CN116927509A - Waterproof construction method and waterproof structure - Google Patents

Waterproof construction method and waterproof structure Download PDF

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Publication number
CN116927509A
CN116927509A CN202210331074.8A CN202210331074A CN116927509A CN 116927509 A CN116927509 A CN 116927509A CN 202210331074 A CN202210331074 A CN 202210331074A CN 116927509 A CN116927509 A CN 116927509A
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curable composition
layer
waterproof
polymer
group
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川上敦史
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Kaneka Corp
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Kaneka Corp
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    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
    • E04G21/00—Preparing, conveying, or working-up building materials or building elements in situ; Other devices or measures for constructional work
    • E04G21/14—Conveying or assembling building elements
    • E04G21/16—Tools or apparatus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/66—Sealings
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/66—Sealings
    • E04B1/665—Sheets or foils impervious to water and water vapor
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
    • E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/92—Protection against other undesired influences or dangers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

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  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Chemical & Material Sciences (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Acoustics & Sound (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a waterproof construction method and a waterproof structure, in which a waterproof sheet is bonded to a surface to be waterproof by curing a layer containing a curable composition, wherein the waterproof sheet is bonded to the layer containing the curable composition through a side having a fiber layer on the surface, and the curable composition comprises a polyoxyalkylene polymer containing a hydrolyzable silyl group.

Description

Waterproof construction method and waterproof structure
Technical Field
The present invention relates to the field of construction, and more particularly, to a waterproof construction method for a structure and a waterproof structure obtained by the construction method.
Background
The surface waterproofing method for outdoor building surfaces or industrial products such as heat insulating products, metal products, etc. mainly includes coating a waterproofing membrane layer, covering a coil or flexible sheet waterproofing, etc.
The waterproof method of the coating film is to coat a solution or emulsion of synthetic rubber or synthetic resin composed of 1 component or more on the surface to be constructed to form a continuous membranous waterproof layer with a prescribed thickness. The waterproof coating is relatively simple and convenient to construct, is particularly suitable for waterproof construction of a structure with a complex surface shape, is greatly restricted by the environmental temperature, and particularly has high requirements on the environmental temperature in transportation, storage, stacking and construction operations.
The waterproofing of coiled material or flexible sheet refers to waterproofing treatment by laying a waterproofing coiled material on the surface to be constructed or covering a sheet having a certain flexibility. At present, the construction of the building waterproof engineering generally adopts a mode of paving waterproof coiled materials or flexible sheets. The waterproof coiled materials or flexible sheets are coiled waterproof materials which are formed by taking base paper or fiber fabrics as a base and dip-coating asphalt or other synthetic polymer waterproof materials, and the products mainly comprise asphalt waterproof coiled materials/sheets and polymer waterproof coiled materials/sheets, and the construction methods comprise a hot-melt construction method, a pre-paving anti-bonding method, a single-sided anti-bonding method, a wet paving self-bonding method and the like.
The main construction process adopting the hot melt coiled material is as follows: the method has the advantages of firm bonding, lap joint safety, high universality of application environment temperature and base materials, and the like, and is a mainstream construction mode for a long time. However, when asphalt is melted, smoke and smell of the melted asphalt seriously pollute the surrounding environment, and in addition, there is a safety hazard that operators may burn, so that the use of the asphalt in densely populated areas and urban centers should be avoided as much as possible. As a further improvement, asphalt waterproofing sheets with an adhesive layer, i.e. self-adhesive rolls, have also emerged, the construction of which involves the laying and bonding of the self-adhesive face of the self-adhesive roll onto a base surface.
In addition, cold bonding is also commonly used in coiled material or flexible sheet construction. In general, when a waterproof roll or a flexible sheet made of a polymer resin is used, a curable layer containing a curable composition may be formed on the surface of the resin in advance or before use, and then the waterproof roll or the flexible sheet may be bonded to a surface to be treated by curing the curable layer. Generally, such curable compositions are solvent-borne adhesives, which are insufficient in terms of adhesion, heat resistance, durability in use, and the like, because it is difficult to form a sufficient thickness.
It is also known that an organic polymer having at least 1 reactive silicon group in the molecule can undergo a curing reaction with moisture (moisture in air) even at room temperature to obtain a rubber-like cured product having good mechanical properties. Such polymers have been disclosed in the literature (patent documents 1 and 2) and industrially produced, and are widely used for sealing materials, adhesives, paints and the like.
Although there is the above-described attempt for waterproofing using a roll of waterproofing or flexible sheet, there is still room for further improvement in terms of improving the waterproof bonding effect.
List of references
Patent literature
Patent document 1: JP Japanese patent laid-open No. 52-73998A
Patent document 2: JP (Kokai) Hei 11-130931A
Disclosure of Invention
Problems to be solved by the invention
The present invention has found that when a waterproof sheet is directly bonded to a surface to be waterproofed with an adhesive composition, there is a problem that the bonding strength is insufficient, and that when a building material such as concrete is waterproofed, there is a problem that the cured adhesive layer has a problem in maintaining the bonding strength in terms of alkali resistance, heat resistance, and the like.
In view of the above problems still existing in the art regarding the waterproof construction method for a structure described above, the present invention is primarily directed to providing a waterproof construction method in which a waterproof sheet is bonded to a surface to be waterproof by curing of a layer containing a curable composition, wherein the waterproof sheet is bonded to the layer containing the curable composition through a side having a fiber layer on the surface, and the curable composition comprises a polyoxyalkylene polymer containing a hydrolyzable silyl group.
Further, the present invention also provides a waterproof structure having improved adhesion, alkali resistance and heat resistance.
Solution for solving the problem
Through long-term research by the inventor, the technical problems can be solved through implementation of the following technical scheme:
[1] the invention firstly provides a waterproof construction method, wherein the method at least comprises the following working procedures A-C:
step A: forming a layer containing a curable composition on the surface to be waterproofed, wherein the curable composition comprises a polyoxyalkylene polymer containing a hydrolyzable silyl group;
and (B) working procedure: laminating a polymer sheet having a fiber layer on the surface side thereof such that the layer containing the curable composition faces the fiber layer;
and (C) working procedure: the curable composition is cured to form a cured layer.
[2] Further, the invention also provides another alternative waterproof construction method, wherein the method at least comprises the following working procedures A '-C':
procedure a': forming a layer containing a curable composition on a fiber layer of a polymer sheet having the fiber layer on a surface side, wherein the curable composition comprises a polyoxyalkylene polymer containing a hydrolyzable silyl group;
procedure B': laminating the polymer sheet obtained in the step A' with the surface to be waterproofed via the layer containing the curable composition;
Procedure C': the curable composition is cured to form a cured layer.
[3] The waterproof construction method according to [1] or [2], wherein the fiber layer is a nonwoven fabric layer.
[4] The method for waterproofing according to any one of [1] to [3], wherein the curable composition further comprises a silane compound which is a silane compound obtained by partially condensing an aminosilane compound having a reactive silicon group with each other or a silane compound obtained by partially condensing an aminosilane compound having a reactive silicon group with an alkoxysilane compound other than aminosilane.
