JP4286172B2 - Adhesive composition - Google Patents

Description

The present invention is a room temperature curable adhesive composition with excellent adhesion performance, weather resistance, water resistance, storage stability, etc., and excellent displacement followability, and more specifically used as a sealing material, filler, adhesive, etc. The present invention relates to a modified silicone-based adhesive composition.

In recent years, exterior materials such as ceramic sizing materials, metal sizing materials, and tiles have been actively adopted as outer wall materials.
Such an exterior material is attached to the surface of a base material made of metal or wood by using screws / metal fittings or a combination of screws / metal fittings and an adhesive. Fillers are used, and silicone adhesives, urethane resin adhesives, and the like are used for the adhesive layer.

Sealing materials or fillers used for joints include one-part curable silicone resin-based, modified silicone resin-based sealing materials and fillers, or epoxy resin-based, urethane resin-based sealing materials, Fillers are mainly used.
Among these, silicone-based and modified silicone-based sealing materials and fillers are preferably used because of their adhesion to various adherends, flexibility, displacement followability, and water resistance.
However, when used as a sealing material, filler, etc., if the applied surface is exposed to the outside air for a long period of time, it gradually deteriorates and discolors, or the displacement followability decreases due to the deterioration and cracks occur. In the end, cracks have progressed and sealing materials, fillers, etc. have fallen off the construction site and water has leaked from the joints.

Adhesives used for fixing fixtures and parts for outdoor structures such as street lights, road lighting fixtures, utility poles, power transmission lines, traffic lights, signboards, etc. are room temperature curable and have excellent weather resistance and displacement. Followability, adhesion performance, etc. are required.
However, the adhesives used so far have not been satisfactory with respect to these performances.

Because of this situation, there is a need for sealing materials, fillers, adhesives, etc. that are room-temperature curable and have weather resistance more than ever, with excellent flexibility, displacement followability, and water resistance. It was.
As means for enhancing weather resistance, a method of adding an ultraviolet absorber as disclosed in JP-A No. 2001-271057, a method of mixing an acrylic resin having weather resistance as described in JP-A No. 11-71547, and JP-A No. 2000-204345 A method of using a polysulfide polyether copolymer together as described above has been proposed.
However, there still remain problems such as insufficient weather resistance, increased costs, and rain that causes ultraviolet absorbers, anti-aging agents, etc. to be washed away and accelerated deterioration.

JP 2001-271057 A JP 11-71547 A

  In view of the circumstances as described above, the present invention greatly improves the weather resistance of conventionally used sealing materials, fillers, adhesives, etc., as well as room temperature curability, flexibility, displacement The present invention intends to realize an adhesive composition such as a sealing material, a filler, and an adhesive that are excellent in followability, adhesive performance, workability, and the like and are suitable for outdoor use.

By blending at least a viscosity modifier, carbon black fine powder (hereinafter abbreviated as CBP), a filler, and a curing catalyst with a resin component comprising a modified silicone resin or a modified silicone resin containing an epoxy resin, It solves the problem.

The adhesive composition according to the present invention has room temperature curing properties and is excellent in weather resistance, displacement followability, adhesion performance, and the like, so that it can be used for exterior materials such as ceramic sizing materials, metal sizing materials, tiles. When bonding bricks, etc. to building foundations, if used as a sealant or filler for joints between exterior materials, or as an adhesive layer between exterior materials and construction foundations, the exterior will change due to environmental changes such as temperature and humidity. Even if a dimensional change occurs between the material or the exterior material and the base, troubles such as cracks in the joints and adhesive layer, dropping of the joints, water leakage from the joints, and peeling of the exterior materials Does not occur.
Moreover, even if it is exposed outdoors, it has excellent weather resistance, so that problems such as discoloration and deterioration do not occur.
In addition, in the blending with the dehydrating agent, the reaction can be suppressed by moisture absorption of the modified silicone resin, so that there is no problem such as excellent storage stability and the remaining use is cured, and the construction management becomes simple.

