JP5073489B2 - One-part adhesive - Google Patents

Description

  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.

  Conventionally, various adhesives having good adhesion to these adherends have been used for bonding various adherends. However, in recent years, the demand for remodeling has been increasing, and problems such as the fact that the adherend is very difficult to peel off due to bonding with an adhesive have arisen. Under these circumstances, many easily peelable adhesives that make it easy to peel off the adherend have been studied, but have not yet reached a satisfactory level in terms of physical properties and cost (for example, JP-A-7-62843). No. or JP-A-2002-3800).

  The use of an adhesive such as an adhesive tape is considered effective in order to obtain easy peelability, but the cost of the adhesive tape is very high, and the work of peeling the release paper is complicated and is discarded due to the release paper. Various problems remain, such as an increase in quantity. As a measure for improving such problems, it is considered effective to apply only the adhesive used for the adhesive tape to the necessary part in the necessary scene. However, acrylic and rubber adhesives generally used for adhesive tapes contain a large amount of solvent, so a process to evaporate the solvent at a high temperature is required after coating. It was difficult to use.

  An object of the present invention is to simplify the handling of the adhesive by directly forming an adhesive that does not require a solvent drying process at a construction site such as a building, and to peel off the adherend by renovation after use. Is to provide a way to make it easier.

  As a result of diligent studies to solve the above-mentioned problems, it is epoch-making when a one-pack type adhesive agent in which a curable composition curable by moisture in the air is filled in a closed container such as a cartridge or a tube is used. The present invention has been found by finding that a field work system can be constructed.

  In the present invention, (A) 20 to 20 parts of (C) a tackifier resin is added to 100 parts by weight of an oxyalkylene polymer having a reactive silicon group capable of forming a siloxane bond and having no urethane bond and urea bond. One-part bonding comprising a curable composition containing 100 parts by weight and further containing 0.05 to 10 parts by weight of (D) a curing catalyst with respect to 100 parts by weight of the total amount of components (A) and (C). It is an agent, Comprising: It is related with the one-pack type bonding agent characterized by filling the said curable composition in the airtight container.

  In the present invention, the oxyalkylene polymer (A) having a reactive silicon group capable of forming a siloxane bond and not having a urethane bond and a urea bond (A) and (B) has substantially one or more molecular chains. A copolymer containing an acrylic acid alkyl ester monomer unit and / or a methacrylic acid alkyl ester monomer unit, and further, tackifying to 100 parts by weight of the total amount of components (A) and (B) Curing containing 20 to 100 parts by weight of resin (C) and 0.05 to 10 parts by weight of curing catalyst (D) with respect to 100 parts by weight of the total amount of components (A), (B) and (C) The present invention relates to a one-component bonding agent comprising an adhesive composition, wherein the curable composition is filled in a sealed 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 number average molecular weight of the oxyalkylene polymer (A) is preferably 10,000 to 100,000, and the molecular weight distribution is preferably 1.6 or less.

  The oxyalkylene polymer (A) is preferably a polymer having a reactive silicon group in which three hydroxyl groups and / or hydrolyzable groups are bonded to one silicon atom.

  The copolymer (B) is preferably a polymer having a reactive silicon group in which three hydroxyl groups and / or hydrolyzable groups are bonded to one silicon atom.

  It is preferable that a curable composition contains 0.1-50 weight part (E) solvent with respect to 100 weight part of total amounts of an oxyalkylene type polymer (A) and a copolymer (B).

  The total weight of the sealed container filled with the curable composition is preferably 10 kg or less.

  Moreover, it is preferable to use the one-component bonding agent of the present invention for on-site coating.

  Furthermore, the present invention is a method for laminating a pair of adherends, a step of applying a curable composition filled in the sealed container to one adherend, and after proceeding with curing, The present invention relates to a method for bonding an adherend including a step of bonding the other adherend to a semi-cured or cured curable composition.

  It is preferable to include a coating step of discharging the curable composition from the sealed container onto the adherend and directly forming a coating film of the curable composition having a thickness of 30 μm to 3 mm on the adherend.

  It is preferable that the closed container filled with the curable composition is heated to set the temperature of the curable composition at the time of discharge to 40 to 140 ° C.

  It is preferable to heat the sealed container filled with the curable composition with a heater having a heater member.

  The sealed container is a cartridge can, and the cartridge can filled with the curable composition is preferably heated by a heating cylinder having a hollow cylindrical heater member in a state where the cartridge can is housed in an extrusion gun.

  It is preferable to discharge a curable composition by connecting a coating nozzle having a rectangular opening to a sealed container.

  The adherend is preferably an interior material.

  The airtight container used in the present invention can be used without any particular limitation as long as it has low moisture permeability and can fill the filled bonding agent from the coating outlet. In particular, 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, it is preferably 10 kg or less, more preferably 5 kg or less, even more preferably 3 kg or less, more preferably 1 kg or less in a state where the curable composition is filled. Particularly preferred. On the other hand, if the amount is too small, the working efficiency tends to decrease, so 0.1 kg or more is preferable. In addition, even if it is less than that, for example, about 1 g, it is sufficiently practical for DIY.

  The viscosity of the curable composition used in the present invention is preferably 3 to 50 Pa · s / 80 ° C, more preferably 5 to 30 Pa · s / 80 ° C, and 5 to 20 Pa · s / 80 ° C. More preferably. The viscosity of the curable composition is preferably within this range from the viewpoint of ensuring workability. The viscosity was measured at 80 ° C. using an E-type viscometer (3 ° × R14 cone).

  In the curable composition used in the present invention, after coating, a polymer having a reactive silicon group is hydrolyzed and condensed by moisture in the air, and is gradually cured. 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 good. Excellent adhesion. The stage at which this adhesive strength has started to develop refers to a state in which the composition is not yet completely cured, and the composition adheres to the finger by finger touch or the like. In the specification, it is defined as “semi-cured state”.

  On the other hand, at the stage where the composition is cured and the composition does not adhere to the finger due to finger touch or the like, the composition functions as a peelable pressure-sensitive adhesive and can be adhered even after the adherends are bonded together. The body can be easily peeled off and repositioned. 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. The pressure-sensitive adhesive generally exhibits peelability, but in the present invention, the expression “peelable pressure-sensitive adhesive” is used in order to clarify the difference from a permanent pressure-sensitive adhesive that cohesively breaks after use and does not exhibit peelability.

  Depending on the type of adherend used, even if the composition is bonded in a semi-cured state, it may function as a peelable adhesive after curing.

  The curable composition used in the present invention is preferably cured within 90 minutes after coating to form an adhesive layer. More preferably, it is within 60 minutes, and most preferably 3 to 30 minutes. If the curing is faster than 3 minutes, the substrate may not be sufficiently wetted and sufficient adhesiveness may not be ensured. If the pressure-sensitive adhesive layer is formed after 90 minutes, it is not preferable from the viewpoint of workability.