[5] The method for waterproofing according to any one of [1] to [4], wherein the curable composition comprises an inorganic filler, wherein the inorganic filler comprises calcium carbonate having an average particle diameter of 1 μm or less.
[6] The method for waterproofing according to any one of [1] to [5], wherein the curable composition further comprises one or more of an epoxy resin and a hydrolyzable silyl group-containing acrylic resin.
[7] The method for waterproofing according to any one of [1] to [6], wherein the polymer sheet is a thermoplastic polyolefin sheet having a fiber layer on the surface side.
[8] Further, the present invention also provides a waterproofing method for a structure, wherein the method comprises the waterproofing method according to any one of the above [1] to [7 ].
[9] The method of waterproofing a structure according to [8], wherein the structure comprises a building, a heat insulator or a metal product.
[10] The present invention also provides a waterproof structure for a structure, comprising a cured layer formed on a surface of the structure to be waterproof-treated, and a polymer sheet bonded via the cured layer;
wherein the cured layer is a layer formed by curing a curable composition comprising a polyoxyalkylene polymer having a hydrolyzable silyl group;
the polymer sheet has a fiber layer on the surface side to which the cured layer is bonded.
[11] The waterproof structure according to [10], wherein the fiber layer is a nonwoven fabric layer.
ADVANTAGEOUS EFFECTS OF INVENTION
By implementing the technical scheme, the invention can obtain the following technical effects:
1) The use of the polyoxyalkylene polymer having a hydrolyzable silyl group in the curable composition and the provision of the fiber layer on the surface to be bonded of the polymer sheet can significantly improve the bonding strength between the polymer waterproof sheet and the surface to be waterproofed;
2) By using the above construction method, the alkali resistance and heat resistance of the adhesion between the waterproof sheet and the surface to be treated can be significantly improved, and even when subjected to alkaline conditions or high temperature conditions, good adhesion strength can be maintained for a long period of time, and thus good durability and environmental stability can be obtained.
Drawings
Fig. 1: the invention relates to a waterproof structure schematic diagram of a structure
Detailed Description
The following describes embodiments of the present invention, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications are possible within the scope of the invention as claimed, and embodiments and examples obtained by appropriately combining the technical means disclosed in the different embodiments and examples are also included in the technical scope of the present invention. All documents described in the present specification are incorporated by reference in the present specification.
Unless defined otherwise, technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The use of the terms "a" and "an" and "the" and similar referents in the context of describing the specification (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.
In the present specification, "sheet" refers to a waterproof material that exhibits a sheet shape when stretched; "web" refers to a roll of "sheet" obtained by crimping. Therefore, the "waterproof sheet" and the "waterproof roll" to which the present invention pertains have substantially the same meaning in terms of composition and properties, and differ only in the form in which they exist.
In the present specification, a numerical range expressed by using "a to B values" or "a to B values" means a range including the end point value A, B.
In the present specification, the "(meth) acrylate" means "acrylate and/or methacrylate", and the "(meth) acrylic acid" means "acrylic acid and/or methacrylic acid". The same other expressions have the same meanings as those.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process. In this specification, "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Reference throughout this specification to "some embodiments," "other embodiments," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the elements may be combined in any suitable manner in the various embodiments.
The term "comprising" and any variations thereof in the description of the invention and in the claims is intended to cover a non-exclusive inclusion. For example, a process, method, or system, article, or apparatus that comprises a list of steps or elements is not limited to only those listed but may optionally include additional steps or elements not listed or inherent to such process, method, article, or apparatus.
The invention provides a waterproof construction method and a waterproof structure for improving the bonding strength, alkali resistance and heat resistance of a waterproof sheet and a waterproof treated surface in waterproof construction. The present invention is achieved by using a polyoxyalkylene polymer containing a hydrolyzable silyl group in a curable composition and providing a fiber layer on the surface to be bonded of a polymer sheet.
< Polymer sheet >
The polymer sheet of the present invention is a sheet (including a roll) having a waterproof function, and in some specific cases, the polymer sheet of the present invention does not substantially allow permeation of water molecules. The polymer sheet of the present invention is a polymer sheet having a fiber layer on at least one surface side of the sheet. That is, the polymer sheet of the present invention includes a polymer material layer and a fiber layer.
The material of the (sheet-like) polymer material layer in the polymer sheet of the present invention is not particularly limited, and a resin-based waterproof layer may be used, and these layers may be sheet-like products obtained by extrusion, roll forming, injection molding, or the like, and preferably the sheet-like products are crimpable products.
The material of the resin-based waterproof layer is not particularly limited in principle, and may be selected from (halogenated) polyolefin-based resins, polyvinyl chloride-based resins, polyurethane-based resins, polyester-based resins, polyacrylic resins, and the like.
In some preferred embodiments of the present invention, the material of the polymer material layer of the present invention is preferably a thermoplastic polyolefin-based resin or a thermoplastic halogen-containing resin thereof from the viewpoint of convenience of use and durability. Examples which may be mentioned are: homopolymers of ethylene, propylene, alpha-olefins; copolymers of alpha-olefins with ethylene, propylene or styrene; homopolymers of diolefins or copolymers of diolefins with other vinyl monomers; chlorinated polyolefins, such as polyvinyl chloride and the like.
The copolymer may be a random copolymer or a block copolymer. The alpha-olefin may be an alpha-olefin having 4 to 18 carbon atoms, and specific examples thereof include butene-1, isobutylene, hexene-1, 4 methylpentene-1, pentene-1, octene-1, nonene-1, decene-1 and the like. As the diolefin, isoprene, butadiene and the like are specifically mentioned.
In some preferred embodiments of the present invention, the polymer material layer of the present invention is selected from olefin-based thermoplastic elastomer (TPO) waterproof sheet, polyvinyl chloride (PVC) waterproof sheet, ethylene-propylene-diene rubber (EPDM) waterproof sheet, high-density polyethylene (HDPE) waterproof sheet, and the like.
In addition, in some embodiments of the present invention, the polymer material layer may be a single layer or a multilayer laminated structure. The polymer material layers of the multilayer laminated structure may be the same or different in material.
In other specific embodiments of the present invention, the polymer material layer may be a reinforced composite material, and there is no particular limitation on the reinforcing phase, and may be one or more of organic particles, inorganic particles, long fibers, or chopped fibers.
In the present invention, the polymer sheet has a fiber layer on the bonded side. The invention discovers that the bonding strength between the macromolecule waterproof sheet and the waterproof treated surface can be obviously improved by arranging the fiber layer.
As the material of the fiber layer, there may be mentioned, for example: polyolefin fibers (polyethylene fibers, polypropylene fibers, etc.), polyester fibers, polyamide fibers, polyacrylonitrile fibers, etc. Further, the fiber layer of the present invention may be a fiber layer obtained by spinning a fiber monofilament or multifilament, or may be a non-woven fabric (non-woven fabric) layer. Also, in some preferred embodiments of the present invention, a nonwoven fabric layer is used as the fiber layer of the present invention, and the nonwoven fabric layer may be a spunbonded nonwoven fabric, a melt-blown nonwoven fabric or a water needle nonwoven fabric.
