bond it has at least one highly reactive carbon-halogen bond
  • At least one highly reactive carbon-halogen bond is obtained at the terminal, obtained by radical polymerization of vinyl monomers using an organic halide or sulfonyl halide as an initiator and a transition metal complex as a catalyst (atom transfer radical polymerization). It is preferable to use a single bulle polymer.
  • the point force (A ⁇ f) method that is easier to control is more preferable.
  • hydrosilane compound having a crosslinkable silyl group is not particularly limited, but representative examples thereof include compounds represented by the general formula (11).
  • a compound having a crosslinkable group represented by the formula (wherein R U , Y and a are the same as those in the general formula (3)) is preferable from the viewpoint of easy availability.
  • a transition metal catalyst is usually used.
  • the transition metal catalyst include platinum alone; A platinum solid dispersed in a carrier such as alumina, silica, carbon black; chloroauric acid; complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc .; platinum-olefin complex; platinum (0) -divinyltetramethyl Examples include disiloxane complexes.
  • catalysts other than platinum compounds include RhCKPPh), RhCl, RuCl, IrCl, FeCl, A1C1, Pd
  • Examples of the method for producing a bulle polymer having at least one hydroxyl group used in the methods (B) and (A_g) to (A_j) include the following methods, but are not limited to these methods. is not.
  • an alkenyl alcohol such as 10-undecenol, 5-hexenol or allylic alcohol is used at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. How to react.
  • (B_d) A method of radical polymerization of a butyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator as disclosed in, for example, JP-A-6-239912 and JP-A-8-283310.
  • (B_e) A method of radically polymerizing a bull monomer by using alcohol excessively as disclosed in, for example, JP-A-6-116312.
  • (Bf) Hydrolysis or hydroxyl group-containing compound of a bulle polymer halogen having at least one highly reactive carbon-halogen bond by a method such as disclosed in, for example, JP-A-4-132706 To introduce a hydroxyl group at the terminal by reacting with
  • (B_g) A method of substituting a halogen by reacting a bur polymer having at least one highly reactive carbon-halogen bond with a stabilized carbanion having a hydroxyl group as shown in the general formula (14).
  • R 18 and R 19 those having a structure of —CO 2 R, —C ( ⁇ ) R and —CN are particularly preferable.
  • a method of preparing an enolate anion by reacting a simple metal such as zinc or an organometallic compound, and then reacting with an aldehyde or a ketone.
  • R 21 is the same as the general formula (9).
  • M + is the same as the general formula (8).
  • R 22 is the same as the general formula (10).
  • M + is the same as the general formula (8).
  • R 14 is the same as the general formula ( 7 ).
  • R 21 is the same as the general formula ( 9 ).
  • the compound represented by the general formula (17) is not particularly limited, but alkenyl alcohols such as 10-undecenol, 5-hexenol, and aryl alcohol are preferred because they are easily available. .
  • a bulle polymer is synthesized using a living radical polymerization method. It is preferable.
  • the method (B_b) is more preferable because it is easier to control.
  • an organic halide or a halogenated sulfonyl compound is used as an initiator, transition It is preferable to use a bulle polymer having at least one highly reactive carbon-halogen bond at the terminal, obtained by radical polymerization of a bulle monomer using a metal complex as a catalyst (atom transfer radical polymerization method).
  • the method (Bi) is preferred because it is easier to control.
  • examples of the compound having a group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group in one molecule include, for example, ⁇ -isocyanatopropylpropylmethoxysilane, y-isocyanatopropylmethyldimethoxysilane. ⁇ -isocyanatopropyltriethoxysilane and the like, and generally known catalysts for urethanization reaction can be used if necessary.
  • Examples of the compound having a polymerizable alkenyl group and a crosslinkable silyl group in one molecule used in the method (C) include, for example, ⁇ -trimethoxysilylpropyl (meth) atalylate, y-methyldimethoxy. Examples thereof include those represented by the following general formula (18) such as silylpropyl (meth) acrylate.
  • R 10 , R U , Y, a, b and 1 are the same as in general formula (3).
