JPS646238B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a so-called "hot melt type" sealing or caulking material that is heated to a semi-molten state during construction and applied to areas to be sealed or caulked, and has excellent sealing or caulking properties, non-slump properties, and low-temperature application. Improved properties such as weather resistance, low tack resistance, chemical resistance, stain resistance, and durability. Related to hot melt type sealing or caulking materials. More specifically, the present invention relates to waxes that are solid at room temperature (25°C) and melt and become liquid at 40° to 200°C, and have a viscosity of 1000 cps at 200°C.
In the following waxes, acrylic and/or methacrylic monomers are dispersed and polymerized under the melting conditions of the wax. A heat-sensitive type in which the wax is about 5 to about 200 parts by weight per 100 parts by weight of the polymer or copolymer, which is composed of dispersed particles of a polymer or copolymer with a glass transition point of about -50°C to about +20°C. This invention relates to a hot melt sealing or caulking material containing 100 parts by weight of a polymerization reaction product and 75 to 120 parts by weight of an inorganic filler having an oil absorption of about 35 or more uniformly dispersed in the reaction product. For example, filling gaps around window frames, buried pipes, and other gaps, filling joints in concrete and mortar, filling gaps at various joints in bathtubs, pools, containers, automobiles, ships, etc., and filling gaps in furniture and partitions. Sealing materials or caulking materials are used to fill gaps and in a wide range of other fields. Such sealants or caulking materials include hardening sealants or caulking materials such as silicone, thiocol, and urethane, oil-based sealants or caulking materials such as drying oils and alkyd resins, and acrylic emulsions. Non-hot melt sealants or caulks, such as emulsion sealants, are commonly used. Conventionally, in hot-melt type sealants or caulking materials to which the sealant or caulking material of the present invention belongs, acrylic and/or methacrylic polymers or copolymer resins have been used for their weather resistance, low cost, low volume shrinkage, Although advantages such as quick curing time can be expected, it is difficult to provide the appropriate heat sensitivity required for hot-melt sealants or caulking materials, so these resins are not satisfactory as hot-melt sealants or caulking materials. I couldn't expect it to be used as much as possible. In particular, these resins are virtually impossible to form into homogeneous hot melt blends with heat-sensitive materials, such as waxes, to impart adequate heat-sensitivity. In order to provide good dispersibility, a large amount of heat-sensitive material must be blended.
As a result, even if available heat sensitivity can be imparted, the resin concentration is unduly reduced, causing a problem in which the desired performance as a sealing material or caulking material cannot be obtained. For these reasons, sealants or caulking materials containing acrylic and/or methacrylic resin components that are in practical use include:
For example, combinations of ethylene-ethyl acrylate (weight ratio, approximately 77:23) copolymer whose main component is ethylene, low softening point polypropylene with a softening point of approximately 105°C, butyl rubber, ethylene-propylene copolymer rubber, etc. is being used to a certain extent. In this type of combination, a greater than equal amount of the low softening point polypropylene is used based on the weight of the copolymer;
Its sealing or caulking performance is unsatisfactory, and it shows unsatisfactory results in many respects, for example, application characteristics such as a sharp decrease in viscosity upon heating, weather resistance, low tackiness, stain resistance, and durability. The present inventors have found that the preferred advantages of acrylic and/or methacrylic resins can be maintained, and the application suitability exhibits excellent sealing or caulking properties, non-slump properties, low-temperature applicability, and sharp viscosity reduction properties upon heating; Weather resistance, low tack resistance,
We are conducting research to provide a resin-wax type sealing or caulking material based on acrylic and/or methacrylic resins that has improved properties such as chemical resistance, stain resistance, and durability. It came. As a result, it is solid at room temperature (25℃) and
Waxes that melt and become liquid at 40° to 200°C, and have a viscosity of 1000 cps or less at 200°C, contain acrylic and/or methacrylic monomers under the melting conditions of the waxes. The glass transition point of the monomer uniformly dispersed in the wax after the reaction obtained by dispersion polymerization of