The thickness of the fibrous layer of the present invention is not particularly limited, and in some specific embodiments may be 0.1 to 8mm, preferably may be 0.2 to 3mm, and more preferably 0.3 to 2mm. The nonwoven fabric layer of the present invention may be partially incorporated into the surface layer of the polymer material layer.
The method of forming the polymer sheet having a fiber layer of the present invention is not particularly limited in principle, and various known compounding or lamination methods in the art may be employed, and examples thereof include, in specific embodiments, forming the fiber layer on the surface of the polymer material layer by a method such as an adhesive or hot pressing.
In addition, in some preferred embodiments, for the polymeric sheet of the present invention, it has the above-described fibrous layer on only one side surface and the other side is directly exposed to the environment.
< curable composition >
In the present invention, (curing) of a layer containing a curable composition is used to achieve adhesion of the polymer sheet fiber layer side to the surface to be water-repellent treated of the structure.
In the present invention, the curable composition includes a polyoxyalkylene polymer having a hydrolyzable silyl group, and thus the adhesion between the water-repellent sheet and the surface to be water-repellent treated can be improved.
The components, physical properties, production methods, and the like of the curable composition of the present invention will be described in order.
(polyoxyalkylene polymer having hydrolyzable silyl group)
As the polyoxyalkylene polymer having a hydrolyzable silyl group, there is a polyoxyalkylene segment as a main chain.
As the polymer fragment constituting the main chain, there may be exemplified sources such as: one or more kinds of polyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, and the like. Among them, the polyoxyalkylene polymer has a low glass transition temperature and a high moisture permeability, and the cured layer obtained has excellent cold resistance and adhesion, which contributes to improvement of the adhesive strength of the cured layer containing the curable composition. Further, in a preferred embodiment of the present invention, the polyoxyalkylene polymer having a hydrolyzable silyl group employs a polymer main chain structure including polyoxypropylene.
The polyoxyalkylene polymer is obtained by ring-opening polymerization of an epoxy compound. Examples of the synthesis method of the polyoxyalkylene polymer include: polymerization methods based on a basic catalyst such as KOH, polymerization methods based on a transition metal compound-porphyrin complex catalyst such as a complex obtained by reacting an organoaluminum compound with porphyrin disclosed in Japanese patent application laid-open No. 61-215623, polymerization methods based on a double metal cyanide complex catalyst (for example, zinc hexacyanocobaltate glyme complex catalyst) disclosed in Japanese patent application laid-open No. 10-273512, polymerization methods using a catalyst containing a phosphazene compound exemplified in Japanese patent application laid-open No. 11-060722, and the like disclosed in Japanese patent application laid-open No. 59-15336, U.S. patent 3278457, U.S. patent 3278458, U.S. patent 3278459, U.S. patent 3427256, U.S. patent 3427334, U.S. patent 3427335, and the like, but are not limited to these synthesis methods.
The hydrolyzable silyl group of the present invention is a group having a hydrolyzable group bonded to a silicon atom, and is a group that can be crosslinked by accelerating the reaction to form a siloxane bond by a silanol condensation catalyst. The hydrolyzable group represents a group that reacts with water to form a hydroxyl group.
In some embodiments of the present invention, the polyoxyalkylene polymer having hydrolyzable silyl groups has one or more hydrolyzable silyl groups represented by the general formula (1):
-Si(R 1 ) 3-a X a (1)
wherein R is 1 Each independently is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a hydroxyl-containing group, an aralkyl group having 7 to 20 carbon atoms or a group consisting of-OSi (R') 3 A triorganosiloxy group represented wherein each R' is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; each X independently represents a hydrolyzable group; a is an integer of 1 to 3.
The hydrolyzable group is not particularly limited in principle, and may be a hydrolyzable group generally known in the art. In some specific embodiments, for example, halogen atoms, alkoxy groups, acyloxy groups, amino groups, amide groups, aminoxy groups, mercapto groups, alkenyloxy groups, and the like may be cited. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoxime group (ketoxime group), an amino group, an amide group, an aminoxy group, a mercapto group, and an alkenyloxy group are preferable, and an alkoxy group is particularly preferable from the viewpoint of stable hydrolyzability and easy handling.
The number of the hydrolyzable groups bonded to 1 silicon atom may be in the range of 1 to 3. Further, these groups may be the same or different.
From the viewpoint of curability, a in the above general formula (1) is preferably 2 or 3, and particularly when rapid curability of the composition is required, 3 is preferred, and when storage stability of the composition is required, 2 is preferred.
R in the above general formula (1) 1 Examples thereof include: alkyl groups such as methyl and ethyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups, or-OSi (R') 3 And triorganosiloxy groups represented. Among these, methyl groups are particularly preferable from the viewpoint of the raw material utilization rate.
More specifically, examples of the hydrolyzable silyl group include: trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, diisopropyloxymethylsilyl, (chloromethyl) dimethoxysilyl, (methoxymethyl) dimethoxysilyl, methyldimethoxysilyl, and the like. From the viewpoint of high reactivity and good curability, trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, (methoxymethyl) dimethoxysilyl and methyldimethoxysilyl are preferable, trimethoxysilyl, (methoxymethyl) dimethoxysilyl and methyldimethoxysilyl are more preferable, and trimethoxysilyl is still more preferable. From the viewpoint of storage stability, dimethoxymethylsilyl group and triethoxysilyl group are preferable.
The method for introducing the hydrolyzable silyl group into the polymer chain is not particularly limited, and may be carried out by a known method. For example, the following methods are mentioned.
(I) A polyoxyalkylene polymer having an unsaturated group is obtained by reacting a polyoxyalkylene polymer having a functional group such as a hydroxyl group with an organic compound having an active group reactive with the functional group and an unsaturated group (for example, an epoxy compound having a saturated group). Next, the resulting polyoxyalkylene polymer having an unsaturated group is reacted with a hydrosilane compound having a hydrolyzable silyl group (hydrosilation).
(II) reacting an unsaturated group-containing polyoxyalkylene polymer obtained in the same manner as in (I) with a compound having a mercapto group and a hydrolyzable silyl group.
(III) reacting a polyoxyalkylene polymer having a functional group such as a hydroxyl group, an epoxy group, or an isocyanate group in the molecule with a compound having a functional group reactive with the functional group and a hydrolyzable silyl group.
Among the above methods, the method of (I) or the method of (III) reacting a polyoxyalkylene polymer having a hydroxyl group at the end with a compound having an isocyanate group and a hydrolyzable silyl group is preferable because a high conversion can be obtained in a short reaction time. In addition, in general, the polyoxyalkylene polymer having a hydrolyzable silyl group obtained by the method of (I) has a lower viscosity than the polyoxyalkylene polymer obtained by the method of (III), and a curable composition excellent in workability can be obtained when the polyoxyalkylene polymer having a hydrolyzable silyl group obtained by the method of (I) is used, and the mercapto silane-based odor of the polyoxyalkylene polymer obtained by the method of (II) is strong, so that the method of (I) is particularly preferable in the present invention.