Hereinafter, the adhesive composition according to the present invention will be described in detail.
The adhesive composition according to the present invention has a viscosity of a resin component composed of 100 parts by weight of a modified silicone resin or 100 parts by weight of a resin in which 50 parts by weight or less of an epoxy resin is blended with respect to 100 parts by weight of a modified silicone resin. It is composed of 50 to 100 parts by weight of a modifier, 5 to 15 parts by weight of CBP, 200 to 400 parts by weight of a filler and a curing catalyst.

The modified silicone resin is a polymer having a hydrolyzable silicon functional group at the terminal and a main chain essentially having a polyether structure, and the main chain includes a polyoxyethylene main chain and a polyoxypropylene main chain. Examples include a chain, a polyoxybutylene main chain, and an acrylic main chain, and a polyoxypropylene main chain is preferable from the viewpoint of balance of physical properties.
As the hydrolyzable silicon functional group, a methoxysilyl group is preferable from the viewpoint of reactivity and physical properties after reaction.
The number average molecular weight of the polymer is preferably 4,000 to 30,000, and the number average molecular weight of 10,000 to 30,000 is particularly suitable from the viewpoint of cohesive force.
Specific examples of the modified silicone resin include, for example, trade names “EST-250”, “SAX-770”, “SAT200”, “SAT430”, “MS polymer S203” manufactured by Kaneka Chemical Co., Ltd. “MS Polymer S303”, “Execester 3620”, “Excester 3430”, “Excester 2420”, “Excester 2410” manufactured by Asahi Glass Co., Ltd., and the like can be used alone or in combination. Can do.

Examples of the curing catalyst for the modified silicone resin include metal salts of organic carboxylic acids such as tin octylate, tin stearate, tin naphthenate and lead octylate, di-n-butyltin-dilaurate, di-n- In addition to organic tin such as butyltin-diphthalate, alkyl titanates may be used. These curing catalysts are blended in the modified silicone resin in an amount of 0.1 to 10 parts by weight or 100 parts by weight.

The epoxy resins include bisphenol A type, bisphenol F type, bisphenol AD type epoxy resins, hydrogenated products thereof, nopolac type, glycidyl type and glycidylamine type epoxy resins, as well as polyoxypropylene and polyoxyethylene. And glycidyl ether, a urethane-modified epoxy resin having a urethane bond, an ester-modified epoxy resin having an ester bond, a rubber-modified epoxy resin modified with a rubber component, and the like. The epoxy resin is blended and adjusted at a blending ratio of 50 parts by weight or less with respect to 100 parts by weight of the modified silicone resin. The blending of 50 parts by weight or more is not preferable because the cured product tends to be brittle.

Ketimines are used as a curing catalyst for the epoxy resin.
The ketimines are dehydration condensation reaction products of an amine compound having two or more amino groups in one molecule and a ketone compound, and in the absence of moisture due to the weak basicity of nitrogen in the molecule, an epoxy resin Is highly reactive, such as easily reacting with moisture in the air, so primary moisture is easily generated when moisture is absorbed and the reaction with the epoxy resin proceeds, and curing proceeds unless moisture is absorbed. There is no advantage.
This feature can be used for one-pack type epoxy resins. Specific examples include polyoxypropylenediamine and methylisobutylketone dehydrated, polyoxypropylenetriamine and methylisobutylketone dehydrated. And those obtained by dehydration reaction of polyoxyalkylene diamine and methyl isobutyl ketone, and those obtained by dehydration reaction of hexamethylene diamine and methyl isobutyl ketone.

The viscosity modifier is used for adjusting the viscosity of the adhesive composition. As a specific example, a plasticizer used as a plasticizer for vinyl chloride resin, for example, phthalic acid such as dioctyl phthalate, dibutyl phthalate and diisodecyl phthalate Adipates and polyesters such as polymethylene, trimellitic acid, diisobutyl adipate, diisodecyl adipate and diisooctyl adipate, as well as polyethers such as polyoxypropylene glycol and its derivatives, polystyrene oligomers such as polyalphastyrene and polystyrene , Oligomers such as polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, hydrogenated polybutene, and the like.
The viscosity modifier is blended in the range of 50 to 100 parts by weight with respect to 100 parts by weight of the resin component. If it is 50 parts by weight or less, the viscosity of the adhesive composition becomes too high, which is not preferable. On the other hand, since the tackiness is low at 100 parts by weight or more, there is a problem that a deviation occurs when the adhesive composition is applied to the base and the adherend is stacked.