A heat-sensitive polymerization reaction product consisting of dispersed particles of a polymer or copolymer at 20°C, in which the wax is present in an amount of about 5 to about 200 parts by weight per 100 parts by weight of the polymer or copolymer. The above-mentioned holt-melt type sealing or caulking material uses a type polymerization reaction product as a resin component and contains an inorganic filler with an oil absorption of about 35 or more in an amount of 75 to 120 parts by weight per 100 parts by weight of the resin component. It has been discovered that this material can be an excellent holt-melt type sealing or caulking material that solves many problems at once and has the above-mentioned improved properties. In particular, among the above-mentioned specific waxes, a heat-sensitive polymerization reaction product of a dispersion polymerization type under melting conditions is particularly preferred, and the use of such a product containing dispersed particles of a specific particle size dispersed in a wax matrix and conventional , contrary to the conventional wisdom that an inorganic filler with as low oil absorption as possible should be blended because it may adversely affect the performance of the sealing or caulking material, we decided to use the highest possible oil absorption, especially around Combined with the use of an inorganic filler with an oil absorption of 35 or more, it is possible to achieve both of the above-mentioned improved properties, and to provide a hot-melt sealing or caulking material that is particularly suitable for easy-to-apply cartridge extrusion application. I understood. It is therefore an object of the present invention to provide a hot melt sealing or caulking material which has the above-mentioned improved properties and is particularly suitable for cartridge extrusion applications. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. Regarding a wide range of heat-sensitive polymerization reaction products that can include heat-sensitive polymerization reaction products of dispersion polymerization type under melting conditions in the waxes used in the hot-melt sealing or caulking materials of the present invention, and the method for producing the same, No. 51-37304 and has already been disclosed in detail. In the present invention,
Among the waxes that can be produced in the same manner as the above proposal,
A heat-sensitive polymerization reaction consisting of dispersed particles of the monomer uniformly dispersed in the wax after the reaction obtained by dispersing and polymerizing an acrylic and/or methacrylic monomer under melting conditions of the wax. The products are selected and utilized. This proposal includes the use of acrylic and/or methacrylic resins, which have not been previously available in the field of hot melt sealants or caulking materials, by making them into heat-sensitive polymerization reaction products formed by the proposed method. It can be used in the field of hot-melt sealing or caulking materials, and moreover, it can be useful in forming excellent hot-melt sealing or caulking materials having the above-mentioned improved properties. There is no disclosure of any knowledge useful in reaching the selection of the present invention, such as the fact that contrary to common technical knowledge, it is advisable to use an inorganic filler with as large an oil absorption amount as possible. In the heat-sensitive polymerization reaction product used in the present invention,
The average particle diameter of the dispersed particles of the acrylic and/or methacrylic polymer or copolymer uniformly dispersed in the wax matrix after the reaction is:
It is preferably about 5.0μ to about 0.1μ, more preferably about 2μ to about 0.5μ. In the present invention, in addition to the acrylic and/or methacrylic monomers, the acrylic and/or methacrylic monomers used to form the dispersion polymerization type heat-sensitive polymerization reaction product in the melted wax are , comonomers that can be copolymerized with these monomers can be used in combination. The acrylic and/or methacrylic monomer is about 50 mol% or more of the total monomers,
More preferably, it accounts for about 65 mol% or more. Examples of polymers or copolymers that form such dispersed particles include polymers or copolymers of esters of acrylic acid and/or methacrylic acid, and comonomers copolymerizable with these esters. A preferred example is a copolymer with a body. When selecting a type of comonomer other than acrylic and/or methacrylic, it is preferable to use it while satisfying the above-mentioned quantity conditions. Examples of such polymers or copolymers include:
Esters of acrylic acid and/or methacrylic acid, such as methyl, ethyl, propyl, butyl, pentyl, cyclohexyl, octyl, decyl, lauryl, tridecyl, myristyl, cetyl, stearyl , methoxyethyl-, ethoxyethyl-, butoxyethyl-, methoxypolyethylene-, glycol-, hydroxyethyl-, hydroxypropyl-, 2hydroxy-3chloropropyl-, dimethylaminoethyl-, glycidyl-, tetrafurfuryl-,
Examples include homopolymers or copolymers of 2,3 dibromopropyl, 2-chloroethyl, tribromophenyl, allyl, ethylene glycol, and polyethylene glycol esters. Furthermore, the above esters of acrylic acid and/or methacrylic acid and vinyl esters such as vinyl acetate, vinyl propionate, etc.; unsaturated acids such as acrylic acid, methacrylic acid, itaconic acid, etc.; trimethylolpropane triacrylate or methacrylate, acrylic acid chloride,