Examples of the hydrosilane compound used in the method of (I) include: halosilanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyldichlorosilane, etc.; alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, and 1- [2- (trimethoxysilyl) ethyl ] -1, 3-tetramethyldisiloxane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane, but are not limited to these compounds.
Further, in the present invention, halosilanes and alkoxysilanes, particularly alkoxysilanes, are particularly preferred, since the resulting curable composition is stable in hydrolyzability and easy to handle. Among the alkoxysilanes, methyldimethoxysilane is preferred because it is easily available, and the curable composition containing the resulting polyoxyalkylene polymer has high curability, storage stability, elongation characteristics, and tensile strength. In addition, trimethoxysilane is particularly preferred from the viewpoint of curability and restorability of the resulting curable composition.
Examples of the method (II) include a method of introducing a compound having a mercapto group and a hydrolyzable silyl group into an unsaturated bond site of a polyoxyalkylene polymer by a radical addition reaction in the presence of a radical initiator and/or a radical generating source, but are not limited thereto. Examples of the compound having a mercapto group and a hydrolyzable silyl group include: gamma-mercaptopropyl trimethoxysilane, gamma-mercaptopropyl methyl dimethoxy silane, gamma-mercaptopropyl triethoxy silane, gamma-mercaptopropyl methyl diethoxy silane, mercaptomethyl trimethoxy silane, mercaptomethyl triethoxy silane, etc., but are not limited to these compounds.
Examples of the method (III) for reacting a polyoxyalkylene polymer having a hydroxyl group with a compound having an isocyanate group and a hydrolyzable silyl group include, but are not limited to, the method disclosed in Japanese unexamined patent publication No. Hei 3-47825. Examples of the compound having an isocyanate group and a hydrolyzable silyl group include: gamma-isocyanatopropyl trimethoxysilane, gamma-isocyanatopropyl methyldimethoxysilane, gamma-isocyanatopropyl triethoxysilane, gamma-isocyanatopropyl methyldiethoxysilane, isocyanatomethyl trimethoxysilane, isocyanatomethyl triethoxysilane, isocyanatomethyl dimethoxymethylsilane, isocyanatomethyl diethoxymethylsilane, and the like, but are not limited to these compounds.
Further, the hydrolyzable silyl group-containing polyoxyalkylene polymer of the present invention may be used alone or in combination of 2 or more.
The hydrolyzable silyl group-containing polyoxyalkylene polymer of the present invention may be of any type of linear or branched. The number average molecular weight (Mn) of the hydrolyzable silyl group-containing polyoxyalkylene polymer can be measured by GPC (polystyrene standards), and in some preferred embodiments of the present invention may be 1,000 ～ 100,000, more preferably 2,000 to 50,000, and particularly preferably 3,000 to 30,000. When the number average molecular weight is less than 1,000, there is a possibility that elongation of the cured layer becomes insufficient in some cases, and when it exceeds 100,000, the curable composition becomes high in viscosity, and thus there is a tendency that workability is not desirable. The molecular weight distribution (Mw/Mn) of the hydrolyzable silyl group-containing polyoxyalkylene polymer as measured by GPC is preferably 2 or less, more preferably 1.5 or less, still more preferably 1.4 or less.
In addition, from the viewpoint of mechanical strength, the number of hydrolyzable silyl groups contained in the polyoxyalkylene polymer of the present invention is preferably 1 or more, more preferably 1.1 to 5, still more preferably 1.1 to 3, particularly preferably 1.1 to 2 on average in 1 molecule. If the number average of hydrolyzable silyl groups contained in the molecule is less than 1, there is a concern that curability becomes insufficient and it is difficult to obtain a cured layer having good rubber elasticity in some cases.
In the present invention, the hydrolyzable silyl group may be located at the main chain end or at the side chain end of the polyoxyalkylene polymer. In addition, the terminal groups may be located at both the main chain terminal and the side chain terminal of the polyoxyalkylene polymer. In particular, when the hydrolyzable silyl group is located only at the terminal of the main chain, the effective mesh length in the finally formed cured layer becomes long, and thus a rubber-like cured layer exhibiting high strength, high elongation and low elastic modulus is easily obtained.
In some preferred embodiments of the present invention, the polyoxyalkylene polymer containing hydrolyzable silyl groups is selected from at least one of the following groups: a polyoxyalkylene polymer having an average of 1.1 to 5 silyl groups per 1 molecule selected from at least one of trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, (methoxymethyl) dimethoxysilyl and methyldimethoxysilyl, and having a number average molecular weight of 1,000 ～ 100,000. In other preferred embodiments of the present invention, the polyoxyalkylene polymer having hydrolyzable silyl groups is selected from at least one of the following groups: a polyoxyalkylene polymer having an average of 1.1 to 3 silyl groups selected from at least one of trimethoxysilyl group, (methoxymethyl) dimethoxysilyl group and methyldimethoxysilyl group per 1 molecule and a number average molecular weight of 2,000 to 50,000.
As other sources of the hydrolyzable silyl group containing polyoxyalkylene polymer, there may be mentioned, for example: the polyoxyalkylene polymer proposed in Japanese patent publication No. 45-36319, japanese patent publication No. 46-12154, japanese patent publication No. 50-156599, japanese patent publication No. 54-6096, japanese patent publication No. 55-13767, japanese patent publication No. 55-13468, japanese patent publication No. 57-164123, japanese patent publication No. 3-2450, U.S. Pat. No. 3632557, U.S. Pat. No. 4345053, U.S. Pat. No. 4366307, U.S. Pat. No. 4960844, etc., and the polyoxyalkylene polymer proposed in Japanese patent publication No. 61-197631, japanese patent publication No. 61-215622, japanese patent publication No. 61-215623, japanese patent publication No. 61-218632, japanese patent publication No. 3-72527, japanese patent publication No. 3-47825, japanese patent publication No. 8-231707, etc., having a number average molecular weight (Mn) of 6,000 or more and a molecular weight distribution (Mw/Mn) of 1.6 or less, are not limited thereto.
Further, the hydrolyzable silyl group-containing polyoxyalkylene polymer of the present invention may use MS polymers from Kaneka, for example, S203H, S303H, SAT010, SAX350, SAX400, SAX750 and S227; s2410, S2420, S3430, S3630, 888E, 6735D, S5830 from AGC company; STP-E10, STPE-30, STPE-15, STPE-35, WP-1, WP-2 from Wacker corporation; 350A, 380, 3318T, 3368T, 3623T, 30000T, 12000DS, etc. from Risun corporation. In some preferred embodiments of the present invention, SAX350, SAX750 or a mixture thereof is used.
