JP5605906B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition containing a reactive silicon group-containing polyoxyalkylene polymer, a modified styrene / ethylene / butylene block copolymer, and a liquid polyolefin polymer. Moreover, it is related with the adhesive for waterproof sheets and the adhesive for floors which use this curable composition. In particular, the present invention relates to a curable composition having excellent adhesion to a difficult-to-adhere substrate based on polyethylene or ionomer resin.

  It is known that an organic polymer having a reactive silicon group in a molecule becomes a rubber-like cured product when a reactive silicon group hydrolyzed by moisture forms a siloxane bond. Among such organic polymers having a reactive silicon group, a polymer whose main chain is polyoxyalkylene has already been industrially produced, and is a sealing material, adhesive, injection material, putty material, paint. It is widely used for such applications.

  In these applications, adhesiveness to various materials is required, so that adhesion is improved by adding an adhesion-imparting agent such as a silane coupling agent or a titanium coupling agent. (For example, Patent Document 1 and Patent Document 2). In addition, improvement in adhesion by adding an epoxy resin (for example, Patent Document 3) and improvement in adhesion by adding a compatible acrylic resin (for example, Patent Document 4) have been performed.

  In recent years, studies have been made on improving the adhesion of a polypropylene material to a difficult-to-adhere substrate such as TPO (thermoplastic polyolefin) by adding a polyolefin polymer (for example, Patent Document 5). .

JP-A-57-182350 JP 59-024771 JP-A-61-268720 Japanese Unexamined Patent Publication No. Sho 63-112642 WO2007 / 142067

For polyethylene or ionomer resin-based substrates, which are one of the difficult-to-adhere substrates used for roofing waterproof sheets and films, non-vinyl chloride flooring, etc., those having sufficient adhesive properties are still available. It wasn't.
The current tarpaulin is usually a polypropylene or polypropylene film stretched over a bitumen sheet, and the film and bitumen (only the lower layer) are melted and pasted with a burner at the time of enforcement, but there is a risk of fire and smell There is a need for an adhesive that can be applied at room temperature. As the waterproof film, polyethylene-based Tyvek (manufactured by Dupont) is the most common, but since an aqueous adhesive is used, the adhesiveness is not sufficient (peeling off at the interface), and there is a need for a solventless adhesive is there.

  In addition, non-vinyl chloride flooring is on the market, and water-based adhesives or two-component polyurethane adhesives are currently used as adhesives, but their adhesiveness and adhesive strength are not sufficient, and solvent-free adhesives are used. There is a demand for drugs. A water-based adhesive has strength but is interface fracture. A two-component polyurethane adhesive is adhesively broken but has low strength. Non-PVC flooring materials use difficult-to-adhere polyethylene resins and ionomer resins (resins in which the molecules of ethylene-methacrylic acid copolymer are intermolecularly bonded with metal ions such as sodium and zinc). It is.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that a curable composition comprising a reactive silicon group-containing polyoxyalkylene polymer and a modified styrene / ethylene / butylene block copolymer and a liquid polyolefin polymer. By using the composition, it discovered that the adhesiveness to a hardly-adhesive base material was securable, and came to this invention.

That is, the present invention
(1) (A) Polyoxyalkylene polymer having a reactive silicon group represented by the following general formula (1), (B) modified styrene / ethylene / butylene block copolymer, and (C) liquid polyolefin The present invention relates to a curable composition containing a polymer.
—Si (R ¹ _3-a ) X _a (1)
(In the formula, R ¹ represents 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 a triorganosiloxy group represented by (RO) ₃ Si—. And when two R ¹ are present, they may be the same or different, where R is a monovalent hydrocarbon group having 1 to 20 carbon atoms and 3 R X 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 or different. 2 or 3 is shown.)
(2) The curable composition according to (1), wherein the main chain skeleton of the component (A) is a polyoxypropylene polymer.
(3) The component (A) has a group represented by the following general formula (2) in the molecule, and relates to the curable composition as described in (1) or (2).
—NR ² —C (═O) — (2)
(Wherein, ^{R 2} represents a hydrogen atom or 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.)
(4) The curable composition according to any one of (1) to (3), wherein the component (B) is a maleic anhydride-modified styrene / ethylene / butylene block copolymer It is.
(5) The curable composition according to any one of (1) to (4), wherein the component (B) is a styrene / ethylene / butylene block copolymer grafted with maleic anhydride. It is about.
(6) The component (C) is a liquid conjugated polyene polymer, and relates to the curable composition as described in any one of (1) to (5).
(7) The component (C) is a liquid polyisoprene polymer, and relates to the curable composition as described in (6).
(8) The curable composition according to (7), wherein the main chain skeleton of the component (C) is a copolymer of polyisoprene and styrene.
(9) The curable composition as described in any one of (1) to (8), wherein the component (C) is a hydrogenated polymer.
(10) The present invention relates to a waterproof sheet and a film adhesive using the curable composition according to any one of (1) to (9).
(11) The present invention relates to a floor adhesive comprising the curable composition according to any one of (1) to (9).
(12) The present invention relates to an adhesive for adhering a polyethylene resin or ionomer resin using the curable composition according to any one of (1) to (9).
(13) The present invention relates to a cured product of the curable composition according to any one of (1) to (9).