The main chain of the oxyalkylene polymer (A) used in the present invention has a repeating unit represented by -R-O- (R represents a divalent alkylene group having 2 to 4 carbon atoms). is there. R is _{specifically, -CH 2 -, - CH 2} CH 2 -, - CH (CH 3) CH 2 -, - CH (CH 2 CH 3) CH 2 -, - CH 2 CH 2 CH 2 CH 2 _{-, - C (CH 3)} 2 CH 2 - and the like. These may be one kind or may be composed of two or more kinds of repeating units. The oxyalkylene polymer (A) composed of the main chain having the above repeating unit is effectively used. Among these, —CH (CH ₃ ) CH ₂ — is particularly preferable from the viewpoint of availability.

  In addition, the oxyalkylene polymer (A) does not have a urethane bond or a urea bond in the main chain skeleton, which lowers these properties, in order to suppress viscosity increase and ensure workability and heat resistance. . Furthermore, the oxyalkylene polymer (A) is preferably a polymer composed of a plurality of atoms selected from oxygen atoms, carbon atoms, hydrogen atoms, silicon atoms and halogen atoms.

  The oxyalkylene polymer (A) may be linear or branched, or a mixture thereof. In addition, other monomers may be included, but the monomer unit represented by -R-O- is preferably present in the polymer in an amount of 50% by weight or more, and is present in an amount of 80% by weight or more. More preferably.

The production method of the main chain skeleton of the oxyalkylene polymer (A) is not particularly limited, and can be obtained by various methods. For example, for example,
(A1) Initiators such as dihydric alcohols, polyhydric alcohols and various oligomers having a hydroxyl group, and alkali metals such as KOH and NaOH, acidic catalysts, aluminoporphyrin metal complexes and cobalt cyanide zinc-glyme complex catalysts A method obtained by ring-opening polymerization of a monoepoxide such as ethylene oxide or propylene oxide in the presence of a known catalyst such as a cyanide complex catalyst;
(A2) Chain extension of a bifunctional or higher functional alkyl halide such as CH ₂ Cl ₂ or CH ₂ Br _{2 in} the presence of a basic compound such as KOH, NaOH, KOCH ₃ or NaOCH ₃ A method obtained by reaction,
Among these, since a polymer having a narrow molecular weight distribution and a low viscosity is obtained, the ring-opening polymerization of the monoepoxide using the double metal cyanide complex catalyst in the above (a1) is performed. preferable.

The reactive silicon group of the reactive silicon group-containing oxyalkylene polymer (A) is a group containing a silicon atom to which a hydroxyl group or a hydrolyzable group is bonded, and is a group that can be crosslinked by a silanol condensation reaction. It is not particularly limited. For example, the general formula (1):
_{^{- (Si (R 1 2-}} b) (X b) O) m Si (R 2) 3-a X a (1)
(In the formula, R ¹ and R ² are all tri groups represented by an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ³ ) ₃ SiO—. An organosiloxy group, when two or more R ¹ or R ² are present, they may be the same or different, where R ³ is a monovalent hydrocarbon having 1 to 20 carbon atoms; And three R ³ groups may be the same or different, and X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, they may be the same. A represents 0, 1, 2 or 3, b represents 0, 1 or 2, provided that a + Σb> 0, and m − (Si (R ¹ _2−b ) (X _b) O) - for b at the base, they may be the same, or different Good .m are mentioned groups represented by the show.) An integer of 0 to 19.

Specific examples of R ¹ and R ² include alkyl groups such as a methyl group and an ethyl group, and aryl groups such as a phenyl group, and a methyl group is particularly preferable.

  The hydrolyzable group in X is not particularly limited and may be any conventionally known hydrolyzable group. Specifically, for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide Group, aminooxy group, mercapto group and the like. Of these, alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group are preferable because they are mildly hydrolyzable and easy to handle.

  One to three hydroxyl groups or hydrolyzable groups can be bonded to one silicon atom, and (a + Σb) is preferably 3 to 5. The hydroxyl groups and hydrolyzable groups present in the reactive silicon group may be the same or different.

  The number of silicon atoms in the reactive silicon group may be one or two or more, but may be about 20 in the case of a reactive silicon group in which silicon atoms are linked by a siloxane bond or the like.

In addition, as a reactive silicon group, the following general formula (2):
-Si (R ² ) _3-a X _a (2)
(Wherein R ² and X are the same as those in the general formula (1) and a is 1, 2 or 3), preferably a trimethoxysilyl group, a triethoxysilyl group, a tri Examples thereof include an isopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a diisopropoxymethylsilyl group. Among these, since high activity and good curability are obtained, three hydroxyl groups and / or hydrolysis on one silicon atom such as trimethoxysilyl group, triethoxysilyl group, dimethoxymethylsilyl group, etc. A reactive silicon group to which a functional group is bonded is more preferred, and among these, a trimethoxysilyl group is most preferred, particularly from the viewpoint of the adhesive development rate.

  There may be at least one reactive silicon group, preferably 1.1 to 5, in the oxyalkylene polymer (A). When the number of reactive silicon groups contained in one molecule of the polymer is less than one, the curability becomes insufficient, and it tends to be difficult to express good rubber elasticity. On the other hand, if the number is more than 5, the network structure becomes too dense, and the flexibility of the cured product tends to decrease.

  The reactive silicon group may be present at the molecular chain terminal of the oxyalkylene polymer (A), or may be present inside, but if the reactive silicon group is present at the molecular chain terminal, the high strength, A rubber-like cured product exhibiting high elongation and low elastic modulus is easily obtained, which is more preferable.

The method for introducing the reactive silicon group into the oxyalkylene polymer (A) is not particularly limited, and various methods can be used. In particular, the general formula (3) per molecule:
^{_{H 2 C = C (R 4}} ) -R 5 -O- (3)
(Wherein, R ⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁵ is a divalent organic group having 1 to 20 carbon atoms). (A) and general formula (4):
HR ^6- (Si (R ¹ _2-b ) (X _b ) O) _m Si (R ² ) _3-a X _a (4)
(In the formula, R ¹ , R ² , X, a, b and m are the same as those in the general formula (1), R ⁶ is a divalent organic group having 0 to 20 carbon atoms or — (Si (R ⁷ ) (R _{^{8) O) n -Si (R}} 7) (R 8) -R 9 - in a group represented by, R ⁷ and R ⁸ is an alkyl group or a phenyl group having 1 to 6 carbon atoms, with the same R ⁹ is a divalent organic group having 1 to 6 carbon atoms, n is a reactive silicon group-containing compound represented by 1 to 10), and the presence of a group 10 transition metal catalyst The method of making it react under is preferable.

  In addition, the reaction between a hydroxyl-terminated ether polymer and a reactive silicon group-containing isocyanate compound, the reaction between an isocyanate group-terminated oxyalkylene polymer and a reactive silicon group-containing amine compound, or an unsaturated terminal oxyalkylene-based polymer. Reactive silicon group-containing oxyalkylene obtained by a method that generates urethane bonds and urea bonds from the viewpoint of ensuring workability and heat resistance, which can also be obtained by reacting the coalescence with a reactive silicon group-containing mercapto compound. Does not contain a polymer.

As a method for producing an oxyalkylene polymer having an unsaturated group represented by the general formula (3) at the terminal, a conventionally known method may be used. For example, a compound having an unsaturated bond in a hydroxyl-terminated ether polymer. And the like, and a method of bonding by an ether bond, an ester bond, a carbonate bond or the like. For example, when an unsaturated group is introduced by an ether bond, -OM (M is Na or K or the like) is generated by metal oxidation of the hydroxyl terminal of the ether-based polymer, and then the general formula (5):
^{_{H 2 C = C (R 4}} ) -R 5 -Y (5)
(In the formula, R ⁴ and R ⁵ are the same as those in the general formula (3), Y is a halogen atom).