In the present invention, the content of the above-mentioned hydrolyzable silyl group-containing polyoxyalkylene polymer in the curable composition of the present invention may be 10% by weight or more, preferably 15% by weight or more, and the upper limit of the content thereof may be 50% by weight or less, preferably 40% by weight or less, from the viewpoint of facilitating processing.
(other hydrolyzable silyl group-containing Polymer)
The curable composition of the present invention may contain a hydrolyzable silyl group-containing polymer in addition to the hydrolyzable silyl group-containing polyoxyalkylene polymer described above.
For such polymers, the following polymer backbones may be present: hydrocarbon polymers such as ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, copolymers of isoprene or butadiene and acrylonitrile and/or styrene, and copolymers of polybutadiene, isoprene or butadiene and acrylonitrile and styrene, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; polyester polymers obtained by condensation of dibasic acids such as adipic acid with diols or ring-opening polymerization of lactones; a (meth) acrylic acid ester polymer obtained by radical polymerization of a monomer such as ethyl (meth) acrylate or butyl (meth) acrylate; vinyl polymers obtained by radical polymerization of monomers such as (meth) acrylic acid esters, vinyl acetate, acrylonitrile, and styrene; a graft polymer obtained by polymerizing a vinyl monomer in the organic polymer; polysulfide polymers; nylon 6 obtained by ring-opening polymerization of epsilon-caprolactam, nylon 6/6 obtained by polycondensation of hexamethylenediamine and adipic acid, nylon 6/10 obtained by polycondensation of hexamethylenediamine and sebacic acid, nylon 11 obtained by polycondensation of epsilon-aminoundecanoic acid, nylon 12 obtained by ring-opening polymerization of epsilon-aminododecalactam, and polyamide polymers such as copolymerized nylon having 2 or more components of the above nylon; polycarbonate-based polymers produced by polycondensation of, for example, bisphenol a and phosgene; diallyl phthalate type polymers, and the like.
Further, from the viewpoint of imparting excellent heat resistance and adhesive strength retention to the final cured layer, it is preferable to use an acrylic polymer containing a hydrolyzable silyl group, typically such as KANEKA, for the other hydrolyzable silyl group-containing polymerMA904, etc.
In addition, in some embodiments of the present invention, the other hydrolyzable silyl group-containing polymer may be used in an amount of 50% by weight or less, for example 45% by weight or less, 40% by weight or less, 35% by weight or less, based on the total weight of the curable composition. The lower limit of the other hydrolyzable silyl group-containing polymer is not particularly limited, and may be, for example, 5% by weight or more, 8% by weight or more, 10% by weight or more, or the like.
(inorganic filler)
In the present invention, an inorganic filler may be added to the curable composition in view of improving the adhesive strength of the final cured layer.
The kind of the inorganic filler is not particularly limited, and conventionally known inorganic fillers can be widely used. Specific examples thereof include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, calcined clay, and kaolin, fibrous fillers such as calcium carbonate, dolomite, anhydrous silicic acid, hydrous silicic acid, magnesium carbonate, diatomaceous earth, talc, titanium oxide, bentonite, organobentonite, iron oxide, aluminum micropowder, zinc oxide, active zinc white, and glass fiber. These components may be used singly or in combination of two or more. By adding the inorganic filler, the dispersion stability of the composition and the strength of the cured layer are improved. In particular, calcium carbonate is preferable from the viewpoints of improving handleability, availability, and cost.
The calcium carbonate may be at least 1 or more selected from ground calcium carbonate, precipitated calcium carbonate, and calcium carbonate obtained by subjecting these calcium carbonates to surface treatment. Precipitated calcium carbonate is classified into light calcium carbonate having a major diameter of 1 μm or more and (colloidal) calcium carbonate having an average particle diameter of 1 μm or less, and any of these may be used.
Among them, the inorganic filler of the present invention preferably contains at least (colloidal) calcium carbonate having an average particle diameter of 1 μm or less, and more preferably has an average particle diameter of 0.3 to 1 μm, from the viewpoint of obtaining good mechanical properties.
In addition, calcium carbonate subjected to surface treatment may be used. Examples of the surface treatment agent include fatty acids such as stearic acid, fatty acid esters, modified fatty acids, resin acids such as rosin, paraffin wax, polyethylene wax, and cationic surfactants.
The amount of the inorganic filler is preferably 10 to 500 parts by weight, more preferably 50 to 450 parts by weight, and even more preferably 200 to 400 parts by weight, based on 100 parts by weight of the hydrolyzable silyl group-containing polyoxyalkylene polymer, in terms of securing strength, processability, and the like. If it is less than 10 parts by weight, it is likely to adversely affect dispersion stability and strength, and if it exceeds 500 parts by weight, there is a tendency to increase the viscosity of the system and decrease processability.
(silane Compound)
In the present invention, a silane compound may be used in the curable composition in view of alkali resistance, strength retention, and the like.
The silane compound is a silane compound obtained by partially condensing an aminosilane compound having a reactive silicon group with each other, or a silane compound obtained by partially condensing an aminosilane compound having a reactive silicon group with an alkoxysilane compound other than aminosilane.
Such silane compounds are mainly used for adjusting the adhesiveness, and may be referred to as an adhesiveness-imparting agent (or an adhesion promoter or a tackifier).
Specifically, the silane compound may be a silane compound containing either "(i) a silane compound obtained by partially condensing aminosilane compounds having a reactive silicon group with each other" (hereinafter, also referred to as "component i") or "(ii) a silane compound obtained by partially condensing aminosilane compounds having a reactive silicon group with alkoxysilane compounds other than aminosilane" (hereinafter, also referred to as "component ii"). In the component i, 1 or 2 or more aminosilane compounds having a reactive silicon group may be used. The condensation of the ii component is preferably partial condensation of reactive silicon groups of the aminosilane compound having reactive silicon groups with each other. In the component ii, 1 or 2 or more aminosilane compounds having a reactive silicon group may be used. In the component ii, 1 kind of alkoxysilane compound may be used, or 2 or more kinds may be used in combination. The condensation of the ii component is preferably a partial condensation of a reactive silicon group of an aminosilane compound having a reactive silicon group with an alkoxy group of an alkoxysilane compound.
Examples of the aminosilane compound having a reactive silicon group include N-2-aminoethyl-3-aminopropyl trimethoxysilane, N-2-aminoethyl-3-aminopropyl triethoxysilane, N-2-aminoethyl-3-aminopropyl methyldimethoxy silane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyldimethoxy silane, 3-aminopropyl methyldiethoxy silane, N-phenyl-3-aminopropyl trimethoxysilane, N-phenyl-1-aminomethyltriethoxysilane, N-N-butyl-3-aminopropyl trimethoxysilane, and the like. As the aminosilane compound having a reactive silicon group, 1 kind of them may be used, or 2 or more kinds may be used in combination.