The adhesive composition according to the present invention employs CBP as a means for imparting weather resistance, and a significant improvement in weather resistance is recognized as compared with the conventional one.
Examples of the CBP include furnace carbon black fine powder, channel carbon black fine powder, thermal carbon black fine powder, and acetylene carbon black fine powder. Among these, those having an average particle size of 25 nm or less and a specific surface area of 85 m ² / g or more are more suitable for use than other CBPs because they are more effective in improving the weather resistance.
The reason why the weather resistance is improved by the CBP is presumed that the CBP is a fine particle and has a large specific surface area, and therefore has an ultraviolet absorbing ability and an excellent light shielding performance.
The blending ratio of the CBP is preferably 5 to 15 parts by weight with respect to 100 parts by weight of the resin component. If it is 5 parts by weight or less, a remarkable effect cannot be obtained in improving the weather resistance, and if it is 15 parts by weight or more, the adhesion to the adherend is lowered. It is not preferable because a phenomenon of so-called interfacial fracture is observed.

Examples of the filler include calcium carbonate, talc, kaolin, silica powder, magnesium carbonate, bengara, and the like, and those having a particle diameter of 1 to 100 μm are preferable because of good dispersibility in the resin component. . Among these, those surface-treated with a fatty acid or the like are preferable because they are excellent in dispersibility in the resin component, and thixotropic properties are imparted to the adhesive composition, thereby obtaining an anti-sagging effect.
200 to 400 parts by weight of such a filler is blended with respect to 100 parts by weight of the resin component in consideration of the finished hardness, viscosity, sagging property, dischargeability and the like of the adhesive composition.

  Coupling agents are formulated to improve adhesion and compatibility between resin components and fillers and other compounding agents. Specific examples thereof include amino silane coupling agents and epoxy silane cups. Examples thereof include a ring agent and a ureido silane coupling agent. These coupling agents are appropriately selected depending on the types of the resin component, filler, and other compounding agents, and 2 to 10 parts by weight are appropriately blended with respect to 100 parts by weight of the resin component.

  Antioxidants are formulated as measures to improve the antioxidant and heat resistance of adhesive compositions. Specific examples include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, and hydroquinone-based antioxidants. An antioxidant, a quinoline antioxidant, etc. are mentioned, 0.1-5 weight part of these is suitably mix | blended with respect to 100 weight part of resin components.

Along with the CBP, an ultraviolet absorber is appropriately blended in order to improve the weather resistance of the adhesive composition.
Specific examples thereof include salicylic acid series such as phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4- Bensophenone series such as methoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2-dihydroxy-4--4-dimethoxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2 -Hydroxy-5-tert-butylphenyl) benzotriazole, and the like, 2-ethylhexyl-2-cyano-3, 3-diphenyl acrylate, ethyl-2-cyano-3, 3-diphenyl acrylate, What cyanoacrylate and the like, which from 1 to 10 parts by weight per 100 parts by weight of the resin component is suitably incorporated.

The adhesive composition according to the present invention preferably contains a dehydrating agent in order to suppress the curing reaction due to moisture absorption, which is a characteristic of the modified silicone resin, and to ensure storage stability.
Specific examples of the dehydrating agent include, for example, silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, phenylmethoxysilane, and diphenyldimethoxysilane. Examples include hydrolysable ester compounds such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate.

In order to prevent the adhesive composition, for example, an organic iodide type, isothiazoline type, and benzimidazole type antifungal agent may be blended. These are appropriately blended in an amount of 0.5 to 5 parts by weight per 100 parts by weight of the resin component.
Even when the adhesive composition is applied to an exposed part such as a joint part of the exterior material, the generation of wrinkles can be avoided over a long period of time by blending the antifungal agent.