Specific examples of the unsaturated group-containing compound represented by the general formula (5) include, for example, H ₂ C═CH—CH ₂ —Cl, H ₂ C═C (CH ₃ ) —CH ₂ —Cl, and the like. It is done.

Specific examples of the Group 10 transition metal catalyst include H ₂ PtCl ₆ · H ₂ O, a platinum-vinylsiloxane complex, a platinum-olefin complex, and the like.

  Such a production method is described in, for example, Japanese Patent No. 1247613, Japanese Patent Publication No. 3-31726, International Publication No. 03/15536, Japanese Patent Laid-Open No. 3-72527, and the like.

Reactive silicon represented by the general formula (4), wherein R ⁶ is a group represented by — (Si (R ⁷ ) (R ⁸ ) O) _n —Si (R ⁷ ) (R ⁸ ) —R ⁹ — The group-containing compound has the general formula (6):
^{H (Si (R 7) (} R 8) O) n -Si (R 7) (R 8) H (6)
(Wherein R ⁷ , R ⁸ and n are the same as those in the general formula (4)), and the general formula (7):
CH = CHR ¹⁰ (Si (R ¹ _2-b ) (X _b ) O) _m Si (R ² ) _3-a X _a (7)
(Wherein R ¹ , R ² , X, a, b and m are the same as those in the general formula (1), and R ¹⁰ is a divalent alkyl group having 1 to 6 carbon atoms). Can generally be obtained.

Among the compounds represented by the general formula (4) obtained by the reaction between the general formula (6) and the general formula (7), for example, HSi (CH ₃ ) (CH ₃ ) OSi (CH ₃ ) ( A compound represented by CH ₃ ) CH ₂ CH ₂ Si (OCH ₃ ) ₃ is preferable from the viewpoint of availability.

  The number average molecular weight of the reactive silicon group-containing oxyalkylene polymer (A) of the present invention is 10,000 to 100,000 in terms of polystyrene-reduced number average molecular weight (Mn) by gel permeation chromatography (GPC). Preferably, 15,000-50,000 are more preferable, and 25,000-40,000 are more preferable. It is particularly preferable for the number average molecular weight to be in this range from the standpoint of mechanical properties and handling. Further, the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is not particularly limited, but is preferably 1.6 or less, more preferably 1.5 or less, and 1.4 The following is more preferable. Thus, it is preferable that the molecular weight distribution is narrow even though the number average molecular weight is large, because the viscosity is low before the curing and the handling is easy and the rubber elastic behavior is good after the curing.

  The molecular weight distribution can be measured by various methods, but a method by gel permeation chromatography (GPC) is generally used.

  In addition, the curable composition used in the one-component bonding agent of the present invention has a molecular chain substantially having one or more kinds of alkyl acrylate monomer units and / or methacrylic acid alkyl esters alone. The copolymer (B) containing a body unit is included.

  A copolymer (hereinafter referred to as a copolymer) in which the molecular chain as the component (B) of the present invention substantially comprises one or more alkyl acrylate monomer units and / or alkyl methacrylate monomer units. As the acrylic acid alkyl ester monomer unit in the combination (B)), conventionally known ones can be widely used. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, acrylic acid Isobutyl, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, undecyl acrylate, lauryl acrylate, tridecyl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate, acrylic acid Behenyl, biphenyl acrylate, etc. That. Moreover, as a methacrylic acid alkylester monomer unit, a conventionally well-known thing can be widely used, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid. tert-Butyl, n-hexyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, undecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, myristyl methacrylate, cetyl methacrylate, stearyl methacrylate, behenyl methacrylate, methacrylic acid Biphenyl and the like can be given.

  The molecular chain of the copolymer (B) substantially includes one or more alkyl acrylate monomer units and / or methacrylic acid alkyl ester monomer units. Consisting of the above monomer units means that the ratio of the acrylic acid alkyl ester monomer units and / or methacrylic acid alkyl ester monomer units present in the copolymer (B) exceeds 50%. , Preferably 70% or more.

Among these monomer combinations, in view of compatibility and stability, the molecular chain is substantially (a) an acrylic acid alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms and / or Or a copolymer containing a methacrylic acid alkyl ester monomer unit and (b) an acrylic acid alkyl ester monomer unit having an alkyl group having 10 or more carbon atoms and / or a methacrylic acid alkyl ester monomer unit (hereinafter referred to as “copolymer”). Combined (B) -a) is preferred. The acrylic acid alkyl ester monomer unit and / or methacrylic acid alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms, which is the monomer unit (a) in the copolymer (B), has the general formula (8):
CH ₂ = C (R ¹¹ ) COOR ¹² (8)
(Wherein R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents an alkyl group having 1 to 8 carbon atoms).

R ^{12 in the} general formula (8) is preferably an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, or a 2-ethylhexyl group. An alkyl group having 1 to 4 carbon atoms is more preferable, and an alkyl group having 1 to 2 carbon atoms is further preferable. In addition, the monomer represented by General formula (8) may be one type, and may be used 2 or more types.

Moreover, the acrylic acid alkyl ester monomer unit and / or the methacrylic acid alkyl ester monomer unit having an alkyl group having 10 or more carbon atoms, which is the monomer unit (b), is represented by the general formula (9):
CH ₂ = C (R ¹¹ ) COOR ¹³ (9)
(Wherein R ¹¹ is the same as in formula (8). R ¹³ represents an alkyl group having 10 or more carbon atoms).

R ^{13 in the} general formula (9) is, for example, lauryl group, tridecyl group, cetyl group, stearyl group, C22 alkyl group, biphenyl group or the like, usually 10 to 30, preferably 10 -20 long chain alkyl groups. In addition, the monomer represented by the general formula (9) may be one type, and may be a group in which two or more types are mixed, such as a mixture of 12 and 13 carbon atoms.

  The molecular chain of the copolymer (B) -a substantially contains the monomer units (a) and (b), but the monomer units (a) and (b) here are substantially Including means that the proportion of the monomer units (a) and (b) present in the copolymer (B) -a exceeds 50%, preferably 70% or more. When the proportion of the monomer units of (a) and (b) is less than 50%, the compatibility of the reactive silicon group-containing oxyalkylene polymer (A) and the copolymer (B) -a decreases, and the cloudiness Tend to occur and the adhesive properties tend to decrease.

  The ratio of the monomer unit (a) to the monomer unit (b) is preferably 95: 5 to 40:60, more preferably 90:10 to 60:40, in weight ratio. When the ratio is greater than 95: 5, the compatibility tends to decrease, and when it is less than 40:60, the cost tends to be disadvantageous.

  The copolymer (B) may contain, in addition to the alkyl acrylate monomer unit and / or the methacrylic acid alkyl ester monomer unit, monomer units copolymerizable with these. For example, acrylic acid such as acrylic acid and methacrylic acid; monomer containing an amide group such as acrylamide, methacrylamide, N-methylol acrylamide and N-methylol methacrylamide, and a single amount including an epoxy group such as glycidyl acrylate and glycidyl methacrylate , Monomer containing amino group such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether; other acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, etc. Monomer units to be used.