  • R 14 and R 15 are the same as in general formula (7).
  • R 23 is a direct bond or the number of carbon atoms. 1-20 divalent organic groups which may contain one or more ether linkages, provided that a + lb ⁇ l.
  • the method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond used in the method of (D) includes a transition metal using an organic halide as described above as an initiator. Examples include, but are not limited to, atom transfer radical polymerization using a complex as a catalyst. Examples of the compound having both a crosslinkable silyl group and a stabilized carbanion in one molecule include those represented by the general formula (19).
  • R 10 R U Y ab 1 is the same as in general formula (3).
  • R 18 R 19 M + is the same as in general formula (8).
  • R 2 4 is a direct bond, or carbon number 1 to: 10 R 25 may be hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. (However, it shall be satisfied that a + lb ⁇ l.)
  • the electron withdrawing group of R 18 R 19 has the structure of CO RC ( ⁇ ) R and 1 CN
  • the tackifier resin (B) used in the present invention is not particularly limited, and it is possible to use a commonly used one. Specific examples include terpene resins, aromatic modified terpene resins and hydrogenated terpene resins obtained by hydrogenation of these, terpenes obtained by copolymerizing terpenes with phenols, phenol resins, phenol resins, modified phenol resins, xylene.
  • Phenolic resin cyclopentagen monophenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, and DC PD resin. These may be used alone or in combination of two or more
  • the amount of the tackifying resin (B) used is 20 to 100 parts by weight, preferably 40 to 80 parts by weight, based on 100 parts by weight of the bull polymer (A). If the amount is less than 20 parts by weight, the tack (adhesive strength) tends to be insufficient. If the amount exceeds 100 parts by weight, the curing speed becomes slow, so the time for forming the pressure-sensitive adhesive layer becomes slow, and the workability decreases because the viscosity increases. Tend to.
  • the curing catalyst (C) used in the present invention is not particularly limited, and a silanol condensation catalyst that promotes the reaction of a commonly used reactive carbon group is used.
  • a silanol condensation catalyst that promotes the reaction of a commonly used reactive carbon group is used.
  • Specific examples of such a curing catalyst include, for example, titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetraacetylacetonate, bisacetylacetylatodiisopropoxytitanium; dibutyltin dilaurate, dibutyltin Maleate, Dibutyltin phthalate, Dibutyltin geotate, Dibutyltin jetyl hexanolate, Dibutyltin dimethyl maleate, Dibutyltin jetyl maleate, Dibutyltin dibutylmaleate, Dibutyltin dioctylmaleate, Dibutyltin
  • the amount of these curing catalysts (C) used is 0.05 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight in total of the vinyl polymer (A) and the tackifying resin (B). 0.5 parts by weight or more and 5 parts by weight or less is preferable. If it is less than 0.05 parts by weight, the curing rate tends to be slow and the open time tends to be long. On the other hand, if it exceeds 10 parts by weight, the resulting cured product will adhere to the adherend. There is a tendency for the workability to deteriorate such that the adhesiveness is lowered or the open time becomes too short to make it impossible to apply the composition.
  • the composition used in the present invention can be used without a solvent, but for the purpose of adjusting the viscosity, a solvent is used in combination as the component (D).
  • a solvent is not particularly limited as long as it can dissolve the component (A) and the component (B), and conventionally known solvents can be widely used.
  • solvents such as methanol, ethanol, isopropyl alcohol
  • Use solvents such as ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, aliphatic hydrocarbons, and aromatic hydrocarbons such as toluene and xylene alone or in combination.
  • alcohols are more preferable in view of the toxicity of the solvent.
  • the blending amount is preferably 0.:! To 50 parts by weight with respect to 100 parts by weight of the vinyl polymer (A). When the amount is less than 1 part by weight, the meaning of blending the solvent (D) becomes dilute. Tend to be delayed.
  • the curable composition used in the present invention may contain a silane coupling agent, a filler, a thixotropic agent, a plasticizer, a stabilizer and the like as necessary.