Examples of the alkoxysilane compound include hydrocarbon-containing silanes such as methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltriacetoxysilane, and the like; (b) Silicate compounds such as tetramethyl orthosilicate (tetramethoxysilane or methyl silicate), tetraethyl orthosilicate (tetraethoxysilane or ethyl silicate), tetrapropyl orthosilicate, and tetrabutyl orthosilicate; (c) Epoxy group-containing silanes such as 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, and 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane; (d) Vinyl unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxy silane, 3-acryloxypropyl trimethoxysilane, and methacryloxymethyl trimethoxysilane; (e) Mercaptosilanes such as 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl methyl dimethoxysilane, 3-mercaptopropyl methyl diethoxysilane, mercaptomethyl trimethoxysilane, and mercaptomethyl triethoxysilane; (f) Isocyanurate silanes such as 1,3, 5-tris (3-trimethoxysilylpropyl) isocyanurate; (g) or a partial hydrolysis condensate thereof, and the like. As the alkoxysilane compound, 1 kind of them may be used, or 2 or more kinds may be used in combination.
Further, specific examples of the silane compound of the present invention include X-40-2651 (manufactured by Xinyue chemical Co., ltd.), MS3301 (manufactured by JNC Co., ltd.), MS3302 (manufactured by JNC Co., ltd.), DYNASYLAN1146 (manufactured by EVONIK Co., ltd.), DYNASYLAN1124 (manufactured by EVONIK Co., ltd.), and the like.
The amount of the silane compound used in the present invention may be 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, and more preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the hydrolyzable silyl group-containing polyoxyalkylene polymer.
(epoxy resin)
In the present invention, the curable composition may further include an epoxy resin in view of improving the adhesive strength of the cured layer.
The specific kind of the epoxy resin is not particularly limited, and one or more of aliphatic epoxy, alicyclic epoxy or aromatic epoxy may be used, and preferably an aromatic epoxy resin, for example, an epoxy resin having a bisphenol a structure or the like is used.
Further, as for the amount of the epoxy resin, in some specific embodiments of the present invention, the amount of the epoxy resin may be 50 wt% or less, for example, 45 wt% or less, 40 wt% or less, 35 wt% or less, etc., and the lower limit of the epoxy resin is not particularly limited, for example, 5 wt% or more, 8 wt% or more, 10 wt% or more, etc., based on the total weight of the curable composition.
(other Components)
The curable composition of the present invention may contain other components than the above, within a range that does not impair the effects of the present invention.
Stabilizers may also be added to the curable composition of the present invention. 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 improved. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, and particularly preferred hindered phenols include Irganox 1010 and Irganox 245. The amount of the antioxidant to be used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the hydrolyzable silyl group-containing polyoxyalkylene polymer. When a light stabilizer is used, photo-oxidative degradation of the cured product can be prevented. Examples of light stabilizers include benzotriazole based, hindered amine based, benzoate based compounds and the like. In one embodiment of the invention, a hindered amine light stabilizer such as Tinuvin 770. The amount of the light stabilizer to be used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer having a hydrolyzable silyl group. When an ultraviolet absorber is used, the surface weather resistance of the cured product can be improved. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted toluene-based and metal chelate-based compounds, and benzotriazole-based compounds such as Tinuvin 326 are particularly preferred. The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the hydrolyzable silyl group-containing polyoxyalkylene polymer.
In the present invention, a small amount of carbon black may be blended in order to further improve the tensile strength. Examples thereof include furnace black, lamp black, gas black, channel black, pyrolytic carbon black, and acetylene black obtained by an oil furnace method or a gas furnace method. Carbon black obtained by a furnace method as a main stream is preferable from the viewpoint of availability. Specific examples of the carbon black are commercially available products such as HIBLACK30, HIBLACK10, HIBLACK5L, HIBLACK L, and the like. The carbon black may be used alone or in combination of 2 or more. The amount of the carbon black to be used is preferably 0.1 to 8 parts by weight, more preferably 0.3 to 5 parts by weight, particularly preferably 1 to 3 parts by weight, based on 100 parts by weight of the hydrolyzable silyl group-containing polyoxyalkylene polymer. In the embodiments of the present invention, the amount of carbon black is small, and thus, it is not considered to be the other inorganic filler described in the present invention.
In some embodiments of the invention, a dehydrating agent is also added. Examples of the dehydrating agent include: synthetic zeolite, activated alumina, silica gel, quicklime, magnesia, alkoxysilane compounds (e.g., n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methyl silicate, ethyl silicate, gamma-mercaptopropylmethyldimethoxysilane, gamma-mercaptopropylmethyldiethoxysilane, gamma-glycidoxypropyl trimethoxysilane, etc.), oxazolidines compounds, isocyanate compounds, and the like. In one embodiment of the present invention vinyltrimethoxysilane is used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the hydrolyzable silyl group-containing polyoxyalkylene polymer.
In some embodiments of the present invention, a curing catalyst is also added in order to promote curing. Silanol condensation catalysts known in the art can be used. Specific examples of silanol condensation catalysts include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetra (acetylacetonate), titanium bis (acetylacetonate) diisopropoxide, titanium bis (ethoxyacetoacetyl) diisopropoxide, and the like; organic compounds such as dimethyltin diacetate, dibutyltin bis (acetylacetonate), dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate), dibutyltin bis (ethylmaleate), dibutyltin bis (butylmaleate), dibutyltin bis (octylmaleate), dibutyltin bis (tridecylmaleate), dibutyltin bis (benzylmaleate), dibutyltin diacetate, dioctyltin bis (ethylmaleate), dioctyltin bis (octylmaleate), dibutyltin dimethoxide, dibutyltin bis (nonylphenol), dibutyltin oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetylacetonate), dibutyltin oxide-silicate compound reactant, dioctyltin oxide-phthalate reactant, dioctyltin dilaurate, dioctyltin diacetate, and dioctyltin bis (acetylacetonate); organoaluminum compounds such as aluminum tris (acetylacetonate), aluminum tris (ethylacetylacetonate), aluminum ethylacetoacetate diisopropyloxy and the like; zirconium compounds such as zirconium tetra (acetylacetonate); carboxylic acids and/or carboxylic acid metal salts; an amidine compound; amine compounds such as butylamine, octylamine, di-n-butylamine, laurylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleamide, cyclohexylamine, benzylamine, diethylaminopropylamine, and salts thereof with carboxylic acids. Specific examples of references also include silanol condensation catalysts known in the art such as other acidic catalysts and basic catalysts. These catalysts may be used alone or in combination of two or more. The silanol condensation catalyst is preferably used in an amount of 0.01 to 5 parts by weight, particularly preferably from 0.1 to 2 parts by weight, relative to 100 parts by weight of the hydrolyzable silyl group-containing polyoxyalkylene polymer. The amount used is less than 0.01 parts by weight, the composition is not easily cured, and if the amount used exceeds 5 parts by weight, there is a tendency that storage stability and adhesiveness are lowered. Dibutyl tin dilaurate is preferred from the standpoint of both curability and cost.