  Although there is no restriction | limiting in particular in the molecular weight of a copolymer (B) component, The number average molecular weight in polystyrene conversion in GPC is what is 500-100,000. Furthermore, the thing of 2,000-50,000 is preferable and the thing of 5,000-30,000 is more preferable. It is particularly preferable that the number average molecular weight is in this range from the viewpoint of ease of handling and adhesive properties.

  The copolymer (B) can be obtained by a usual vinyl polymerization method. For example, it can be obtained by polymerization by a solution polymerization method or a bulk polymerization method using a radical reaction, but is not particularly limited to these methods. The reaction is usually carried out by adding the monomer, radical initiator, chain transfer agent, solvent and the like and reacting at 50 to 150 ° C.

  Examples of the radical initiator include azobisisobutyronitrile and benzoyl peroxide. Examples of the chain transfer agent include mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, lauryl mercaptan, and halogen-containing compounds. Can be given. As the solvent, for example, non-reactive solvents such as ethers, hydrocarbons and esters are preferably used.

  The copolymer (B) preferably has a silicon-containing group (hereinafter referred to as a reactive silicon group) that can be cross-linked by forming a siloxane bond from the viewpoint of adhesive properties, final adhesive strength, and the like. .

The method for introducing a reactive silicon group into the copolymer (B) is not particularly limited, and can be obtained by various methods. For example,
(I) a method of copolymerizing a compound having a polymerizable unsaturated bond and a reactive silicon group together with the monomers (a) and (b);
(II) A copolymer having a polymerizable unsaturated bond and a reactive functional group (hereinafter referred to as a Y ′ group) (for example, acrylic acid) is copolymerized with the monomers (a) and (b), and then the copolymer is produced. A method of reacting a compound with a compound having a functional group capable of reacting with a reactive silicon group and a Y ′ group (hereinafter referred to as Y ″ group) (for example, a compound having an isocyanate group and —Si (OCH ₃ ) ₃ group);
(III) a method of copolymerizing the monomers (a) and (b) in the presence of a mercaptan containing a reactive silicon group as a chain transfer agent;
(IV) a method of copolymerizing monomers (a) and (b) using an azobisnitrile compound or disulfide compound containing a reactive silicon group as an initiator,
(V) a method of polymerizing the monomers (a) and (b) by a living radical polymerization method and introducing a reactive silicon group at the molecular end;
Etc. Also, the methods (I) to (V) can be arbitrarily combined. For example, as a combination of (I) and (III), a compound having a polymerizable unsaturated bond and a reactive silicon group in the presence of a mercaptan containing a reactive silicon group as a chain transfer agent is added to the monomer (a). It is also possible to take a method of copolymerizing both (b) and (b).

The compound having a polymerizable unsaturated bond and a reactive silicon group described in (I) is represented by the general formula (10):
^{_{CH 2 = C (R 11)}} COOR 14 - [Si (R 1 2-b) (X b) O] m Si (R 2 3-a) X a (10)
(In the formula, R ¹¹ is the same as in the general formula (8). R ¹⁴ represents a divalent alkylene group having 1 to 6 carbon atoms. R ¹ , R ² , X, a, b and m are the general formula (1). Or the general formula (11):
^{_{CH 2 = C (R 11)}} - [Si (R 1 2-b) (X b) O] m Si (R 2 3-a) X a (11)
(Wherein R ¹ , R ² , X, a, b and m are the same as in general formula (1). R ¹¹ is the same as in general formula (8)).

R ^{14 in the} general formula (10) is preferably a divalent alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group or a propylene group, and more preferably a divalent alkylene group having 1 to 4 carbon atoms. preferable.

  The monomer represented by the general formula (10) or (11) may be one kind or two or more kinds.

  Examples of the compound represented by the general formula (10) or (11) having a polymerizable unsaturated bond and a reactive silicon group include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-, such as γ-methacryloxypropylalkylpolyalkoxysilane such as γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyltriethoxysilane Examples thereof include vinylalkyl polyalkoxysilanes such as acryloxypropylalkylpolyalkoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, and vinyltriethoxysilane.

  Examples of the Y ′ group and Y ″ group described in (II) include a combination of various groups. For example, an amino group, a hydroxyl group and a carboxyl group are exemplified as the Y ′ group, and an isocyanate group is exemplified as the Y ″ group. Can do. As another example, as described in JP-A-62-70405, JP-A-09-272714, and JP-A-59-168014, the Y ′ group is an allyl group, a Y ″ group. Examples thereof include a silicon hydride group (H—Si), in which the Y ′ group and the Y ″ group can be bonded by a hydrosilylation reaction in the presence of a group 10 transition metal.

  Examples of the mercaptan containing a reactive silicon group used as the chain transfer agent described in (III) include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropyltriethoxysilane. it can. Further, as described in JP-A-60-228516, the presence of a mercaptan containing monomers (a) and (b) as a bifunctional radical polymerizable compound and an alkoxysilyl group as a chain transfer agent A method of copolymerization under the above is also possible.

  Examples of the azobisnitrile compound or disulfide compound containing a reactive silicon group described in (IV) include alkoxysilyl groups described in JP-A-60-23405 and JP-A-62-70405. Examples thereof include azobisnitrile compounds containing a disulfide and disulfide compounds containing an alkoxysilyl group.

  Examples of the method described in (V) include the methods described in JP-A No. 09-272714.

  In addition, there is a method in which a mercaptan having a reactive silicon group and a radical polymerization initiator having a reactive silicon group are used in combination, as described in JP-A Nos. 59-168014 and 60-228516. I can give you.

  The number of reactive silicon groups contained in the copolymer (B) is not particularly limited, but it has an average of 0 per molecule of the copolymer (B) from the viewpoint of the effect on adhesive force and cost. The number is preferably 1 or more and 2.0 or less, and more preferably 0.5 or more and 1.5 or less.

  Moreover, it is preferable from the point of the adhesive expression rate to have three hydroxyl groups and / or hydrolyzable groups on one silicon atom.

  The proportion of the reactive silicon group-containing oxyalkylene polymer (A) and the copolymer (B) used in the composition used in the present invention is such that the amount of the copolymer (B) is reactive silicon group-containing oxy. The range of 10 to 200 parts by weight with respect to 100 parts by weight of the alkylene polymer (A) is preferable from the viewpoint of the effect of the expression of characteristics, more preferably 20 to 160 parts by weight, and usually intended use. It is selected according to performance.

  As tackifying resin (C) used for this invention, there is no restriction | limiting in particular and what is normally used can be used. Specific examples include terpene resins, aromatic modified terpene resins and hydrogenated terpene resins obtained by hydrogenation thereof, terpene-phenol resins obtained by copolymerizing terpenes with phenols, phenol resins, modified phenol resins, xylene-phenols. Resin, cyclopentadiene-phenol 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, DCPD resin and the like. These may be used alone or in combination of two or more.