  By using the curable composition of this invention, it has the adhesiveness outstanding with respect to the polyethylene resin base material and ionomer resin base material which are conventionally known as a hard-to-bond base material. Therefore, it is useful as an adhesive for such a difficult-to-adhere substrate.

Examples of the main chain skeleton in the polyoxyalkylene polymer having a reactive silicon group (A) of the present invention include those having a repeating unit represented by the general formula (3).
—R ³ —O— (3)
(In the formula, R ³ is a divalent organic group and represents a linear or branched alkylene group having 1 to 14 carbon atoms).
Specific examples of the repeating unit represented by the general formula (3) include, for example, —CH ₂ CH ₂ O—, —CH (CH ₃ ) CH ₂ O—, —CH (C ₂ H ₅ ) CH ₂ O—. _{, -C (CH 3) 2 CH} 2 O -, - CH 2 CH 2 CH 2 CH 2 O- and the like.

The main chain skeleton of the polyoxyalkylene polymer may consist of only one type of repeating unit or may consist of two or more types of repeating units. In particular, polyoxypropylene having a repeating unit of —CH (CH ₃ ) CH ₂ O— is amorphous, which is preferable from the viewpoint that the polymer can be appropriately reduced in viscosity and can be provided with appropriate flexibility in the cured product. .

  As a method for synthesizing a polyoxyalkylene polymer, for example, a polymerization method using an alkali catalyst such as KOH, for example, a complex obtained by reacting an organoaluminum compound and porphyrin disclosed in JP-A-61-215623 A polymerization method using a transition metal compound-porphyrin complex catalyst, for example, a polymerization method using a double metal cyanide complex catalyst shown in JP-B-46-27250 and JP-B-59-15336 can be exemplified, but is particularly limited. It is not a thing.

The reactive silicon group in the polyoxyalkylene polymer having a reactive silicon group (A) of the present invention has a hydroxyl group or hydrolyzable group bonded to a silicon atom, and is reacted by a reaction catalyzed by a silanol condensation catalyst. It is a group capable of forming a siloxane bond. Examples of the reactive silicon group include a group represented by the following general formula (1).
—Si (R ¹ _3-a ) X _a (1)
(In the formula, R ¹ represents 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 a triorganosiloxy group represented by (RO) ₃ Si—. And when two R ¹ are present, they may be the same or different, where R is a monovalent hydrocarbon group having 1 to 20 carbon atoms and 3 R X 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 or different. 2 or 3 is shown.)

  When X of the said General formula (1) is a hydrolysable group, it will not specifically limit, What is necessary is just a well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group are particularly preferable in terms of mild hydrolysis and easy handling.

R ^{1 in the} general formula (1) is not particularly limited and may be a known one. Specific examples include an alkyl group such as a methyl group, an ethyl group, a propyl group, and an isopropyl group, an aryl group such as a phenyl group, and an aralkyl group such as a benzyl group. Among these, a methyl group is particularly preferable from the viewpoint of raw material availability.

  The specific structure of the reactive silicon group represented by the general formula (1) is not particularly limited as long as it is a known structure. In particular, from the viewpoint of reactivity and availability, a trimethoxysilyl group, a methyldimethoxysilyl group, a triethoxysilyl group, and a methyldiethoxysilyl group are preferable.

  In addition, the reactive silicon group may be used alone or in combination of two or more.

  Introduction of the reactive silicon group into the polyoxyalkylene polymer may be performed by a known method. For example, the following method is mentioned.

  (I) An organic polymer containing an unsaturated group by reacting an organic polymer having a functional group such as a hydroxyl group in the molecule with an organic compound having an active group and an unsaturated group that are reactive with the functional group. A polymer is obtained. Alternatively, for example, when an epoxide is ring-opened to obtain an organic polymer, an unsaturated group-containing epoxide is subjected to ring-opening copolymerization to obtain an unsaturated group-containing organic polymer. An unsaturated group-containing organic polymer is obtained by copolymerizing a monomer having the above. Next, hydrosilane having a reactive silicon group is allowed to act on the obtained reaction product to effect hydrosilylation.

In the method (i), in order to introduce a reactive silicon group at a high introduction rate, CH ₂ ═C (R ⁴ ) —CH ₂ — or CH (R ⁴ ) ═CH ₂ —CH ₂ — R ⁴ is preferably introduced by adding a hydrosilane compound to an organic polymer containing an unsaturated group represented by hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. More preferably, R ⁴ is hydrogen or a methyl group, and it is particularly important that R ⁴ is a methyl group in order to make the introduction rate of the reactive silicon group 85% or more.

  Specific examples of the hydrosilane compound used in the method (i) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, and methyldiethoxysilane. Alkoxysilanes such as methyldimethoxysilane and phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; bis (dimethylketoximate) methylsilane, bis (cyclohexylketoximate) methylsilane Examples thereof include, but are not limited to, ketoximate silanes. Among these, halogenated silanes and alkoxysilanes are particularly preferable, and alkoxysilanes are particularly preferable because the hydrolyzability of the resulting composition is gentle and easy to handle.