  • silane coupling agent examples include amino group-containing silanes such as N- ( ⁇ -aminoethyl) ⁇ aminopropyltrimethoxysilane; ⁇ - epoxy group-containing silane such as mercaptopropyltrisilane Bis-unsaturated silane-containing silanes such as bi-trimethoxysilane; y-isocyanate propyl-trimethoxy silane-containing isocyanate-containing silanes, and the like. They may be used, or two or more types may be mixed and used. Of these, aminosilane and its reactants, epoxy silane, and isocyanate silane are particularly preferred from the viewpoint of adhesion.
  • the silane coupling agent is preferably used in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the bull polymer ( ⁇ ). 2 to 10 parts by weight is more preferable.
  • the filler include, for example, calcium carbonate, magnesium carbonate, and titanium oxide. , Carbon black, fused silica, precipitated silica, diatomaceous earth, white clay, kaolin, clay, talc, wood powder, talmi shell powder, rice husk powder, anhydrous silicate, quartz powder, aluminum powder, zinc powder, asbestos, Inorganic fillers such as glass fiber, carbon fiber, glass beads, alumina, glass balloon, shirasu balloon, silica balloon calcium oxide, magnesium oxide and silicon oxide, wood filler such as pulp and cotton chips, powder rubber, recycled rubber
  • organic fillers include fine powders of thermoplastic or thermosetting resins, hollow bodies such as polyethylene, etc. These fillers may be used alone or in combination of two or more. . Among these, calcium carbonate is particularly preferable from the viewpoints of quality and economy.
  • thixotropic agent examples include hydrogenated castor oil, organic amide wax, organic bentonite, calcium stearate and the like. These thixotropic agents may be used alone. You may use the above together.
  • the thixotropic agent is preferably used in an amount of 0.5 to 50 parts by weight, based on 100 parts by weight of the bull polymer (A). It is more preferable.
  • plasticizer examples include, for example, phthalic acid esters such as dioctyl phthalate and diisodecyl phthalate; aliphatic dibasic acid esters such as dioctyl adipate; epoxidized soybean oil, epoxidized amani
  • phthalic acid esters such as dioctyl phthalate and diisodecyl phthalate
  • aliphatic dibasic acid esters such as dioctyl adipate
  • epoxidized soybean oil epoxidized amani
  • epoxy plasticizers such as oil
  • polyethers such as polypropylene glycol and derivatives thereof
  • vinyl polymers obtained by polymerizing bulle monomers by various methods, and the like may be used alone or in combination of two or more.
  • the amount of the plasticizer used is preferably 20 to 300 parts by weight, more preferably 30 to 200 parts by weight, based on 100 parts by weight of the vinyl polymer (A). If it is less than 20 parts by weight, the effect as a plasticizer tends to be lost, and if it exceeds 300 parts by weight, the mechanical strength of the cured product tends to be insufficient.
  • the stabilizer include an antioxidant, a light stabilizer, and an ultraviolet absorber.
  • the weather resistance of the cured product can be enhanced.
  • the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols S, and hindered phenols are particularly preferable.
  • the antioxidant is used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl polymer (A). 0.2 to 5 parts by weight is preferably used. More preferred.
  • the photooxidation deterioration of the cured product can be prevented.
  • the light stabilizer include benzotriazole, hindered amine, and benzoate compounds. Particularly, a hindered amine is preferable.
  • the light stabilizer is used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the bull polymer (A). 0.2 to 5 parts by weight is preferably used. More preferred.
  • ultraviolet absorber When an ultraviolet absorber is used, the surface weather resistance of the cured product can be increased.
  • ultraviolet absorbers include benzophenone, benzotriazole, salicylate, substituted tolyl, and metal chelate compounds, with benzotriazole being particularly preferred.
  • the amount of the UV absorber used is preferably from 0.:! To 10 parts by weight based on 100 parts by weight of the bull polymer (A). 0.2 to 5 parts by weight should be used. Is more preferable.
  • a phenol-based nya hindered phenol-based antioxidant it is preferable to use a phenol-based nya hindered phenol-based antioxidant, a hindered amine-based light stabilizer, and a benzotriazole-based ultraviolet absorber in combination.