In the adhesive composition of the present invention, a resin component, a viscosity modifier, CBP, an ultraviolet absorber, a filler, other compounding agents, and the like are blended in a predetermined amount in a planetary mixer and heated to about 100 ° C., preferably vacuum. After reducing the pressure to 50 mmHg or less and stirring to make the moisture value in the composition 500 ppm or less, cooling to 60 ° C. or less, further adding a coupling agent and a curing catalyst, and stirring to prepare a sealed container, Filled in airtight packaging containers such as cartridges and aluminum packs.

  As a method of coating or filling, predetermined parts such as exterior parts, joints such as outdoor workpieces, connecting parts, coating parts, etc. by coating means such as cartridge guns and irons, and filling means such as cartridge guns and injectors. However, it is preferable to adjust the viscosity to 200 to 400 Pa · s / 23 ° C. as the cartridge gun type and the viscosity from 300 to 1000 Pa · s / 23 ° C. as the iron type from the viewpoint of coating properties and dischargeability.

Hereinafter, the adhesive composition of the present invention will be described with reference to examples and comparative examples.
In addition, all the numerical values of the formulations shown in Tables 1 to 3 indicate parts by weight.
MS polymer S303 (manufactured by Kaneka Chemical Co., Ltd., hereinafter abbreviated as S303) as a modified silicone resin, Epicoat 828 (manufactured by Shell, bisphenol A type epoxy system, hereinafter abbreviated as BPAE), Diisodecyl phthalate (hereinafter abbreviated as DIDP), diisononyl phthalate (hereinafter abbreviated as DINP) as a viscosity modifier, Tinuvin 327 (manufactured by Ciba Specialty Chemical Co., Ltd., chemical name benzotriazole, hereinafter abbreviated as UVA) ), Tinuvin 770 (manufactured by Ciba Specialty Chemical Co., Ltd., chemical name hindered amine, hereinafter abbreviated as HALS) as a light stabilizer, and IRGANOX 1010 (manufactured by Ciba Specialty Chemical Co., Ltd., chemical name hindered). Phenol system, hereinafter abbreviated to 1010.), Asahi Thermal carbon as CBP (Asahi Carbon Co., Ltd., average particle diameter 80 nm, specific surface area ^24m 2 / g to AC abbreviated hereinafter.), Sanburatsuku 605 (manufactured by Asahi Carbon Co., Ltd., Average particle size 25 nm, specific surface area 85 m ² / g, hereinafter abbreviated as # 605), Dispalon 6500 as a thixotropic agent (manufactured by Enomoto Kasei Co., Ltd., amide wax system, hereinafter abbreviated as 6500), calcium carbonate as a filler, white SB (calcium shiroishi, average particle size 5 μm, hereinafter abbreviated as SB), white gloss CCR (manufactured by Shiraishi Kogyo Co., Ltd., average particle size 0.08 μm, hereinafter abbreviated as CCR), vinylsilane-based dehydrating agent A- 171 (manufactured by Nippon Unicar Co., Ltd., hereinafter abbreviated as A-171). Xylon-based coupling agent A-187 (manufactured by Nihon Unicar Co., Ltd., hereinafter abbreviated as A187), tin-based catalyst SCAT-1 (manufactured by Sankyo Gosei Co., Ltd., hereinafter abbreviated as SCAT) as a curing catalyst for the modified silicone resin Epoxyt K100, which is a ketimine as an epoxy resin curing agent (Nitto Kasei Co., Ltd., hereinafter abbreviated as K100) is blended according to the blending values in Tables 1 to 3 to prepare adhesive compositions of Examples and Comparative Examples. did.
As described above, resin components, viscosity modifiers, CBP, fillers, UV absorbers, etc. are blended in a predetermined amount in a planetary mixer, heated to about 100 ° C., reduced to 50 mmHg or less, and stirred while reducing pressure and stirring. After setting the moisture value to 500 ppm or less, the mixture was cooled to 60 ° C. or less, and a coupling agent and a curing catalyst were blended and stirred to prepare adhesive compositions of Examples and Comparative Examples.
The measurement results of the property value, weather resistance, adhesion performance, displacement resistance, and film physical properties were as shown in Tables 1 to 3.