  (Ii) A compound having a mercapto group and a reactive silicon group is reacted with the organic polymer containing an unsaturated group obtained in the same manner as in the method (i).

  As a synthesis method of (ii), for example, a compound having a mercapto group and a reactive silicon group is introduced into an unsaturated bond site of an organic polymer by a radical addition reaction in the presence of a radical initiator and / or a radical generation source. Examples of the method include, but are not limited to. Specific examples of the compound having a mercapto group and a reactive silicon group include, for example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxy. Although silane etc. are mention | raise | lifted, it is not limited to these.

  (Iii) An organic polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in the molecule is reacted with a compound having a reactive functional group and a reactive silicon group.

  As a method of reacting an organic polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a reactive silicon group in the synthesis method of (iii), for example, a method disclosed in JP-A-3-47825, etc. However, it is not particularly limited. Specific examples of the compound having an isocyanate group and a reactive silicon group include, for example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-isocyanatepropylmethyldiethoxy. Although silane etc. are mention | raise | lifted, it is not limited to these.

  Among the above methods, since the polymer obtained by the method (ii) has a strong odor due to mercaptosilane, the method (i) or the method (iii) is preferable.

Furthermore, among the methods (iii), a method of reacting a polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a reactive silicon group is preferable because a high conversion can be obtained in a relatively short reaction time. The oxyalkylene polymer obtained by such a reaction becomes a polymer having a group represented by the following general formula (2) together with a reactive silicon group.
—NR ² —C (═O) — (2)
(Wherein, ^{R 2} represents a hydrogen atom or 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.)

  In addition, the (A) component which has group represented by the said General formula (2) is obtained also by methods other than the above. Specific examples include diisocyanate compounds such as aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate, and aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate, and the above general formula. What is obtained from a chain extension reaction with a polyol having a repeating unit of (3) has a group of general formula (2) regardless of the method for introducing a reactive silicon group.

  Speaking of the method for introducing reactive silicon groups, the organic polymer having reactive silicon groups obtained by the method (i) has a lower viscosity and better workability than the polymer obtained by the method (iii). It is preferable in that it becomes a product. On the other hand, the method (iii) is preferable in that the introduction of the silyl group into the hydroxyl group-containing polymer can be achieved in one step, so that the component (A) can be produced with good productivity.

  The component (A) may be linear or branched, and the number average molecular weight thereof is preferably 3,000 or more and preferably 100,000 or less in terms of polystyrene by gel permeation chromatography (GPC). Is. More preferably, it is 10,000 or more and 50,000 or less. If the number average molecular weight is less than 10,000, the composition tends to have a high hardness and an inconvenient tendency. If the number average molecular weight exceeds 50,000, the composition tends to be inconvenient in terms of workability because of high viscosity.

  The reactive silicon group in the component (A) may be bonded to the terminal or the inside of the polyoxyalkylene polymer, or may be bonded to both the terminal and the inside. In particular, when a reactive silicon group is bonded only to the molecular terminal, a network of polymer components contained in the composition is efficiently constructed, so that a rubber-like cured product having high strength and high elongation can be obtained. It is preferable from the viewpoint of being easily made.

Although a method of measuring the introduction rate of the reactive silicon group in the component (A) various methods are conceivable, by ^{1 H-NMR} spectrum, and calculating the integral value of terminal or the like which is introduced in the reactive silicon group Can do. The introduction rate of reactive silicon groups is a numerical value expressed as a percentage by dividing the number of reactive silicon groups present in the molecule by the number of molecular ends. That is, the introduction rate in the case of a linear polymer having two reactive silicon groups on average in one molecule (that is, a polymer having two molecular ends) is calculated as 100%. For this reason, in a polymer in which a large number of reactive silicon groups are present at sites other than the molecular ends, the calculated value of the introduction rate may exceed 100%.

  The average number of reactive silicon groups in one molecule of the component (A) polymer is preferably 1 or more, and preferably 1.1 to 5. When the number of reactive silicon groups contained in the molecule is less than 1, the cured product may have insufficient curability, and good rubber elasticity may not be obtained. This is not preferable because it becomes hard and brittle and has poor rubber elasticity.

  (A) Specific examples of the polyoxyalkylene polymer having a reactive silicon group include, for example, JP-B Nos. 45-36319, 46-12154, JP-A Nos. 50-156599, 54-6096, 55-13767, 55-13468, 57-164123, Japanese Patent Publication No. 3-2450, U.S. Patent 3,632,557, U.S. Patent 4,345,053, U.S. Patent 4,366,307, United States Patents proposed in Japanese Patent Nos. 4,960,844, etc., and Japanese Patent Laid-Open Nos. 61-197631, 61-215622, 61-215623, and 61-218632 A polyoxyal having a reactive silicon group with a narrow molecular weight distribution and a high molecular weight having a number average molecular weight of 6,000 or more and a molecular weight distribution (Mw / Mn) of 1.6 or less Ren polymer can be exemplified, but not particularly limited thereto.