  In particular, it is preferable to contain at least one compound that is compatible with the oxyalkylene polymer (A) and / or copolymer (B) at 23 ° C. and at least one compound that is incompatible with each other in order to exhibit excellent adhesive properties. . As the compound compatible with the oxyalkylene polymer (A) and / or the copolymer (B), a terpene-phenol resin is preferable. Further, as the incompatible compound, a hydrogenated terpene resin is preferable.

  The amount of the tackifier resin (C) used is 100 parts by weight of the oxyalkylene polymer (A) (when the copolymer (B) is included, the oxyalkylene polymer (A) and the copolymer (B) 20 to 100 parts by weight, preferably 40 to 80 parts by weight based on 100 parts by weight of the total amount. If it is less than 20 parts by weight, the tack (adhesive strength) is insufficient, and if it exceeds 100 parts by weight, the curing rate is slowed down, and the pressure-sensitive adhesive layer formation time is slowed down. is there.

  The curing catalyst (D) used in the present invention is not particularly limited, and a silanol condensation catalyst that promotes a reaction of a reactive silicon group that is usually used is used. Specific examples of such curing catalysts include, for example, titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetraacetylacetonate, bisacetylacetonatodiisopropoxytitanium; dibutyltin dilaurate, dibutyltin maleate, dibutyltin Phthalate, dibutyltin dioctate, dibutyltin diethylhexanolate, dibutyltin dimethylmaleate, dibutyltin diethylmaleate, dibutyltin dibutylmaleate, dibutyltin dioctylmaleate, dibutyltin ditridecylmaleate, dibutyltin dibenzylmaleate, Dibutyltin diacetate, dioctyltin diethyl maleate, dioctyltin dioctyl maleate, dibutyltin dimethoxide, dibutyltin dinonylphenoxide, dibutenyl Tetravalent organotin compounds such as oxide, dibutyltin diacetylacetonate, dibutyltin diethylacetoacetonate, reaction product of dibutyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate ester; aluminum trisacetylacetate Organic aluminum compounds such as narate, aluminum trisethyl acetoacetate and diisopropoxyaluminum ethyl acetoacetate; and zirconium compounds such as zirconium tetraacetylacetonate. Other reactants such as amine compounds, acidic phosphate esters, reactants of acidic phosphate esters and amine compounds, saturated or unsaturated polyvalent carboxylic acids or acid anhydrides thereof, salts of carboxylic acid compounds and amine compounds, etc. And lead octylate.

  The amount of these curing catalysts (D) used is a total of 100 parts by weight of the oxyalkylene polymer (A) and the tackifier resin (C) (in the case of containing the copolymer (B), It is 0.05 weight part or more and 10 weight part or less with respect to a unification | combination (A), a copolymer (B), and tackifying resin (C) 100 weight part. Preferably, it is 0.5 to 5 parts by weight. If it is less than 0.05 part by weight, the curing rate tends to be slow and the open time tends to be long. On the other hand, when the amount is 10 parts by weight or more, the workability such that the adhesiveness of the obtained cured product to the adherend is lowered or the open time becomes too short and the composition cannot be applied tends to be lowered.

  Unlike the conventional solvent type, the composition used in the present invention can be used without a solvent, but for the purpose of adjusting the viscosity, it is also possible to use a solvent as the component (E). . Such a solvent is not particularly limited as long as it can dissolve the component (A), the component (B), and the component (C), and conventionally known solvents can be widely used. For example, methanol, ethanol, isopropyl alcohol Alcohols such as acetone, methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, aliphatic hydrocarbons such as n-hexane and n-heptane, aromatic hydrocarbons such as toluene and xylene, etc. Solvents can be used alone or in combination. Among these, alcohols are more preferable in view of solvent toxicity.

  When the solvent (E) is blended with the curable composition, the blending amount is 100 parts by weight of the oxyalkylene polymer (A) (when the copolymer (B) is used, the oxyalkylene polymer (A) is used. ) And the copolymer (B) in a total amount of 100 parts by weight) is preferably 0.1 to 50 parts by weight. When the amount is less than 0.1 part by weight, the meaning of blending the solvent (E) is dilute. When the amount is more than 50 parts by weight, the volatilization amount during coating is increased, the working environment is deteriorated, and the curing is Tend to be late.

  In addition to the above, 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.

  Specific examples of the silane coupling agent include amino group-containing silanes such as N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane. An epoxy group-containing silane such as γ-glycidoxypropyltrimethoxysilane; a vinyl-type unsaturated group-containing silane such as vinyltrimethoxysilane; an isocyanate group-containing silane such as γ-isocyanatopropyltrimethoxysilane; These silane coupling agents may be used alone or in combination of two or more. Among these, aminosilane, its reaction product, epoxy silane, and isocyanate silane are particularly preferable from the viewpoint of adhesiveness.

  The silane coupling agent is 100 parts by weight of the oxyalkylene polymer (A) (when the copolymer (B) is used, the total of the oxyalkylene polymer (A) and the copolymer (B) is 100 parts by weight. ) To 1 to 20 parts by weight, preferably 2 to 10 parts by weight.

  Specific examples of the filler include, for example, calcium carbonate, magnesium carbonate, titanium oxide, carbon black, fused silica, precipitated silica, diatomaceous earth, white clay, kaolin, clay, talc, wood powder, walnut shell powder, rice husk Inorganic fillers such as powder, silicic anhydride, quartz powder, aluminum powder, zinc powder, asbestos, glass fiber, carbon fiber, glass beads, alumina, glass balloon, shirasu balloon, silica balloon calcium oxide, magnesium oxide, silicon oxide Wood fillers such as pulp and cotton chips, powder rubber, recycled rubber, fine powder of thermoplastic or thermosetting resin, hollow bodies such as polyethylene, etc. are listed as organic fillers, and these fillers can be used alone. You may use, and may use 2 or more types together. Among these, calcium carbonate is particularly preferable from the viewpoints of quality and economy.

  When the amount of the filler used is increased, workability is reduced due to an increase in viscosity, and the adhesive properties of a cured product obtained by curing the curable composition are also reduced. Therefore, 100 parts by weight of the oxyalkylene polymer (A) ( When using a copolymer (B), it is preferable to use 10-200 weight part with respect to an oxyalkylene type polymer (A) and a copolymer (B) 100 weight part in total), and 20-100. More preferably, parts by weight are used.

  Specific examples of the thixotropic agent include hydrogenated castor oil, organic amide wax, organic bentonite, calcium stearate and the like. These thixotropic agents may be used alone or in combination of two or more. May be.

  The amount of the thixotropic agent used is 100 parts by weight of the oxyalkylene polymer (A) from the point of thixotropy (when the copolymer (B) is used, the oxyalkylene polymer (A) and the copolymer are used. It is preferable to use 0.1-50 weight part with respect to (B) total amount 100 weight part), and it is more preferable to use 5-30 weight part.

  Specific examples of the plasticizer include, for example, phthalic acid esters such as dioctyl phthalate and diisodecyl phthalate; aliphatic dibasic acid esters such as dioctyl adipate; and epoxy plasticizers such as epoxidized soybean oil and epoxidized linseed oil Polyethers such as polypropylene glycol and derivatives thereof, and vinyl polymers obtained by polymerizing vinyl monomers by various methods. These plasticizers may be used alone or in combination of two or more.