Test / Evaluation Method Viscosity Viscosity at 23 ° C (unit Pa · s) by BS type viscometer (rotor NO7, 10rpm)
Measure.
2. Weather resistance test Daipura metal weather (model KU-R5, manufactured by Daipura Wintes Co., Ltd.), a metal halide tester established by the Japan Testing Machine Industry Association on October 3, 2000, filter used: KF-1 / 295 780 nm)
The test was carried out at 20 ° C. and 65 RH% for 24 hours after applying the adhesive compositions of Examples and Comparative Examples to the steel sheet surface to a thickness of 2 mm and curing them in a constant temperature room at 20 ° C. for 2 days. The piece {L (4 hours irradiation / illuminance 75 mW / cm ² , 6
3 ° C., 50% RH) +30 seconds water shower + D (4 hours condensation / 30 ° C., 95% RH) +30 seconds water shower}
This cycle is repeated to perform a metallizing weather test for each test time, and visually confirm the appearance change.
3. Adhesion test Ceramic material siding (AG-WALL SWA-21 manufactured by Asahi Glass Co., Ltd.) with a thickness of 12 mm and porcelain tile (Danto MN-50 / 2T) with a thickness of 9 mm, length 40 mm x width 40 mm are used as the adherend Then, after applying cement mortar to the surface of ceramic sizing with 5mm pitch with crease, put porcelain tile 1
a standard test specimen that was cured for 7 days under an atmosphere of 23 ° C. and 50% RH after bonding with a load of 30 seconds in kg,
Further, the test piece was immersed in a 60 ° C. saturated calcium hydroxide aqueous solution for 7 days, then washed with water, and then immersed in water at 23 ° C. for 1 day. 1185 type),
The plane tensile adhesive force (unit: N / mm ² ) was measured at a pulling speed of 3 mm / min.
In the columns of adhesive strength in Tables 1 to 3, the upper row shows the adhesive strength (unit: N / mm ² ), the lower row shows the broken state (cf is adhesive cohesive failure, Bf is siding material failure, and Af is adhesive interface peeling. It represents all destruction states at 100%.
Example 30Cf / 70Bf represents 30% cohesive failure, 70% material failure. ) Is displayed.
4). Displacement Resistance / After applying the adhesive compositions of Examples and Comparative Examples to a slate plate with a reference line drawn at the center with a 5 mm pitch combing iron, a porcelain tile (thickness 9 mm, length 40 mm x width 40 mm) Company MN-50 / 2T) with the horizontal center line aligned to the reference line and immediately put it upright, measuring the deviation length of the center line of the porcelain tile from the reference line after 24 hours To do. When the deviation is 5 mm or less, the evaluation is ○, and when the deviation is 5 mm or more, the evaluation is ×.
5. Film properties Using dumbbell No. 2 type (thickness 2 mm, total length 115 mm, distance between marked lines 25 mm, width of parallel part 6 mm) based on dumbbell JISK7113 (1995 edition), the chuck between the tensile tester is fixed to 50 mm, The film was pulled at a tension rate of 100 mm / min, and an elongation rate of 30% or more was evaluated as ◯, and less than 30% was evaluated as ×.

The adhesive composition according to the present invention is room temperature curable, and is excellent in weather resistance, displacement followability, and adhesive performance, so that it is constructed outdoors, tiles, bricks, ceramic sizing materials, metal sizing materials It is suitable for sealing joints of exterior materials, filling or bonding to construction bases, or bonding of fixtures for outdoor works such as signs, traffic lights, lighting fixtures, sealing and filling of connecting parts, etc. Can be used with confidence during the period.

Claims (1)

Carbon black fine powder having an average particle diameter of 25 nm or less in a resin component comprising 100 parts by weight of a modified silicone resin or 100 parts by weight of a resin in which 50 parts by weight or less of an epoxy resin is blended with 100 parts by weight of a modified silicone resin An adhesive composition comprising at least 5 to 15 parts by weight , a viscosity modifier of 50 to 100 parts by weight , a filler of 200 to 400 parts by weight , and a curing catalyst.