  The polyoxyalkylene polymer having a reactive silicon group may be used alone or in combination of two or more.

The (B) modified styrene / ethylene / butylene block copolymer used in the present invention is not particularly limited, and known ones can be used. Examples of modified styrene / ethylene / butylene block copolymers include maleic anhydride modified styrene / ethylene / butylene block copolymers, maleic acid modified styrene / ethylene / butylene block copolymers, carboxylic acid modified styrene / ethylene / butylene blocks. Examples include, but are not limited to, copolymers, epoxy-modified styrene / ethylene / butylene block copolymers, and imino-modified styrene / ethylene / butylene block copolymers. Among these, a maleic anhydride-modified styrene / ethylene / butylene block copolymer is preferable because of its availability and excellent physical properties of the resulting cured product. Specifically, a product obtained by graft-modifying maleic anhydride on a styrene / ethylene / butylene block copolymer can be used. Specific products include, for example, Kraton resins FG1901 and FG1924. These modified styrene / ethylene / butylene block copolymers may be used alone or in combination of two or more.
(B) Although the compounding ratio of (B) component with respect to 100 weight part of (A) component is not specifically limited, 2-40 parts are preferable and 5-20 parts are especially preferable. When the amount is less than 2 parts, there is a problem of adhesion deterioration, and when it is more than 40 parts, there is a problem of compatibility.
It is preferable to use the component (B) after being dissolved in a phthalate ester such as DIDP in advance from the viewpoint of mixing workability with the component (A).

  The (C) liquid polyolefin polymer used in the present invention is not particularly limited, and known ones can be used. Specifically, a liquid polymer of ethylene hydrocarbon, or a liquid conjugated polyene polymer such as a liquid polyisoprene polymer or a liquid polybutadiene polymer can be used. Polymers are preferred, and liquid polyisoprene polymers are more preferred. Specific examples of the liquid polyisoprene polymer include a liquid polyisoprene homopolymer, a copolymer of isoprene and styrene, a copolymer of isoprene and butadiene, a maleic anhydride-modified polyisoprene, and a hydrogenated polyisoprene. can give. Among these liquid polyisoprene polymers, a copolymer of polyisoprene and styrene and hydrogenated polyisoprene are preferable. Specific examples of the liquid polybutadiene polymer include a liquid polybutadiene homopolymer, a copolymer of butadiene and styrene, a maleic anhydride-modified polybutadiene, a hydrogenated polybutadiene, and the like. Specific examples of the ethylene hydrocarbon liquid polymer include polybutene, hydrogenated polybutene, polyisobutylene, hydrogenated polyisobutylene, poly α-olefin, hydrogenated poly α-olefin, and the like. The ratio of the olefin monomer unit in the liquid polyolefin polymer is not particularly limited, but is preferably 50% by weight or more. In the case of a hydrogenated polyolefin, it can be represented by the proportion of olefin monomer units in the polymer before hydrogenation, and the proportion of olefin monomer units in the polymer is 50% by weight or more. Preferably there is. Specific products include Kuraray's LIR, for example.

The component (C) may be linear or branched, and the number average molecular weight thereof is preferably 3,000 or more and preferably 100,000 or less in terms of polystyrene by gel permeation chromatography (GPC). Is. More preferably, it is 8,000 or more and 50,000 or less. Particularly preferably, it is 15,000 or more and 35,000 or less. This is because if the number average molecular weight is less than 3,000, the adhesion improving effect tends to be insufficient, and if it exceeds 50,000, the viscosity becomes high and the workability tends to be inconvenient.
These liquid polyolefin polymers may be used alone or in combination of two or more.
(A) Although the compounding ratio of (C) component with respect to 100 weight part of components is not specifically limited, 2-40 parts are preferable and 5-30 parts are especially preferable. When the amount is less than 2 parts, there is a problem of adhesion deterioration, and when it is more than 40 parts, there is a problem of compatibility.

  In the present invention, it is preferable to add a plasticizer for the purpose of improving the workability of the curable composition and the purpose of improving the dispersion stability of the component (A) and the component (B).

  A plasticizer is not specifically limited, A well-known thing can be used. Specifically, for example, alkyl sulfonic acid phenyl esters such as mesamol (Mesamol, Bayer), mesamol II (Mesamol II, Bayer); aromatic oligomers such as biphenyl and triphenyl, complete or partial aromatic oligomers Hydrogenated products; paraffins such as paraffin oil and chlorinated paraffin oil; cycloparaffins such as naphthenic oil; phthalic acid esters such as dibutyl phthalate, di (2-ethylhexyl) phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate; Non-aromatic dibasic acid esters such as di (2-ethylhexyl) adipate, di-n-octyl adipate, diisononyl adipate, diisodecyl adipate, di (2-ethylhexyl) sebacate; linseed oil, Fatty acid oils such as soybean oil and tung oil; aromatic esters such as tri-2-ethylhexyl trimellitic acid and triisodecyl trimellitic acid; fatty acid esters such as butyl oleate and the like can be used. These plasticizers may be used alone or in combination of two or more.