  • additives may be added to the curable composition used in the present invention as needed for the purpose of adjusting the physical properties of the curable composition or the cured product.
  • additives include, for example, flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents. , Solvents and fungicides. These various additives may be used alone or in combination of two or more.
  • the coating thickness of the curable composition used in the present invention is preferably 30 ⁇ m to 3 mm, more preferably 50 to 111 to 1111111, more preferably 50 to 500 to 111, and more preferably 60 to 250. It is particularly preferable for ⁇ ⁇ . When the coating thickness exceeds 3mm, the water supply to the deep part is slow. Does not proceed, there is a tendency for the speed of expression of adhesive properties to be slow. It is particularly preferable that the coating thickness is in the above range from the viewpoint of ensuring the adhesive property expression speed and securing the adhesive strength.
  • the curable composition used in the present invention uses a low-viscosity polymer, it can be sufficiently applied at room temperature even when mixed with the tackifier resin (B), but has better workability. Therefore, it is preferable to apply the curable composition used in the present invention to a temperature of 40 to 140 ° C. 50 to 120 ° C is more preferable to 50 to 100 ° C. C is more preferable. Heating the curable composition used in the present invention to the above temperature is preferable from the viewpoints of workability and ensuring the stability of the curable composition.
  • the heating method is not particularly limited, and any conventionally known method can be used. preferable. Furthermore, it is preferable to heat the sealed container filled with the curable composition with a heater having a heater member. Further, a method of covering and heating the cartridge can with a heating cylinder having a hollow cylindrical heater member in a state where the cartridge can is used as a sealed container, and the cartridge can filled with the curable composition is housed in an extrusion gun. Is most preferable.
  • the one-pack type bonding agent of the present invention is filled with a curable composition in an airtight container, the curable composition is discharged onto an adherend to directly form a coating film having a desired thickness. be able to . For this reason, it is possible to reduce the necessity of separately preparing coating tools such as brushes and applicators.
  • the Nozzle opening has a length in the longitudinal direction of 5 to 50 mm and a length in the short side direction of 0.5 to 5 mm.
  • the length in the longitudinal direction is preferably 5 to 40 mm, more preferably 5 to 30 mm.
  • the length in the short side direction is preferably 0.5 to 3 mm, more preferably 0.5 to 1.5 mm.
  • the one-pack type on-site coating bonding agent filled in the sealed container of the present invention is used for bonding various adherends used at various work sites.
  • the adherend referred to in the present invention includes both a base material and a base material bonded thereto.
  • Examples of the base material include inorganic base such as concrete, flexible board, pearlite board, calcium silicate board, mortar, PC board, ALC board, gypsum board, tile, plywood, MDF, particle board, and hardware.
  • Wooden substrates such as boards and flooring materials, studs, runners, aluminum plates, various panels on which aluminum films are bonded, various metal substrates such as fender metal plates, polyethylene, polypropylene, polystyrene, polychlorinated butyl, polyethylene terephthalate
  • plastic plates and foams such as polycarbonate, polytetrafluoroethylene, polyvinylidene fluoride, EVA, and melamine, and plastic substrates such as various panels on which these plastic films are bonded.
  • the base material to be bonded to the base is, for example, cement board, wood wool cement board, flexible board, calcium silicate board, gypsum board, glass wool board, rock wool board, marble, stone, tile, Inorganic base materials such as decorative glass, plywood, fiberboard, MDF, particle board, hard board, natural wood board, flooring material, baseboard, waist wall material, surrounding base materials such as surrounding edges, metal base material , Polyethylene, Polypropylene, Polystyrene, Polyvinyl chloride, Polyethylene terephthalate, Polycarbonate, Cellulose diacetate, Polytetrafluoroethylene, Polyvinylidene fluoride, EVA, Melamine, Polymonochloro trifluoroethylene, Polyethersulfone, Polymethyl Plastics such as pentene and polyphenylene sulfide Chick plate or decorative material, film, Shiobiya Orefuin-based flooring, baseboards, spandrel wall material, around the edge, such as a plastic-based material
  • the one-pack type on-site coating adhesive filled in the sealed container of the present invention is filled with a curable composition in a sealed container, and the total amount of the sealed container is, for example, 10 kg. It is lightweight so that it becomes as follows. Therefore, for example, the curable composition can be brought to a desired temperature by covering the sealed container with a heater having a heater member. In addition, since it is lightweight, the sealed container can be carried and applied to the application site of the bonding agent, so it is preferably used for bonding the interior material.