  The amount of the plasticizer used is 100 parts by weight of the oxyalkylene polymer (A) (when the copolymer (B) is used, the total amount of the oxyalkylene polymer (A) and the copolymer (B) is 100 weights. Part) is preferably used in an amount of 20 to 300 parts by weight, more preferably 30 to 200 parts by weight. If it is less than 20 parts by weight, the effect as a plasticizer tends not to be exhibited, and if it exceeds 300 parts by weight, the mechanical strength of the cured product tends to be insufficient.

  Specific examples of the stabilizer include an antioxidant, a light stabilizer, and an ultraviolet absorber.

  If an antioxidant is used, the weather resistance of the cured product can be increased. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred.

  The amount of the antioxidant used is 100 parts by weight of the oxyalkylene polymer (A) (when the copolymer (B) is used, the total amount of the oxyalkylene polymer (A) and the copolymer (B) is 100. 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight.

  When a light stabilizer is used, photooxidation deterioration of the cured product can be prevented. Examples of the light stabilizer include benzotriazole-based, hindered amine-based, and benzoate-based compounds, and hindered amine-based compounds are particularly preferable.

  The amount of the light stabilizer used is 100 parts by weight of the oxyalkylene polymer (A) (when the copolymer (B) is used, the total amount of the oxyalkylene polymer (A) and the copolymer (B) is 100. 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight.

  When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of ultraviolet absorbers include benzophenone, benzotriazole, salicylate, substituted tolyl, and metal chelate compounds, with benzotriazole being particularly preferred.

  The amount of the ultraviolet absorber used is 100 parts by weight of the oxyalkylene polymer (A) (when the copolymer (B) is used, the total amount of the oxyalkylene polymer (A) and the copolymer (B) is 100. 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight.

  Further, it is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in combination.

  Furthermore, you may add various additives to the curable composition used for this invention as needed for the purpose of adjustment of various physical properties of a curable composition or hardened | cured material. Examples of such additives include, for example, flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, Examples include 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 μm to 3 mm, more preferably 50 to 1 mm, further preferably 50 to 500 μm, and particularly preferably 60 to 250 μm. If the coating thickness exceeds 3 mm, water supply to the deep part is slow, and the curing reaction of the polymer does not proceed, so that the speed of developing the adhesive property tends to be slow. It is particularly preferable that the coating thickness is in the above range from the viewpoints of the adhesive property expression speed and adhesion strength securing.

  Since the curable composition used in the present invention uses a low-viscosity polymer, it can be sufficiently coated at room temperature even when mixed with a tackifier resin. It is preferable to heat and apply the curable composition used in the invention to 40 to 140 ° C, more preferably 50 to 120 ° C, and still more preferably 50 to 100 ° C. Heating the curable composition used in the present invention to the above temperature is particularly preferable from the viewpoint of workability and ensuring the stability of the curable composition.

  When heating and using a curable composition, the heating method can use a conventionally well-known method without a restriction | limiting, However, It is preferable to heat immediately before use especially in the state with which it filled with the airtight container. Furthermore, it is preferable to heat the sealed container with a heater having a heater member filled with the curable composition. Further, the most preferable method is to use a cartridge can as a hermetically sealed container and cover the cartridge can with a heating cylinder having a hollow cylindrical heater member while the cartridge can filled with the curable composition is housed in an extrusion gun. preferable.

  Since the one-pack type bonding agent of the present invention is filled with a curable composition in an airtight container, the curable composition can be discharged onto an adherend to directly form a coating film having a desired thickness. . Therefore, it is possible to reduce the necessity of separately preparing a coating tool such as a brush or an applicator.

  When applying the curable composition, a nozzle that can be connected to an airtight container can be used. In particular, the use of a nozzle with a coating portion having a rectangular opening applies the curable composition uniformly. Is preferable. Moreover, it is preferable that this nozzle opening part is 5-50 mm in the length of a longitudinal direction, and is 0.5-5 mm in the length of a short side direction. Furthermore, the length in the longitudinal direction is preferably 5 to 40 mm, and most preferably 5 to 30 mm. Moreover, it is preferable that the length of a short side direction is 0.5-3 mm, and it is most preferable that it is 0.5-1.5 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 as referred to in the present invention includes both a base material and a base material bonded thereto.

  As the base material, for example, concrete base, flexible board, pearlite board, calcium silicate board, mortar, PC board, ALC board, gypsum board, tile, etc., inorganic base board, plywood, MDF, particle board, hard board, flooring material, etc. Wood substrates, studs, runners, aluminum plates, various panels with aluminum films bonded together, metal substrates such as various anti-rust metal plates, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polytetrafluoro Examples thereof include various plastic plates and foams such as polyethylene, polyvinylidene fluoride, EVA and melamine, and plastic bases such as various panels on which these plastic films are bonded.

  In addition, as a base material bonded to the base, for example, cement board, wood wool cement board, flexible board, calcium silicate board, gypsum board, glass wool board, rock wool board, marble, stone, tile, decorative glass, etc. Base material, plywood, fiberboard, MDF, particle board, hard board, natural wood board, flooring material, baseboard, waist wall material, surrounding base material such as metal base material, polyethylene, polypropylene, polystyrene Plastics such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, cellulose diacetate, polytetrafluoroethylene, polyvinylidene fluoride, EVA, melamine, polymonochlorotrifluoroethylene, polyethersulfone, polymethylpentene, polyphenylene sulfide, etc. Plate or decorative material, film, floor coverings of PVC and olefin-based, baseboards, Koshikabezai, around the edge, such as a plastic-based material, such as wallpaper and the like.

  In particular, the one-pack type on-site coating adhesive filled in the sealed container of the present invention is lightweight so that the total weight of the sealed container is, for example, 10 kg or less. It is possible to cover the sealed container and bring the curable composition to a desired temperature. Furthermore, in the present invention, the curable composition is filled in a sealed container, and since the filling amount is also lightweight, the sealed container can be carried and applied to the application site of the bonding agent. It is preferable to use for bonding.

  Examples of interior materials include floor materials (floor finishing materials), wall materials, and ceiling materials.

  As flooring materials, vinyl floor sheet, olefin floor sheet, carpet, cork carpet, grass carpet, wood carpet, solid flooring material, WPC flooring material, single board flooring material, sound insulation flooring material, natural stone material, synthetic stone material, composition Examples thereof include vinyl floor tiles, homogeneous vinyl floor tiles, carpet tiles, linoleum floor tiles, rubber floor tiles, terrazzo tiles, and glass building materials.

  Cement board, wood cement board, flexible board, calcium silicate board, gypsum board, glass wool board, rock wool board, marble, stone, tile, decorative glass and other inorganic panels, plywood, fiber board, MDF , Particle board, hard board, wood panel such as natural wood board, metal panel, plastic panel such as polystyrene, melamine, wood system, PVC, olefin flooring, baseboard, waist wall material, surrounding edge, Wallpaper.

  Examples of the ceiling material include gypsum board, decorative plywood, and sound absorption tex.

  Among these, it is particularly preferable to use the one-pack type on-site coating bonding agent filled in the sealed container of the present invention for bonding floor materials (floor finishing materials).