  Among these plasticizers, alkylsulfonic acid phenyl ester and phthalic acid ester are particularly preferable from the viewpoint of improving the dispersion stability of component (A) and component (B).

The plasticizer is preferably used in an amount of 5 to 80 parts by weight, more preferably 10 to 60 parts by weight, based on 100 parts by weight of the component (A).
In the component (A) of the present invention, a vinyl polymer having a reactive silicon group can be blended and used.

  A method of blending a vinyl polymer having a reactive silicon group has been proposed in JP-A Nos. 59-122541, 63-112642, and JP-A-6-172631.

A preferred specific example is an acrylate monomer unit having a reactive silicon group and a molecular chain substantially having an alkyl group having 1 to 8 carbon atoms represented by the following general formula (4) and / or A copolymer comprising a methacrylic acid ester monomer unit and an acrylic acid ester monomer unit and / or a methacrylic acid ester monomer unit having an alkyl group having 10 or more carbon atoms represented by the following general formula (5) And a polyoxyalkylene polymer having a reactive silicon group.
—CH ₂ —C (R ⁵ ) (COOR ⁶ ) — (4)
(Wherein R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group having 1 to 8 carbon atoms)
^{_{-CH 2 -C (R 5) (}} COOR 7) - (5)
(Wherein R ⁵ is the same as above, and R ⁷ is an alkyl group having 10 or more carbon atoms)

As R < ⁶ > of the said General formula (4), C1-C8, such as a methyl group, an ethyl group, a propyl group, n-butyl group, a tert- butyl group, 2-ethylhexyl group, Preferably it is 1-4. More preferred are 1 to 2 alkyl groups. The alkyl group of R ⁶ may alone, or may be a mixture of two or more.

R ^{7 in the} general formula (5) is, for example, a long chain having 10 or more carbon atoms such as lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group, etc., usually 10-30, preferably 10-20. And an alkyl group. The alkyl group R ⁷ may alone, or may be a mixture of two or more.

  The molecular chain of the vinyl copolymer is substantially composed of monomer units of the general formula (4) and the general formula (5). It means that the total of the monomer units of the formula (4) and the general formula (5) exceeds 50% by weight. Preferably, the total of the monomer units of the general formula (4) and the general formula (5) is 70% by weight or more.

  Further, the abundance ratio of the monomer unit of the general formula (4) and the monomer unit of the general formula (5) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40 by weight ratio. .

  Examples of monomer units other than the general formula (4) and general formula (5) that may be contained in the copolymer include acrylic acid such as acrylic acid and methacrylic acid; acrylamide, methacrylamide, N- Monomers containing amide groups such as methylolacrylamide and N-methylolmethacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, and amino groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate and aminoethyl vinyl ether; other acrylonitrile, styrene, α -Monomer units derived from methyl styrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

  The copolymer preferably has a number average molecular weight of 500 to 100,000 from the viewpoint of ease of handling.

Examples of the reactive silicon group possessed by the copolymer include a group represented by the general formula (6).
—Si (R ¹ _3-a ) X _a (6)
(Wherein R ¹ , X and a are the same as above)

  The number of reactive silicon groups in the copolymer is preferably 1 or more on average per molecule, more preferably 1.1 or more, and particularly preferably 1.5 or more from the viewpoint of obtaining sufficient curability.

  Specific examples of the hydrolyzable group in the general formula (6) include, for example, a halogen atom, 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. Etc.

  Furthermore, as a method for producing an organic polymer blended with a vinyl polymer having a reactive silicon group, an acrylate monomer in the presence of a polyoxyalkylene polymer having a reactive silicon group And / or a method of polymerizing a methacrylic acid ester monomer can be used. This production method is specifically disclosed in JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, etc. It is not limited to these.

  You may add an epoxy resin to the curable composition of this invention as needed.

  The epoxy resin is not particularly limited, and known ones can be used. Specifically, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, urethane-modified epoxy resin, alicyclic epoxy resin, novolac type epoxy resin, polyalkylene glycol diglycidyl ether, Examples thereof include polyglycidyl ethers of polyhydric alcohols such as glycerin, flame retardant epoxy resins such as diglycidyl ether of tetrabromobisphenol A, and diglycidyl ethers of alkylene oxide adducts of bisphenol A.

  Among these epoxy resins, those containing at least two epoxy groups in the molecule are preferable from the viewpoints of high reactivity at the time of curing and the cured product easily forming a three-dimensional network. In particular, bisphenol A type epoxy resin or novolak type epoxy resin is preferable.

  When adding an epoxy resin to the curable composition of this invention, you may use together the hardening | curing agent for hardening an epoxy resin. There is no limitation in particular as an epoxy resin hardening | curing agent which can be used, A well-known epoxy resin hardening | curing agent can be used. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated poly Primary and secondary amines such as ether; tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol and tripropylamine, and salts of these tertiary amines; polyamide resins; imidazole compounds; dicyandiamide compounds; Examples include carboxylic anhydrides such as phthalic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride; alcohol compounds; phenol compounds; carboxylic acid compounds. These curing agents may be used alone or in combination of two or more.