  • interior materials include floor materials (floor finishing materials), wall materials, and ceiling materials.
  • Floor finish materials include bull floor sheets, olefin floor sheets, carpets, cork car pets, grass carpets, wood carpets, solid flooring materials, WPC flooring materials, Single board flooring material, sound insulation flooring material, natural stone material, synthetic stone material, composition vinyl floor tile, homogenous vinyl floor tile, carpet tile, linoleum floor tile, rubber floor tile, terrazzo tile, glass building material, etc. .
  • Wall materials include cement board, wood wool cement board, flexible board, calcium silicate board, plaster board, glass wool board, rock wool board, marble, stone, tile, decorative glass, plywood, etc. , Fiberboard, MDF, particle board, hard board, wood panel such as natural wood board, metal panel, plastic panel such as polystyrene, melamine, wood, PVC, olefin-based flooring, baseboard, waist Wall materials, edges, and wall paper are examples.
  • Examples of the ceiling material include gypsum board, decorative plywood, and sound absorbing tex.
  • the one-pack type coating agent for on-site coating filled in the sealed container of the present invention is preferably used for bonding floor materials (floor finishing materials).
  • the site where the one-pack type bonding agent filled in the sealed container of the present invention is used refers to a construction site where the above-mentioned various adherends are bonded, and particularly, interior materials, that is, flooring walls This shows the construction site where materials and ceiling materials are pasted together.
  • the curable composition used in the present invention can be prepared as a one-component type in which all the compounding components are preliminarily blended and stored and cured by moisture in the air after construction.
  • the method for preparing the curable composition used in the present invention is not particularly limited.
  • the above-described components are blended and kneaded using a mixer, a roll, a kneader, or the like at room temperature or under heating.
  • Ordinary methods such as using a small amount of a solvent to dissolve and mixing the components can be used.
  • the undecenoic acid potassium is methanol (250 mL), 10-undecenoic acid (150 g, 0.
  • the number average molecular weight of the obtained polymer was about 26000, and the molecular weight distribution was 1.2. When the average number of silyl groups introduced per molecule of the polymer was determined by 1 HN MR analysis, it was about 1.4.
  • Components (A) and (B) (in addition to these in Comparative Example 3) are mixed in the proportions shown in Table 1, dissolved by adding toluene, and then devolatilized by heating under reduced pressure at 90 ° C. did. Subsequently, silane coupling is added and stirred for 30 minutes. Finally, component (C) (in addition to component (D) in Example 4) is added and stirred for 30 minutes, then degassed under reduced pressure and made of aluminum. A tube (100 ml) was filled with the composition. Examples:! To 4 and aluminum tubes filled with the curable compositions of Comparative Examples 1 to 4 all had a weight of 110 g. The obtained composition was heated to 80 ° C or used in the evaluation at room temperature (23 ° C). All evaluations were performed in an atmosphere with a temperature of 23 ⁇ 2 ° C and a relative humidity of 50 ⁇ 10%.
  • the thickness of the cured composition whose thickness was adjusted by an applicator was measured using a micro gauge.
  • the composition was applied onto a flexible plate and the thickness was adjusted with an applicator.
  • the composition surface was pressed with a finger over time, and the time until the composition did not deform and did not adhere to the fingertip was measured.
  • Bonding after 90 minutes Apply the curable composition to a flexible board (width 80mm, length 150mm, thickness 4mm), adjust the thickness with an applicator, and 90 minutes later, PET film (corona discharge treatment; width 25mm) , 200 mm long and 0.05 mm thick) and cured for 1 week. After curing, a 180 ° peel test was performed with a tensile tester (tensile speed 200 mm / min), and the tensile strength and fracture state were observed (initial adhesion). The case where the tensile strength was 20N / 25mm or more was marked as ⁇ , and the case where the tensile strength was less than 20N / 25mm was marked as X.