  The site where the one-pack type bonding agent filled in the hermetic container of the present invention is used refers to a construction site where the above-mentioned various adherends are bonded, particularly interior materials, that is, floor materials, wall materials, and ceiling materials. It shows the construction site where the materials are pasted together.

  The curable composition used in the present invention can be prepared as a one-component type in which all the ingredients are pre-blended and sealed 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. For example, the above-described components are blended and kneaded using a mixer, roll, kneader, etc. at room temperature or under heating, or a suitable solvent is used. Ordinary methods such as dissolving the components using a small amount and mixing them can be used.

  The curable composition used for this invention is demonstrated based on an Example. EXAMPLES Hereinafter, the present invention will be specifically described with reference to synthesis examples and examples, but the present invention is not limited to these synthesis examples and examples.

(Synthesis Example 1)
A polyoxypropylene diol having a number average molecular weight of 2,000 is used as an initiator, and propylene oxide is polymerized using a zinc hexacyanocobaltate glyme complex catalyst to obtain a poly having a number average molecular weight of 29,000 (polystyrene conversion value obtained from GPC). Oxypropylene diol was obtained. After the obtained polyoxypropylene diol and sodium methoxide were reacted, allyl chloride was reacted to convert the terminal hydroxyl group into an unsaturated group. The number average molecular weight having a dimethoxymethylsilyl group at the molecular end by reacting 1 mol of dimethoxymethylsilane in the presence of a platinum divinyldisiloxane complex with 1 mol of unsaturated group of this unsaturated group-terminated polyoxypropylene polymer. A polyoxypropylene polymer having a molecular weight distribution of 30,000 and a molecular weight distribution of 1.3 (polystyrene conversion value determined from GPC) was obtained (Polymer A).

(Synthesis Example 2)
Polyoxypropylene diol having a number average molecular weight of 2,000 is used as an initiator, and propylene oxide is polymerized using a zinc hexacyanocobaltate glyme complex catalyst to obtain a poly having a number average molecular weight of 25,000 (polystyrene conversion value determined from GPC). Oxypropylene diol was obtained. After the obtained polyoxypropylene diol and sodium methoxide were reacted, allyl chloride was reacted to convert the terminal hydroxyl group into an unsaturated group. The number of trimethoxysilyl groups at the molecular ends is obtained by reacting 0.70 mol of trimethoxysilane in the presence of a platinum divinyldisiloxane complex with 1 mol of unsaturated groups of this unsaturated group-terminated polyoxypropylene polymer. A polyoxypropylene polymer having an average molecular weight of 26,000 and a molecular weight distribution of 1.3 (polystyrene conversion value determined from GPC) was obtained (Polymer B).

(Synthesis Example 3)
In 40 g of toluene heated to 105 ° C., 15 g of methyl methacrylate, 60 g of butyl acrylate, 20 g of stearyl methacrylate, 4.5 g of 3-methacryloxypropyldimethoxymethylsilane and 2,2′-azobisisobutyrate as a polymerization initiator A solution prepared by dissolving 2.0 g of ronitrile in 15 g of toluene was dropped over 5 hours, and then stirred for 2 hours. Further, by adding a solution prepared by dissolving 0.17 g of 2,2′-azobisisobutyronitrile in 10 g of toluene and stirring for 2 hours, a solid content concentration of 60% by weight and a number average molecular weight of 9,800 (GPC Obtained in terms of polystyrene), and an acrylic copolymer having 2.0 reactive silicon groups per molecule was obtained (Polymer C).

(Synthesis Example 4)
In 40 g of toluene heated to 105 ° C., 15 g of methyl methacrylate, 60 g of butyl acrylate, 20 g of stearyl methacrylate, 4.5 g of 3-methacryloxypropyltrimethoxysilane and 2,2′-azobisisobutyrate as a polymerization initiator A solution of 1.3 g of nitrile dissolved in 15 g of toluene was added dropwise over 5 hours, followed by stirring for 2 hours. Furthermore, by adding a solution prepared by dissolving 0.10 g of 2,2′-azobisisobutyronitrile in 10 g of toluene and stirring for 2 hours, a solid content concentration of 40% by weight and a number average molecular weight of 11,000 (GPC (Polystyrene conversion value), and an acrylic copolymer having 2.2 reactive silicon groups per molecule was obtained (Polymer D).

( Reference Examples 1, 5 and 6, Examples 2 to 4 and 7 to 9, Comparative Examples 1 to 5)
Components (A), (B) and (C) (in addition to these in Comparative Example 4) were mixed in the proportions shown in Table 1, dissolved by adding toluene, and then heated to 90 ° C. to reduce toluene. It was devolatilized. Subsequently, silane coupling was added and stirred for 30 minutes. Finally, after adding component (D) (further (E) component in Example 9) and stirring for 30 minutes, degassing was performed under reduced pressure, and an aluminum tube (100 ml) was filled with the composition. The weights of the aluminum tubes filled with the curable compositions of Reference Examples 1, 5 and 6, Examples 2 to 4 and 7 to 9, and Comparative Examples 1 to 5 were all 110 g. The aluminum tube was heated so that the obtained composition might be 80 degreeC, or it used for evaluation by room temperature state (23 degreeC). All the evaluations were performed in an atmosphere having a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 10%.

(Viscosity measurement):
The viscosity of the composition at 80 ° C. was measured using an E-type viscometer (3 ° × R14 cone).
(Workability):
The case where the composition could be easily ejected manually from the aluminum tube was marked with ◯, and the case where the composition could not be ejected easily was marked with ×.
(Coating thickness):
About the hardened | cured material which adjusted thickness with the applicator, the thickness measurement by a micro gauge was implemented.
(Adhesive layer formation time):
The composition was applied onto a flexible plate and the thickness was adjusted with an applicator. The surface of the composition 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.
(Adhesiveness):
Lamination after 90 minutes:
After applying the curable composition to a flexible plate (width 80 mm, length 150 mm, thickness 4 mm) and adjusting the thickness with an applicator, PET film (corona discharge treatment; width 25 mm, length 200 mm, thickness 90 minutes later) 0.05 mm) was bonded 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 the fracture state were observed (initial adhesiveness). The case where the tensile strength was 20 N / 25 mm or more was evaluated as ◯, and the case where it was less than 20 N / 25 mm was evaluated as x. Moreover, the case where it peeled between the adhesive layer and PET film was set as (circle), and the other was set as x. Furthermore, about the system which peeled between the adhesive layer and PET film, the new PET film was bonded again, and after 5 kg roller was applied once, it was cured for 1 week, and the peeling test was implemented (re-adhesiveness).
Bonding immediately after application:
After applying the curable composition to a flexible plate and adjusting the thickness with an applicator, the PET film was immediately bonded and cured for one week. After curing, a 180 ° peel test was carried out with a tensile tester, and the tensile strength and fracture state were observed (initial adhesiveness). The case where the tensile strength was 20 N / 25 mm or more was evaluated as ◯, and the case where it was less than 20 N / 25 mm was evaluated as x. Moreover, the case where it peeled between the adhesive layer and PET film was set as (circle), and the other was set as x.

  Furthermore, about the system which peeled between the adhesive layer and PET film, the new PET film was bonded again, and after 5 kg roller was applied once, it was cured for 1 week, and the peeling test was implemented (re-adhesiveness).