  Moreover, a ketimine compound can be used as an epoxy resin curing agent. The ketimine compound exists stably in the absence of moisture, is decomposed into primary amines and ketones by moisture, and the generated primary amine becomes a curing agent for the epoxy resin. When a ketimine compound is used, a one-component composition can be obtained. Such a ketimine compound can be obtained by a condensation reaction between an amine compound and a carbonyl compound.

  If necessary, the curable composition of the present invention may further contain a silanol condensation catalyst, an adhesion-imparting agent, a filler, a thixotropic agent, an antiaging agent, and other various additives.

  It does not specifically limit as a silanol condensation catalyst, A well-known thing can be used. Specifically, for example, titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetraacetylacetonate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctate, dibutyltin diethylhexanolate, dibutyltin dimethyl maleate, Dibutyltin diethyl maleate, dibutyltin dibutyl maleate, dibutyltin dioctyl maleate, dibutyltin ditridecyl maleate, dibutyltin dibenzyl maleate, dibutyltin diacetate, dioctyltin diethyl maleate, dioctyltin dioctyl maleate, dibutyltin dimethoxide, dibutyltin di Nonylphenoxide, dibutenyl tin oxide, dibutyltin diacetyl Tetravalent tin compounds such as setonate, dibutyltin diethyl acetoacetonate, reaction product of dibutyltin oxide and phthalate; divalent tin compounds such as tin octylate, tin naphthenate and tin stearate; aluminum trisacetylacetonate , Organoaluminum compounds such as aluminum trisethylacetoacetate and diisopropoxyaluminum ethylacetoacetate; zirconium compounds such as zirconium tetraacetylacetonate; lead octylate; butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, Triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylamino Propylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo ( 5,4,0) amine compounds such as undecene-7 (DBU), or salts of these amine compounds with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; excess polyamines A silanol condensation catalyst such as: a reaction product of an epoxy compound with a silane coupling agent having an amino group such as γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane; Furthermore, other acidic catalysts and basic catalysts Any known silanol condensation catalyst may be mentioned. These catalysts may be used alone or in combination of two or more.

  The use amount of these curing catalysts is preferably 0.01 to 20 parts by weight, particularly preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of component (A). If the amount of the curing catalyst used is too small, the curing rate becomes slow and the curing reaction does not proceed sufficiently. On the other hand, if the amount of the curing catalyst used is too large, local heat generation or foaming occurs during curing, and it becomes difficult to obtain a good cured product, which is not preferable.

  It does not specifically limit as an adhesive provision agent, Well-known things, such as a silane coupling agent, can be used. Specifically, isocyanate group-containing silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane; Trimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β -Aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane, γ- Ureid Amino group-containing silanes such as propyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane; Mercapto group-containing silanes such as mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycyl Sidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxy Epoxy group-containing silanes such as lan; Vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-acryloyloxypropylmethyltriethoxysilane; Mention may be made of isocyanurate-type silanes such as (silyl) isocyanurate. In addition, derivatives obtained by modifying these can also be used as adhesion-imparting agents.

  The adhesiveness imparting agent used in the present invention is used in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of component (A). In particular, it is preferably used in the range of 0.5 to 10 parts by weight.

  It does not specifically limit as a filler, A well-known thing can be used. Specifically, for example, fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, carbon black, heavy calcium carbonate, colloidal calcium carbonate, surface-treated calcium carbonate, magnesium carbonate, calcium oxide, titanium oxide, water Inorganic fillers such as calcium oxide, diatomaceous earth, calcined clay, clay and talc; organic fillers such as PVC powder and acrylic resin powder; fibrous fillers such as glass fiber; inorganic balloons such as shirasu balloon and glass balloon; phenol Organic balloons such as balloons are examples. These fillers may be used alone or in combination of two or more.

  The filler is preferably used in an amount of 50 to 500 parts by weight, more preferably 60 to 300 parts by weight, based on 100 parts by weight of component (A). When the amount of the filler used is less than 50 parts by weight, the effect as a filler is hardly exhibited, and when it exceeds 500 parts by weight, the viscosity increases and workability may be reduced.

  The thixotropic agent is not particularly limited, and known ones can be used. Specific examples include hydrogenated castor oil, organic amide wax, organic bentonite, and calcium stearate. These thixotropic agents may be used alone or in combination of two or more.

  The thixotropic agent is preferably used in an amount of 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the component (A). If the amount of the thixotropic agent used is less than 0.1 parts by weight, sufficient thixotropy may not be obtained, and if it exceeds 50 parts by weight, it is not preferable from the viewpoint of cost increase.

  It does not specifically limit as an anti-aging agent, A well-known thing can be used. Specifically, for example, phenolic antioxidants, aromatic amine antioxidants, sulfur antioxidants, phosphoric antioxidants, benzotriazole ultraviolet absorbers, benzoate ultraviolet absorbers, benzophenone ultraviolet absorbers , Salicylate ultraviolet absorbers, hindered amine light stabilizers, nickel light stabilizers, and the like.