In some embodiments of the present invention, plasticizers may also be added to the curable compositions of the present invention. As the plasticizer, known plasticizers are used, and specific examples include phthalate compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), butyl benzyl phthalate, etc.; terephthalate compounds such as bis (2-ethylhexyl) -1, 4-benzenedicarboxylate; non-phthalate compounds such as diisononyl 1, 2-cyclohexanedicarboxylate; aliphatic polycarboxylic acid ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate and tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetyl ricinoleate; phenyl alkyl sulfonate; phosphate compounds such as tricresyl phosphate and tributyl phosphate; a trimellitate compound; chlorinated paraffin; hydrocarbon-based oils such as alkylbiphenyls and partially hydrogenated terphenyls; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxystearate. In addition, high molecular plasticizers such as polyalkylene oxides may also be used; (meth) acrylate-based polymers; polyalkylene glycol esters such as diethylene glycol dibenzoate, triethylene glycol dibenzoate and pentaerythritol esters; polyesters obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid, and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol; polyether obtained by urethanizing hydroxyl groups of polyether polyol, polyether obtained by esterifying carboxylic acid, and polyether obtained by etherifying terminal; polystyrene such as polystyrene and poly- α -methylstyrene; polybutadiene, polybutene, polyisobutene, butadiene-acrylonitrile, polychloroprene; hydrogenated alpha-olefins such as hydrogenated polybutadiene oligomers, and the like. These components may be used singly or in combination of two or more. As a particularly preferred plasticizer, diisononyl phthalate is used. The plasticizer is used in an amount of preferably 10 to 120 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of the hydrolyzable silyl group containing polyoxyalkylene polymer. If the amount is less than 10 parts by weight, the effect of viscosity reduction is small and processability becomes insufficient; if the amount exceeds 120 parts by weight, sufficient mechanical properties cannot be obtained.
Further, various additives may be added to the curable composition of the present invention as needed in order to adjust other various physical properties of the curable composition. Examples of such additives include, for example, other organic fillers (e.g., PVC or PMMA powder, etc.), thixotropic agents, flame retardants, radical inhibitors, metal deactivators, ozone deterioration inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments, foaming agents, solvents, mold inhibitors, and the like. The various additives may be used singly or in combination of two or more.
(viscosity of curable composition)
The viscosity of the curable composition of the present invention is not particularly limited as long as the above composition is satisfied. In some preferred embodiments of the present invention, the curable composition of the present invention may have a viscosity of 100pa.s or more, preferably 200pa.s, and for the upper limit of viscosity may be 5000pa.s or less, preferably 4000pa.s or less, in some specific embodiments, from the viewpoint of ease of use.
The viscosity is a viscosity measured by using a brookfield rotational viscometer, and specifically: type B (JIS K7117) viscometer: after allowing the curable composition to stand at room temperature of 23℃for 24 hours, the viscosity at 1rpm was measured and recorded.
(preparation of curable composition)
The curable composition of the present invention may be a one-part composition prepared by mixing all the components and cured by moisture in the air. The curable composition of the present invention may be a two-part composition in which a curing catalyst and other components (for example, a filler, a plasticizer, water, etc.) are blended to prepare a 1 st composition, a hydrolyzable silyl group-containing polyoxyalkylene polymer and, if necessary, other components are blended to prepare a 2 nd composition, and the 1 st composition and the 2 nd composition are mixed and used before use. The curable composition of the present invention may be a multi-fluid composition obtained by preparing three or more kinds of compositions separately and mixing the three or more kinds of compositions before use. From the viewpoint of workability, a one-pack type composition is preferable.
In preparing the curable composition of the present invention, the moisture-containing component is preferably used after dehydration and drying in advance, or dehydration is performed by decompression or the like during kneading. In the case of dehydrating or drying a solid such as a powder, a heat drying method or a reduced pressure dehydrating method is preferable, and in the case of dehydrating or drying a liquid, a reduced pressure dehydrating method or a method using a dehydrating agent is preferable.
The method for producing the curable composition of the present invention is not particularly limited, and for example, a conventional method may be employed in which the above-mentioned components are mixed and kneaded at normal temperature or under heating using a mixer, a roll, a kneader or the like, or a small amount of a solvent is used to dissolve the components and mix them.
< Water-proofing method >
Further, the present invention also provides a waterproof construction method, specifically, a waterproof construction method for a structure to be waterproof out of the inside. In the present invention, the waterproofing method includes a first method and a second method, but from the viewpoint of convenience of construction, it is preferable to use the first method for waterproofing.
The first method includes the following steps a to C:
step A: forming a layer containing a curable composition on the surface to be waterproofed, wherein the curable composition comprises a polyoxyalkylene polymer containing a hydrolyzable silyl group;
and (B) working procedure: laminating a polymer sheet having a fiber layer on the surface side thereof such that the layer containing the curable composition faces the fiber layer;
and (C) working procedure: the curable composition is cured to form a cured layer.
The second method includes the following steps a 'to C':
Procedure a': forming a layer containing a curable composition on a fiber layer of a polymer sheet having the fiber layer on a surface side, wherein the curable composition comprises a polyoxyalkylene polymer containing a hydrolyzable silyl group;
procedure B': laminating the polymer sheet obtained in the step A' with the surface to be waterproofed via the layer containing the curable composition;
procedure C': the curable composition is cured to form a cured layer.
The surface to be waterproofed refers to one surface or a part of the surface to be waterproofed. For example, concrete slabs, concrete surfaces with existing waterproof layers, reinforced or precast concrete surfaces, slate slabs, gypsum surfaces, mortar surfaces, exterior surfaces of heat insulating products, surfaces of metal products (e.g., copper, iron, aluminum products, etc.), and the like. In some embodiments of the invention, the construction surface is a roof surface or a side elevation. The invention is especially suitable for large-area elevation construction.
Further, both the above-described first method and second method of the present invention can be applied to a one-liquid type, two-liquid type or multi-liquid type curable composition.
For the step C or the step C' in the waterproof construction method of the present invention: the layer of curable composition is cured to form a cured layer. The curing process is moisture curing, namely, the construction surface treated by the first two steps is exposed to the atmosphere, a three-dimensional network structure is formed by interaction of the polyoxyalkylene polymer containing hydrolytic silyl groups in the curable composition and moisture in the air, and the curable composition layer is cured into a cured product with rubber elasticity, so that the construction surface, the layer containing the curable composition and the waterproof sheet are bonded.
Further, according to the waterproof construction method, the present invention can obtain a waterproof structure for a structural object as follows: a polymer sheet having a cured layer formed on a surface of a structure to be water-repellent treated and bonded via the cured layer; wherein the cured layer is a layer formed by curing a curable composition comprising a polyoxyalkylene polymer having a hydrolyzable silyl group; the polymer sheet has a fiber layer on the surface side to which the cured layer is bonded. Preferably, the fiber layer is a nonwoven layer.
The structure of the present invention, similar to the foregoing description, may include a building, a thermal insulator, a metal product, or the like.