(Storage stability):
The aluminum tube filled with the composition was allowed to stand at 23 ° C. for 4 weeks, and then heated to the coating temperature to discharge the composition, and the presence or absence of a gel-like material was examined. The case where no gel-like material was observed was marked with ◯, and the case where a gel-like material was confirmed was marked with ×.

  The evaluation results are shown in Table 1.

(Example 10)
The composition of Example 3 was filled into a PE 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 constant temperature bath at 80 ° C., and the filled composition was 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 was bonded onto a flexible plate as a wall base material, but the panel was sufficiently fixed to the wall without shifting from immediately after bonding. Further, the panel was peeled off after one week at room temperature, but the phenomenon such as destruction of the panel was not observed, and the panel could be peeled off relatively easily.

(Comparative Example 6)
Using a commercially available chloroprene solvent-type adhesive (G-17, manufactured by Konishi Co., Ltd.), the panel was attached and peeled off in the same manner as in Example 10. As a result, there was no problem in the initial fixing property of the panel, but peeling was difficult.

(Comparative Example 7)
A commercially available double-sided tape (CV-25, manufactured by Sumitomo 3M Co., Ltd.) was used, and the tape was applied to the same location as the composition was applied in Example 10, and the panel was attached to and pulled from the base material. Peeling was performed. As a result, the initial fixability of the panel and ease of peeling were sufficient, but the work of peeling the release paper from the double-sided tape was a hassle when attaching the panel, and a large amount of release paper was generated as waste. did.

(Example 11)
In the same manner as in Example 10, the cartridge filled composition was heated to 80 ° C., then loaded into a hand gun, covered with a removable mantle heater, and the temperature of the filled composition was 80 ° C. The coating was repeated while maintaining the state. In Example 10, the cartridge was gradually cooled and it became difficult to discharge 40 minutes after the start of use, but in Example 11, the cartridge could be used without any limitation.

(Example 12)
In the same manner as in Example 10, the cartridge was heated so that the composition became 80 ° C., and then loaded into a hand gun equipped with a heater, and coating was repeated while maintaining the temperature of the composition at 80 ° C. In Example 10, the cartridge was gradually cooled and it became difficult to discharge 40 minutes after the start of use, but in Example 12, the cartridge could be used without any limitation.

(Example 13)
The composition of Example 3 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 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 10, the cartridge was gradually cooled and it became difficult to discharge after 40 minutes from the start of use, but in Example 13, the cartridge could be used without any limitation.

(Example 14)
In the same operation as in Example 11, a type in which the coating part was opened in a square shape as a nozzle for the cartridge (nozzle opening part: 11 mm in the longitudinal direction and 2 mm in the short side direction) was used, and a melamine panel (3 × 935) × 2450) was partially coated. At this time, the surface of the composition was smooth and there was no large variation in thickness. After 90 minutes, the panel was bonded onto a flexible plate as a wall base material, but the panel was sufficiently fixed to the wall without shifting from immediately after bonding. Further, the panel was peeled off after one week at room temperature, but the phenomenon such as destruction of the panel was not observed, and the panel could be peeled off relatively easily.

(Example 15)
In the same manner as in Example 14, the composition was partially applied to the flooring material. After 90 minutes, the flooring material was bonded to the plywood as the floor base material, but the flooring material was sufficiently fixed to the floor without shifting from immediately after the bonding. Further, after one week at room temperature, the flooring material was peeled off, but no phenomenon such as destruction of the flooring material was observed, and the flooring material could be peeled off relatively easily.

  As described above, the one-part bonding agent for on-site construction described in the examples forms a pressure-sensitive adhesive layer at an early stage with good workability, initial adherend fixability, long-term easy peelability, re-adhesion, storage Although it is excellent in stability, a system that exhibits these physical properties in a well-balanced manner was not found in the composition of the comparative example. Moreover, in the heat coating using the heater of an Example, it was usable without a restriction | limiting in application time. In addition, by using a nozzle in which the coating portion of the example was opened in a square shape, sufficient bonding was possible even with a long open time after coating.

  According to the present invention, a pressure-sensitive 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 pressure-sensitive adhesive can be simplified. In addition, since the adherend bonded with the pressure-sensitive adhesive is easy to peel off, it is possible to simplify operations such as remodeling after use.

  In the present invention, since a crosslinkable polymer having a reactive silicon group capable of forming a siloxane bond is used, the heating temperature of the curable composition can be designed to be about 40 to 140 ° C. and installed in a factory. No special equipment is required and there are few restrictions on the construction site.

  By this invention, the adhesive which does not require the drying process of a solvent can be formed easily and rapidly at construction sites, such as a building, and handling of an adhesive can be simplified. Moreover, since the adherend bonded with the pressure-sensitive adhesive can be easily peeled off, it is possible to simplify operations such as remodeling after use. Furthermore, the present invention removes various restrictions by filling a hermetic container with a curable composition containing a tackifier, thereby providing a new system for pasting work that did not exist in the past. It is.

Claims (8)

Oxyalkylene polymer (A) having a reactive silicon group capable of forming a siloxane bond and having no urethane bond or urea bond (A) and (B) alkyl acrylate having substantially one or more molecular chains It contains a copolymer containing an ester monomer unit and / or a methacrylic acid alkyl ester monomer unit, and further 20 to 100 parts by weight of an adhesive with respect to 100 parts by weight of the total amount of components (A) and (B) It comprises a curable composition containing 0.05 to 10 parts by weight of the curing catalyst (D) with respect to 100 parts by weight of the total amount of the resin (C) and the components (A), (B) and (C). a one-part bonding agent, the component (B), the molecular chain is substantially (a) alkyl acrylate monomer units having an alkyl group of 1 to 8 carbon atoms and / or methacrylic acid alkyl A copolymer (B) -a containing ester monomer units and (b) acrylic acid alkyl ester monomer unit and / or methacrylic acid alkyl ester monomer unit having an alkyl group having 10 or more carbon atoms, A one-component bonding agent for on- site coating, wherein the curable composition is filled in an airtight container. The one-component bonding agent according to claim 1, wherein the curable composition has a viscosity of 3 to 50 Pa · s / 80 ° C. The one-component bonding agent according to claim 1 or 2 , wherein the curable composition after coating is a curable composition capable of curing within 90 minutes after coating to form an adhesive layer. The one-pack type bonding according to any one of claims 1 to 3 , wherein the oxyalkylene polymer (A) has a number average molecular weight of 10,000 to 100,000 and a molecular weight distribution of 1.6 or less. Agent. Oxyalkylene polymer (A) is either one of claims 1 to 4 on the silicon atom is three hydroxyl groups and / or hydrolyzable group is a polymer having a reactive silicon group bound 1 The one-component bonding agent according to item. Copolymer (B) is, in one claim 1 on the silicon atom is three hydroxyl groups and / or hydrolyzable group is a polymer having a reactive silicon group attached to The one-component bonding agent described. Curable composition, an oxyalkylene polymer (A) and the copolymer per 100 parts by weight of from 0.1 to 50 parts by weight (E) of the preceding claims containing solvent (B) The one-component bonding agent according to any one of the above items. The one-component bonding agent according to any one of claims 1 to 7 , wherein the total weight of the closed container filled with the curable composition is 10 kg or less.