  The antioxidant is preferably used in an amount of 0.01 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight, based on 100 parts by weight of component (A).

  These anti-aging agents may be used alone or in combination of two or more. It may function more effectively when used in combination than when used alone.

  Various additives may be added to the curable composition of the present invention as needed for the purpose of adjusting various physical properties. Examples of such additives include, for example, storage stability improvers, flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants. Pigments, foaming agents, solvents, fungicides and the like. These additives may be used alone or in combination of two or more.

  The manufacturing method of the curable composition of this invention is not specifically limited, It can manufacture by a well-known method. For example, a method of blending each component shown above and kneading using a planetary mixer, paint roll, kneader or the like, a method of dissolving each component using a solvent, and the like can be used. The curable composition of the present invention can be either a one-component type or a two-component type curable composition.

  Although the curable composition of this invention is demonstrated based on the Example shown below, this invention is not limited to these Examples.

(Synthesis Example 1)
After 800 g of polyoxypropylene glycol having a number average molecular weight of 5,200 and 50.2 g of isophorone diisocyanate were mixed in a pressure-resistant reaction vessel equipped with a stirrer, 0.8 g of tin catalyst (10% DOP solution of dibutyltin dilaurate) was added. By stirring at 80 ° C. for 4 hours, an isocyanate group-terminated polymer having a molecular weight of about 15,000 was obtained (molecular weight calculated from titration value (0.579%) of isocyanate group). After cooling to 60 ° C., γ-aminopropyltrimethoxysilane 1.0 [eq / NCO group] is added and stirred for about 30 minutes, whereby the number average molecular weight having a trimethoxysilyl group at the molecular end is 17,000 ( A polyoxypropylene polymer having a molecular weight of polystyrene calculated from GPC was obtained (Polymer A).

(Synthesis Example 2)
A polyoxypropylene diol having a number average molecular weight of 2,000 is used as an initiator, and a propylene oxide is polymerized using a zinc hexacyanocobaltate glyme complex catalyst to obtain a number average molecular weight of 25,500 (polystyrene equivalent molecular weight determined by GPC). Polyoxypropylene glycol was obtained. By adding 1.8 parts by weight of γ-isocyanatopropyltrimethoxysilane to 100 parts by weight of the resulting polypropylene glycol, and reacting at 90 ° C. for 5 hours, a trioxysilyl group-terminated polyoxypropylene-based polymer at the molecular terminal. (Polymer B) was obtained.
Production Example 1 Production of FG1924 (20%) + DIDP (80%) 200 g of FG1924 was added to 800 g of DIDP, and dissolved by stirring at 100 ° C. for 2 hours.
Production Example 2 Production of FG1901 (20%) + DIDP (80%) 200 g of FG1901 was added to 800 g of DIDP and dissolved by stirring at 100 ° C. for 2 hours.
Production Example 3 Production of G1650 (20%) + DIDP (80%) 200 g of G1650 was added to 800 g of DIDP, and dissolved by stirring at 100 ° C. for 2 hours.
(Examples 1-7, Comparative Examples 1-6)
After the kneading and dehydrating operation of various compounding agents having the compositions shown in Table 1 using a 5 liter planetary mixer, the cartridge is filled, and the one-component curable compositions of Examples 1 to 7 and Comparative Examples 1 to 6 are used. The thing was manufactured.

The following evaluation was performed using these obtained one-component curable compositions.
(Adhesion test)
The adhesive composition was applied to various substrates, pasted with plywood, and cured at room temperature for 2 weeks. Thereafter, a cut was made with a knife between the cured adhesive and various substrates, and the adhesive was peeled off by hand to observe the adhesive state. The case where the adhesive remained completely on the various substrate sides was designated as CF, the case where no adhesive remained, AF, and the case where half of the adhesive remained as CF50AF50.
(Peel strength)
The adhesive composition was applied to an Antico ionomer resin base flooring and then cured at room temperature for 2 weeks. Thereafter, peel strength was measured at a tensile rate of 25 mm / min (23 ° C., 50% RH) using an autograph manufactured by Shimadzu Corporation.
Various compounding agents used for evaluation are shown below.
(A) Component / MS polymer S227: manufactured by Kaneka, polyoxyalkylene polymer having a methyldimethoxysilyl group Polymer A: Polymer described in Synthesis Example 1 Polymer B: Polymer described in Synthesis Example 2 Component (B) Component / Clayton FG1924: manufactured by Kraton, maleic anhydride graft-modified styrene / ethylene / butylene block copolymer (30% styrene, maleic anhydride content 0.7 to 1.3% by weight)
・ Clayton FG1901: Made by Kraton, maleic anhydride graft-modified styrene / ethylene / butylene block copolymer (styrene 30%, maleic anhydride content 1.4-2 wt%)
Component (C): LIR-200: manufactured by Kuraray, liquid hydrogenated polyisoprene, molecular weight 25,000
LIR-310: manufactured by Kuraray, liquid styrene polyisoprene, molecular weight 31,000
LIR-230: manufactured by Kuraray, liquid hydrogenated polyisoprene, molecular weight 25,000
LIR-403: manufactured by Kuraray, liquid maleated polyisoprene, molecular weight 25,000
LIR-390: Kuraray, liquid butadiene polyisoprene, molecular weight 48,000
Other additives are shown below.
-Clayton G1650: Clayton, styrene / ethylene / butylene block copolymer-Mesamoll: Bayer, alkyl sulfonic acid phenyl ester-DIDP: diisodecyl phthalate-Omycard 2T-AV: OMYA Calcium carbonate-Carbital 110s: IMERYS Calcium carbonate
-Ti-Pure R902: DuPont, titanium dioxide-Tinuvin 326: Ciba Specialty Chemicals, benzotriazole UV absorber-Tinuvin 770: Ciba Specialty Chemicals, hindered amine light stabilizer-A-171: Vinyltrimethoxysilane ( Dehydrating agent)
A-1110: γ-aminopropyltrimethoxysilane (adhesive agent)
S-1: Organic tin compound (curing catalyst) manufactured by Nitto Kasei
Various base materials used for the evaluation are shown below.
・ Americo ionomer resin-based flooring material ・ Esha PE film bitumen sheet ・ Dupont Tyvek