For buildings, mainly, artificial buildings are referred to, and further, artificial buildings include ground buildings and accessories thereof, above-water buildings such as ships, underwater buildings, and the like. The part of the artificial building suitable for the waterproof construction method is not limited, and the construction can be performed on places needing to be waterproof, such as roofs, balconies, open corridors, roads, outer walls and the like; underground parts (such as underground passages and tunnels) and the like, and places needing waterproof treatment on underground water; bathroom, kitchen, toilet, sink, sewage pool, etc., where water-proof is needed for domestic water; heat storage layers, swimming pools, waste liquid treatment tanks, landfill sites and other places requiring water resistance to industrial water.
For heat insulators or metal products, mainly industrial products requiring a waterproofing treatment, the influence of environmental conditions on these industrial products can be reduced by the waterproofing treatment.
Examples
The invention will be further illustrated by the following specific examples:
(test method)
1) Peel test:
90 ° peel test method, a waterproof sheet is adhered immediately after the curable composition is coated on the adherend. After curing for 168 hours at 23.+ -. 2 ℃, a 90 ℃ peel test was performed at 23.+ -. 2 ℃ and 50 mm/min.
2) Alkali resistance test:
the sample was subjected to alkaline solution (0.1% NaOH aqueous solution+saturated Ca (OH) at 23.+ -. 2 ℃ C.) 2 Solution) for 168 hours, thenTaken out of the alkaline solution, stored at 23.+ -. 2 ℃ for 4 hours, and then subjected to the tensile test of 3) below at 23.+ -. 2 ℃.
3) Tensile test break tensile test:
tensile breaking test of dumbbell type adhesive pieces according to GB/T19250-2013 (Table 4), tensile breaking test was performed at 23.+ -. 2 ℃ and 500mm/min.
4) Tear strength test:
the tear strength test method used in GB/T19250-2013 (Table 4) was carried out at a temperature of 23.+ -. 2 ℃ and a tensile speed of 500mm/min.
5) Heat resistance test:
one cycle of the heat resistance experiment: the test specimens were subjected to the following conditions, 23 ℃ x 17 hours + (85 ℃,85% rh) x 7 hours.
6) Adhesive strength test:
the curable composition was adhered to an adherend at a fixed position, and after curing the curable composition under the given conditions, the cured product was clamped by using a test clamp, and a tensile test (temperature 23.+ -. 2 ℃ C., tensile speed (5.+ -. 1) mm/min) was performed to determine the strength at the interface between the cured layer and the adherend as the adhesive strength.
(fracture surface evaluation/morphology)
A: the cohesive failure rate is more than 80 percent
B: the cohesive failure rate is more than 50% and less than 80%
C: the cohesive failure rate is more than 5% and less than 50%
D: the interface destruction rate is 100%.
Note that: the term "failure rate" as used above means a failure rate expressed as an area ratio, that is, a ratio of a cohesive failure rate with respect to an adhesion area between a curable composition and an adherend.
(formation of curable composition)
The curable compositions used in each of the examples and comparative examples were obtained by mixing the components shown in the respective tables below.
Examples 1 to 2 and comparative examples 1 to 2
The curable compositions obtained after mixing according to the respective component materials and weights given in table 1 were subjected to a 90 ° peel test and gave a peel morphology evaluation:
Table 1:
among them, comparison of examples with comparative examples shows that the use of the waterproof sheet with a nonwoven layer of the present invention can obtain more excellent adhesive properties.
Examples 1,3 to 6 alkali resistance test
The curable compositions obtained after mixing according to the component substances and weights given in table 2 were subjected to tensile testing at break after immersion in alkaline solution:
table 2:
examples 1,7 to 13 tear Strength test
The curable compositions obtained after mixing according to the component materials and weights given in table 3 were subjected to a tear strength test, wherein the calcium carbonate particles had the following average particle sizes:
CCS-18PV:60nm; KALFINE 200A:80nm; omya 1T:2.4 μm; hydrocarb95T 0.9 μm; XL-8500C is less than 1 μm.
Table 3:
examples 14, 15 and 16
The curable compositions were formulated in a two-liquid configuration according to the respective component materials and weights given in tables 4 and 5, and the tests as shown in Table 6 were performed:
table 4:
table 5:
table 6:
examples 1,17 and 18 Heat resistance test
The curable composition was prepared according to the composition of the following table 7, and the adhesive strength was tested, wherein the surface to be waterproofed was an aluminum surface.
Table 7:
industrial applicability
The waterproof construction method disclosed by the invention can be industrially applied.

Claims (11)

1. A waterproof construction method is characterized by at least comprising the following steps of:
step A: forming a layer containing a curable composition on the surface to be waterproofed, wherein the curable composition comprises a polyoxyalkylene polymer containing a hydrolyzable silyl group;
and (B) working procedure: laminating a polymer sheet having a fiber layer on the surface side thereof such that the layer containing the curable composition faces the fiber layer;
and (C) working procedure: the curable composition is cured to form a cured layer.
2. A waterproof construction method is characterized by at least comprising the following steps of:
procedure a': forming a layer containing a curable composition on a fiber layer of a polymer sheet having the fiber layer on a surface side, wherein the curable composition comprises a polyoxyalkylene polymer containing a hydrolyzable silyl group;
procedure B': laminating the polymer sheet obtained in the step A' with the surface to be waterproofed via the layer containing the curable composition;
procedure C': the curable composition is cured to form a cured layer.
3. The waterproof construction method according to claim 1 or 2, wherein the fiber layer is a nonwoven fabric layer.
4. The method according to any one of claims 1 to 3, wherein the curable composition further comprises a silane compound which is a silane compound obtained by partially condensing an aminosilane compound having a reactive silicon group with each other or a silane compound obtained by partially condensing an aminosilane compound having a reactive silicon group with an alkoxysilane compound other than an aminosilane.
5. The method according to any one of claims 1 to 4, wherein the curable composition contains an inorganic filler, wherein the inorganic filler comprises calcium carbonate having an average particle diameter of 1 μm or less.
6. The method according to any one of claims 1 to 5, wherein the curable composition further comprises one or more of an epoxy resin and a hydrolyzable silyl group-containing acrylic resin.
7. The method according to any one of claims 1 to 6, wherein the polymer sheet is a thermoplastic polyolefin sheet having a fiber layer on a surface side.
8. A waterproof construction method of a structure, characterized in that the method comprises the waterproof construction method according to any one of claims 1 to 7.
9. The method of waterproofing a structure according to claim 8, wherein the structure comprises a building, a thermal insulator, or a metal product.
10. A waterproof structure for a structure, comprising a cured layer formed on a surface of the structure to be waterproof-treated, and a polymer sheet bonded via the cured layer;
wherein the cured layer is a layer formed by curing a curable composition comprising a polyoxyalkylene polymer having a hydrolyzable silyl group;
the polymer sheet has a fiber layer on the surface side to which the cured layer is bonded.
11. The waterproof structure of claim 10, wherein the fibrous layer is a nonwoven layer.
CN202210331074.8A 2022-03-30 2022-03-30 Waterproof construction method and waterproof structure Pending CN116927509A (en)

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