Methacrylic acid chloride, sodium, zinc, calcium, aluminum, etc. salts of acrylic acid or methacrylic acid, sulfopropyl acrylate, sodium or ammonium sulfopropyl acrylate, acrylonitrile, methacrylonitrile, acrylic or methacrylamide, N-
Methyloacrylamide, N-butoxymethylacrylamide, diacetone acrylamide,
Acrylic acid or methacrylic acid derivatives such as N-tert-butylacrylamide; aliphatic unsaturated hydrocarbons such as ethylene, propyl, butene, butadiene, isoprene, etc.; aromatic unsaturated hydrocarbons such as styrene, vinyltoluene, etc. Class;
Examples include copolymers with vinyl monomers such as vinyl chloride and vinylidene chloride. In the present invention, in the wax matrix,
acrylic and/or as described above forming dispersed particles;
Alternatively, the glass transition point of the methacrylic polymer or copolymer is preferably about -50° to about +20°C. In the composition of the present invention, the polymer or copolymer preferably has a glass transition temperature range of about 20,000 to about 500,000 from the viewpoint of softness. It usually has a number average molecular weight of about 100%. Examples of waxes used in the formation of the heat-sensitive polymerization reaction product used in the present invention include petroleum-based waxes such as paraffin wax, microcrystalline wax, and petrolatum; fats such as beef tallow and whale tallow; Class; low softening point polyethylene, low softening point polypropylene, low softening point polybutene, low softening point polybutadiene, low softening point copolymers of these olefins, low softening point ethylene/acrylic copolymers, etc. Olefin polymers or copolymers; higher aliphatic alcohols such as cetyl alcohol, stearyl alcohol, etc.; aliphatic polyhydric alcohols such as pentamethylene glycol, hexamethylene glycol, etc.;
Higher aliphatic ethers such as dicetyl ether and glycerin-1-cetyl ether; ketones such as dioctyl ketone and 2,7-octanedione; lauric acid, tridecylic acid, myristic acid, stearic acid, oxystearic acid, etc. higher fatty acids such as myricyl cerotate, methyl behenate, etc.; fatty acid salts such as calcium stearate, ammonium myristate, etc.; halogenated aliphatics such as chlorinated paraffin, stearoyl chloride, etc.; cyclododecane, cyclo Tetradecane, triphenylmethane,
Cyclic compounds such as polyoxyethylene nonyl phenyl ether; rosin and its hydrogenated products;
Petroleum resins; dammar, shellac, copal;
Solid epoxy compounds; etc. can be exemplified. These waxes are selected from those that are solid at room temperature and melt at 40° to 200°C, preferably 40° to 120°C, and become liquid.
This condition may be achieved by using multiple types of waxes as exemplified above. The viscosity of these waxes at 200℃ is
It is better to be less than 1000cps. Further, when carrying out dispersion polymerization of acrylic and/or methacrylic monomers in such waxes under melting conditions of the waxes, it is preferable to carry out the dispersion polymerization in the presence of a dispersant. In the heat-sensitive polymerization reaction product used in the present invention, based on 100 parts of the acrylic and/or methacrylic dispersed particle polymer or copolymer,
The waxes are about 5 to about 200 parts by weight, preferably about 10 to about 60 parts by weight, more preferably about 10 to about 60 parts by weight.
It is 40 parts by weight. If the amount is too small, the reaction product formation reaction will be difficult to operate and it will be difficult to obtain the desired heat sensitivity, and if the amount is too large, properties such as flexibility and adhesion will deteriorate, so use the above-mentioned amounts. It is better. In the hot melt sealing or caulking material of the present invention, the oil absorption is about 35 or more, preferably about 40 to about 70, more preferably about 45 to about 60.
The inorganic filler is uniformly mixed and dispersed in the heat-sensitive polymerization reaction product. Any mixing means can be used as long as it can achieve as uniform mixing and dispersion as possible. For example, mixing means such as a kneader mixer equipped with a heating jacket, a roll mill, and a gear compounder pug mill can be employed. Mixing can be carried out, for example, by setting the jacket temperature of the kneader mixer at about 90°C, rotating the kneader at 40 rpm, adding the heat-sensitive polymerization reaction product heated to about 60°C, and then adding the heat-sensitive polymerization reaction product heated to about 60°C.
This can be done by gradually adding the inorganic filler and other ingredients over 15 minutes and mixing and stirring for about 30 minutes. Examples of the above inorganic fillers include barium carbonate,
Carbonates such as calcium carbonate; barium sulfate,
Examples include sulfates such as calcium sulfate; silicates such as white carbon and diatomaceous earth; and clay minerals such as kaolin, talc, sericite, asbestos, mica, and pentonite.