  • Bonding immediately after application The curable composition was applied to a flexible plate, and after adjusting the thickness with an applicator, the PET film was immediately bonded and cured for 1 week. After curing, a 180 ° peel test was performed using a tensile tester to observe the tensile strength and fracture state (initial adhesion). The case where the tensile strength was 20N / 25mm or more was marked as ⁇ , and the case where the tensile strength was less than 20N / 25mm was marked as X. In addition, the case where it peeled between the pressure-sensitive adhesive layer and the PET film was marked with ⁇ , and the others were marked with X.
  • the aluminum tube filled with the composition is allowed to stand at 23 ° C for 4 weeks and then heated to the coating temperature. Then, the composition was discharged, and the presence or absence of a gel-like material was examined. The case where no gel-like substance was observed was marked with ⁇ , and the case where a gel-like substance was confirmed was marked with X.
  • Table 1 shows the evaluation results.
  • Kizirene resin manufactured by FUJI Co., Ltd.
  • * 5 Ship W tin bisacetyla KOKE Co., Ltd.
  • Example 1 The composition of Example 1 was filled into a smoke cartridge (capacity 333 ml) and sealed. The weight of the PE cartridge filled with the composition was 370 g. The cartridge was placed in a thermostat at 80 ° C. and heated to 80 ° C. and then taken out. The composition was partially applied to a melamine panel (3 ⁇ 935 ⁇ 2450) in a bead shape with a hand gun. After 20 minutes, the panel S was firmly fixed to the wall so that the panel could be displaced immediately after the bonding. In addition, after one week at room temperature, the panel was peeled off, but the phenomenon such as destruction of the panel was not observed, and it was relatively easy to peel off.
  • a commercially available double-sided tape (CV_25, manufactured by Sumitomo 3M Limited) was used, and the tape was affixed to the same location where the composition was applied in Example 5, and the panel was affixed and pulled to the base material. Peeling was performed. As a result, the initial fixability and ease of peeling of the panel were sufficient, and the work of peeling the release paper from the double-sided tape when attaching the panel was laborious, and the release paper as waste was A large amount occurred.
  • Example 5 In the same manner as in Example 5, the cartridge was heated so that the composition became 80 ° C, then loaded into a hand gun, and the gun was covered with a detachable mantle heater to keep the composition at 80 ° C. The coating was repeated. In Example 5, the cartridge was gradually cooled and it became difficult to discharge 40 minutes after the start of use, but in Example 6, it could be used without any time limit.
  • Example 5 In the same manner as in Example 5, the cartridge was heated so that the composition reached 80 ° C., and then loaded into a hand gun equipped with a heater, and coating was repeated while maintaining the composition at 80 ° C. In Example 5, the cartridge was gradually cooled, and it became difficult to discharge after 40 minutes of use. In Example 7, the cartridge could be used without any time limit.
  • Example 1 The composition of Example 1 was filled into an aluminum cartridge (capacity: 310 ml) and sealed. The weight of the aluminum cartridge filled with the composition was 360 g. The sample was loaded into a hand gun equipped with a heater (TR70.3, manufactured by Reka), and the composition was discharged by nitrogen pressure while maintaining the composition at 80 ° C. In Example 5, the cartridge was gradually cooled, and it became difficult to discharge 40 minutes after the start of use. In Example 8, however, the cartridge could be used without any time limit.
  • Example 6 In the same operation as in Example 6, a type in which the coating part was opened in a square shape (nozzle opening part: longitudinal direction l lmm, short side direction 2 mm) was used as the cartridge nose. Partial application to Nore (3 X 935 X 2450). At this time, the surface of the composition was smooth and there was no large variation in thickness. After 90 minutes, the panel was fixed to the wall sufficiently without slipping immediately after bonding. In addition, the panel was peeled off after 1 week at room temperature, but it did not show any phenomenon such as panel breakage and could be peeled off relatively easily.