As is clear from Table 1, the curable composition of the present invention has excellent adhesiveness to a polyethylene resin substrate and an ionomer resin substrate that have been conventionally known as difficult adhesion substrates.

The curable composition of the present invention can be used as a sealing material, an adhesive, a pressure-sensitive adhesive, an injection material, a waterproofing material, a vibration damping material, a soundproofing material, and the like in a wide range of civil engineering, construction, and industrial applications.
Furthermore, the curable composition of the present invention has good adhesion to a hardly adherent adherend, and particularly has good adhesion to a polyethylene resin substrate. Accordingly, the curable composition of the present invention is useful as an adhesive for waterproof films and waterproof sheets for buildings. In particular, Tyvek (manufactured by Du Pont Co., Ltd.) obtained by thermocompression bonding of three-dimensional network fibers of high-density polyethylene. It is useful as an adhesive to (trademark).
Furthermore, since the curable composition of the present invention has good adhesion to a hardly-adhesive adherend, it is useful as an adhesive for floors using a difficult-to-adhere resin-based sheet as a flooring material. Non-vinyl chloride flooring that is particularly difficult to adhere, specifically, polyethylene resin or ionomer resin (resin in which molecules of ethylene-methacrylic acid copolymer are intermolecularly bonded with metal ions such as sodium and zinc). It is useful as a flooring adhesive.

Claims (13)

(A) Polyoxyalkylene polymer having a reactive silicon group represented by the following general formula (1), (B) maleic anhydride modified styrene / ethylene / butylene block copolymer, maleic acid modified styrene / ethylene / At least one modification selected from butylene block copolymer, carboxylic acid modified styrene / ethylene / butylene block copolymer, epoxy modified styrene / ethylene / butylene block copolymer and imino modified styrene / ethylene / butylene block copolymer Containing a styrene / ethylene / butylene block copolymer, and (C) a liquid polyolefin polymer ,
(A) blending ratio of the component (B) relative to 100 parts by weight of component is 2 to 40 parts, (C) a curable composition proportion of the components is characterized by 2 to 40 parts der Rukoto.
-Si (R ¹ _3-a ) X _a (1)
(In the formula, R ¹ represents 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 a triorganosiloxy group represented by (RO) ₃ Si—. And when two R ¹ are present, they may be the same or different, where R is a monovalent hydrocarbon group having 1 to 20 carbon atoms and 3 R X 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 or different. 2 or 3 is shown.) The curable composition according to claim 1, wherein the main chain skeleton of the component (A) is a polyoxypropylene polymer. (A) Component has group represented by following General formula (2) in a molecule | numerator, The curable composition of Claim 1 or 2 characterized by the above-mentioned.
—NR ² —C (═O) — (2)
(In the formula, R ² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.) The curable composition according to any one of claims 1 to 3, wherein the component (B) is a maleic anhydride-modified styrene / ethylene / butylene block copolymer. The curable composition according to any one of claims 1 to 4, wherein the component (B) is a styrene / ethylene / butylene block copolymer grafted with maleic anhydride. (C) A component is a liquid conjugated polyene type polymer, The curable composition of any one of Claims 1-5 characterized by the above-mentioned. The curable composition according to claim 6, wherein the component (C) is a liquid polyisoprene polymer. The curable composition according to claim 7, wherein the main chain skeleton of the component (C) is a copolymer of polyisoprene and styrene. The curable composition according to any one of claims 1 to 8, wherein the component (C) is a hydrogenated polymer. The waterproof sheet and film adhesive which use the curable composition in any one of Claims 1-9. The floor | bed adhesive formed using the curable composition in any one of Claims 1-9. The adhesive for polyethylene resin or ionomer resin adhesion | attachment which uses the curable composition in any one of Claims 1-9. Hardened | cured material of the curable composition in any one of Claims 1-9.