As these inorganic fillers, those having an oil absorption of about 35 or more are selected and used. The use of oil with an oil absorption of less than about 35 is disadvantageous in terms of poor slump resistance and stain resistance, and should be avoided in the present invention. The usage amount of these inorganic fillers is as follows:
75 to 120 per 100 parts by weight of heat-sensitive polymerization reaction product
Parts by weight are preferred. In the present invention, other additives such as plasticizers, stabilizers, ultraviolet absorbers, anti-aging agents, colorants, etc. can be further blended. The amount of such compounding agents to be used can be selected as appropriate, but for example, based on 100 parts by weight of the heat-sensitive polymerization reaction product, 0 to about 30 parts by weight of a plasticizer, 0 to about 5 parts by weight of a stabilizer, 0 to about 5
Examples of amounts used include 0 to about 5 parts by weight of an ultraviolet absorber, 0 to about 5 parts by weight of an antiaging agent, and 0 to about 20 parts by weight of a colorant. Examples of such other additive plasticizers include dialkyl phthalate esters such as dibutyl phthalate and di-n-octyl phthalate;
Phthalate mixed esters such as butyl benzyl phthalate, aliphatic dibasic acid esters such as dioctyl adipate, aliphatic ethers such as diethylene glycol, epoxidized oils such as epoxidized linseed oil, trioctyl trimellitate, chlorinated paraffins , triacetin, polypropylene adipate, and oligomers of ethylene monomers. Examples of the stabilizer include inorganic salts such as dibasic lead phosphite, metal soaps such as lead stearate and zinc stearate, and organic tin compounds such as dibutyltin laurate. In addition, as ultraviolet absorbers, dihydroxybenzophenone, 2-hydroxy-4
Examples include benzophenone UV absorbers such as octylbenzophenone, triazole UV absorbers such as benzotriazole, and salicylic acid ester UV absorbers such as phenyl salicylate. Furthermore, examples of anti-aging agents include aldol-α-naphthylamine, octylated diphenylamine, 2,5-di-tert.butylhydroquinone, and nickel salt of dibutyldioctylcarbamic acid. Furthermore, examples of colorants include white pigments such as titanium oxide and barium sulfate, black pigments such as carbon black and iron black, iron oxide yellow,
Yellow pigments such as Hansa yellow, red pigments such as Bengara, naphthol red, purple pigments such as cobalt violet, blue pigments such as ultramarine, phthalocyanine blue, green pigments such as phthalocyanine green, chrome green, etc. Examples include metal powder pigments such as powder and bronze powder. Oil absorption as used in this specification means ``The amount of linseed oil required to obtain a pasty material with a certain consistency by gradually adding linseed oil to the pigment and kneading it is called oil absorption.
The detailed test method is in accordance with the oil absorption test method described in Paint Handbook (published by Sangyo Tosho Co., Ltd.), pages 38 to 40. The hot-melt sealing or caulking material of the present invention can be used in any shape such as a sheet, rope, tape, or cartridge, but it is particularly suitable for extrusion in a cartridge type, which has good workability. Several embodiments of the material of the present invention will be explained in more detail with reference to Examples below. In addition, in the following examples, % and parts indicate weight % and parts by weight unless otherwise specified. Example 1 Preparation of polymeric composition In a glass reactor equipped with a stirrer, a thermometer, a cooling tube and a heating device, 140% paraffin [melting point 60
°C, viscosity 100 cps or less (200 °C)] 200 parts and ethylene/vinyl acetate copolymer dispersant [Evaflex 150, manufactured by Mitsui Polychemical Co., Ltd., vinyl acetate content 33%, melt index 30 at 180 °C]
After completely dissolving 80 parts and adjusting the temperature to 120°C, a mixture of 400 parts of ethyl acrylate, 200 parts of butyl acrylate, and 3.2 parts of azobisisobutyronitrile as a catalyst was added over 2 hours. ~120℃
After aging for about 2 hours at 120° C., a milky white dispersion-like polymer composition was obtained. The average particle diameter of the dispersed particles of this copolymer dispersion is about 1.2μ, the glass transition point of the copolymer is -38°C, and the heat-sensitive polymerization of 33 parts of the paraffin to 100 parts of the copolymer It was a reaction product. Sealing composition 400 parts of the obtained polymer composition in a kneader at 70°C ~
After kneading at 90℃ for 5 minutes, talc (oil absorption 60) 480
12 parts of titanium white and kneaded for a further 30 minutes (120 parts of inorganic filler per 100 parts of heat-sensitive polymerization reaction product). Table 1 shows the physical properties of the obtained composition. Example 2 A polymer composition obtained in the same manner as in Example 1 was used. Sealing Composition 400 parts of the polymeric composition were mixed in a kneader at 70-90°C for 10 minutes.