  • the composition was partially applied to the flooring material. After 90 minutes, the force of bonding the flooring material to the plywood flooring material The flooring material was sufficiently fixed to the floor without slipping immediately after bonding. In addition, after one week at room temperature, the flooring material was peeled off, but no phenomenon such as destruction of the flooring material was seen, and it was relatively easy to peel off.
  • the one-part on-site construction adhesive described in the examples has a good workability and forms an adhesive layer at an early stage, initial adherend fixability, long-term easy peelability, re-adhesion, storage Although it is excellent in stability, the composition of the comparative example did not show a system that expresses these physical properties in a well-balanced manner.
  • the coating time could be used without any limitation.
  • a nozzle in which the coating part of the example was opened in a square shape sufficient pasting was possible even with a long open time after coating.
  • an adhesive that does not require a solvent drying step can be easily and quickly formed at a construction site such as a building, and the handling of the adhesive can be simplified.
  • the adherend bonded with the pressure-sensitive adhesive can be easily peeled off, it is possible to simplify operations such as reforming after use.
  • the heating temperature of the curable composition can be designed to be about 40 to 140 ° C. With such low temperature heating, there are few restrictions at the construction site.
  • an adhesive that does not require a solvent drying step can be easily and quickly formed at a construction site such as a building, and the handling of the adhesive can be simplified.
  • the adherend bonded with the adhesive is easy to peel off, It is possible to simplify work such as remodeling.
  • the present invention eliminates various limitations by filling a hermetic container with a curable composition containing an adhesive-imparting agent, thereby providing a new system for pasting work that did not exist in the past. Is.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Un adhésif autocollant ne nécessitant aucune étape de séchage du solvant est formé directement sur un chantier de construction ou similaire pour de cette manière simplifier la manipulation des adhésifs autocollants. Cet adhésif autocollant facilite le décollement du substrat après utilisation, par exemple dans un remaniement. L'agent pour stratifiés de type agent contenu dans un emballage unique comprend une composition durcissable laquelle comprend 100 parties en poids d'un polymère vinylique (A) qui a en moyenne au moins un groupe silyle réticulable capable de former une liaison siloxane et 20-100 parties en poids d'une résine d'agent poisseux (B) et contient en plus un catalyseur de durcissement (C) en quantité représentant 0,05-10 parties en poids pour 100 parties en poids de la somme des ingrédients (A) et (B). L'agent pour stratifiés de type agent contenu dans un emballage unique est caractérisé en ce que la composition durcissable est emballée dans un récipient fermé.
PCT/JP2006/312010 2005-06-17 2006-06-15 Agent pour stratifies de type agent contenu dans un emballage unique WO2006134997A1 (fr)

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JP2007521336A JP5021471B2 (ja) 2005-06-17 2006-06-15 一液型貼り合せ剤

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JP2005-177552 2005-06-17
JP2005177552 2005-06-17

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WO (1) WO2006134997A1 (fr)

Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN109125789A (zh) * 2012-03-12 2019-01-04 博斯蒂克股份公司 粘结剂组合物，透气的自粘制品，自粘制品的用途及其制备方法
WO2021171734A1 (fr) * 2020-02-25 2021-09-02 信越化学工業株式会社 Composition d'adhésif à base de silicone sensible à la pression
KR20220008326A (ko) 2019-06-20 2022-01-20 후지필름 가부시키가이샤 가접착제 조성물이 충전된 가접착제 조성물이 든 용기, 가접착제 조성물의 보존 방법, 및 가접착제 조성물이 든 용기의 제조 방법

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11578237B2 (en) 2015-10-07 2023-02-14 Dai Nippon Printing Co., Ltd. Adhesive sheet set and method for producing product

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WO2021171734A1 (fr) * 2020-02-25 2021-09-02 信越化学工業株式会社 Composition d'adhésif à base de silicone sensible à la pression
JP2021134244A (ja) * 2020-02-25 2021-09-13 信越化学工業株式会社 シリコーン粘着剤組成物
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