After kneading in minutes, add light calcium carbonate (oil absorption amount).
45) Add 200 parts, 20 parts of titanium white, and 180 parts of talc,
Kneading was carried out for a further 30 minutes (95 parts of inorganic filler per 100 parts of heat-sensitive polymerization reaction product). Table 1 shows the physical properties of the obtained composition.

[Table] As is clear from Table 1, Example-1, Example-
Both compositions No. 2 are caulking compositions with excellent stain resistance, slump resistance, alkali resistance, and weather resistance. In addition, cohesive failure occurred during adhesion tests,
It showed good adhesion to various adherends. Comparative Example 1 A commercially available butyl rubber hot melt caulking agent (manufactured by Polysar Limited) was used as Comparative Example-1, and the viscosity and cartridge extrudability at various temperatures with the composition of Example-1 are shown in Table-2. Comparative Example-1 did not change its viscosity much with temperature changes, whereas Example-1 showed a rapid viscosity drop at about 120°C and was found to have good cartridge extrudability at about 140°C.

[Table] Comparative Example 2 and Comparative Example 3 Compositions (heat-sensitive polymerization Comparative Example-2 (95 parts of inorganic filler per 100 parts of reaction product) was used as Comparative Example-2, and the same as Example-1 except that 380 parts of calcium carbonate (oil absorption: 33) was used instead of 480 parts of talc in Example 1. A composition (95 parts of inorganic filler per 100 parts of heat-sensitive polymerization reaction product) blended into Comparative Example-3 was used, and the slump property and tack occurrence temperature of the composition at 70°C were compared with those of Example 1 and Example 3. It is shown in Table 3 together with the composition of Example 2.

[Table] Example 3 Using the polymer composition obtained in Example 1, the following materials were kneaded in the same manner as in Example 1. Polymerization composition 400 parts Acrylic ester oligomer (plasticizer: butyl acrylate/2-ethylhexyl acrylate = 50/50, number average molecular weight approximately 1000) 90 parts Light calcium carbonate (oil absorption 45) 200 parts Titanium white 50 parts Talc 200 parts The resulting composition was a caulking composition with excellent stain resistance, slump resistance, alkali resistance, weather resistance, and adhesion to various adherends. Example 4 Butyl acrylate 400 as a polymerization monomer,
The following polymerization operation was carried out according to Example 1 using methyl methacrylate 200. The average particle diameter of the dispersed particles of the obtained copolymer dispersion was about 1.0 μ, and the glass transition point of the copolymer was -21°C. Sealing composition The following were kneaded in the same manner as in Example 1. Polymer composition 400 parts Hydrogenated rosin glycerin ester tackifier [Ester Gum H, manufactured by Arakawa Chemical Co., Ltd., softening point 68~
78℃ 70 parts Light calcium carbonate (oil absorption 45) 300 parts The resulting composition contains 75 parts of inorganic filler per 100 parts of the heat-sensitive polymerization reaction product, and has excellent slump resistance, water resistance, Alkali resistance, chlorine gas resistance,
The resulting caulking composition has excellent sulfur dioxide gas resistance, stain resistance, and adhesion to various adherends.

Claims (1)

[Claims] 1. Solid at room temperature (25°C) and 40° to 200°C
It is a wax that melts into a liquid state at a temperature of 200
Among waxes with a viscosity of 1000 cps or less at °C,
Under the melting conditions of the waxes, acrylic and/or
Or a dispersion of a polymer or copolymer having a glass transition point of about -50°C to about +20°C uniformly dispersed in the wax obtained by dispersing and polymerizing a methacrylic monomer. A heat-sensitive polymerization reaction product containing about 5 to about 200 parts by weight of the wax based on 100 parts by weight of the polymer or copolymer consisting of particles.
and 75 to 120 parts by weight of an inorganic filler having an oil absorption of about 35 or more uniformly dispersed in the reaction product. 2. The hot melt sealing or caulking material according to claim 1, wherein the sealing or caulking material contains a plasticizer for the polymer or copolymer.