JP5606863B2 - Adhesive composition - Google Patents

Description

  The present invention relates to an adhesive composition which reduces bleeding of components in an adhesive and contamination of an adherend due to discoloration of the bleeding component.

  Adhesives using moisture-curing resins having reactive silicon groups such as modified silicone resins can be cured by moisture, have excellent adherence suitability and elasticity. It is also used for bonding tile and sheet decorations. On the other hand, problems have been pointed out that the adherend changes color as time passes after bonding. Although this cause is not clear, it is thought that the bleeding of the component in an adhesive agent has influenced.

Patent Document 1 discloses a tile adhesive that is excellent in weather resistance and excellent in antifouling property of the adhered tile. However, the adhesive prevents discoloration due to dirt components adhering to the tile surface, and the discoloration of the adhesive itself has not been sufficiently studied.
JP 2009-221422

  The subject of this invention is providing the adhesive composition which reduced the contamination of the to-be-adhered body by the bleeding of the component in an adhesive agent, and the bleeding component.

  As a result of investigations by the present inventors, discoloration does not occur only in a specific case in a combination of a catalyst and a plasticizer, which are substantially essential components in an adhesive using a moisture curable resin having a reactive silicon group. The present invention was completed by finding out and further studying.

The present invention relates to an adhesive composition comprising a moisture curable resin having a reactive silicon group, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, and polypropylene glycol It is.

  In the adhesive composition of the present invention, the adherend is hardly contaminated after use. The reason for this is not clear, but it is presumed that bleeding of the components in the adhesive is reduced, and further, discoloration of the bleeding components is suppressed. Therefore, it is particularly suitable for bonding tiles and sheet-like decorative materials.

  The adhesive composition of the present invention contains a moisture curable resin having a reactive silicon group. The moisture curable resin having a reactive silicon group is a resin having a functional group capable of generating a silanol group by reacting with an active hydrogen group-containing compound such as water. Type, deoxime type, deacetic acid type, deamide type, deacetone type and the like. Moreover, the thing which has a polysiloxane structure as a main chain (silicone resin), and the thing which has a polyoxyalkylene structure (modified silicone resin) are mentioned. When used for adhesive coating, it is preferable to use a modified silicone resin having excellent adhesion.

When curing a moisture curable resin having a reactive silicon group, a curing catalyst is usually used. In the present invention, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane is used. .
When other catalysts such as organic tin, inorganic tin, titanium catalyst, bismuth catalyst, metal complex, platinum catalyst, basic substance, and organic phosphorous oxide are used, the adherend may be contaminated. Therefore, these catalysts need not be used at all or must be used within a range not impairing the gist of the present invention.
The amount of 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane used is suitably 0.01 to 20 parts by weight per 100 parts by weight of the moisture curable resin having a reactive silicon group. It is.

  Polypropylene glycol is added to adjust the viscosity and fluidity of the adhesive composition, but is selected in the present invention because of less contamination of the adherend. Looking only at the functions of viscosity and fluidity, phthalate-based diluents such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisononyl phthalate, di-2-ethylhexyl phthalate, dimethyl silicone oil, alkyl Silicone oil such as modified silicone oil, polyether modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, dioctyl adipate, diisononyl adipate, dialkyl azelate, dibutyl sebacate, epoxidized soybean oil, acrylic polymer, etc. The same effect is expected with polypropylene glycol, but it is inferior to polypropylene glycol in that it contaminates the adherend. Therefore, it is necessary not to use a diluent other than polypropylene glycol, or to use it within a range that does not impair the gist of the present invention.

  Resin strength can be improved by adding an epoxy resin to the adhesive composition of the present invention. In addition, water resistance, weather resistance, alkali resistance and the like are improved. 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 glycidyl. Examples thereof include a urethane-modified epoxy resin having an ether bond and a urethane bond, an ester-modified epoxy resin having an ester bond, and a rubber-modified epoxy resin modified with a rubber component. In addition to these epoxy resins, an epoxy group-containing silane coupling agent can be used.

  As the curing agent for the epoxy resin, ketimines that are latent curing agents are preferred. Ketimines are dehydration condensation 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, Although it hardly reacts, primary amine is easily generated when it reacts with moisture in the air and the reaction proceeds with the epoxy resin, and there is an advantage that curing does not proceed unless moisture is absorbed. 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.

In addition, a dehydrating agent, a coupling agent, a filler, an anti-aging agent, a thixotropic agent, a pigment, a preservative, and the like can be appropriately used as necessary.
By adding a dehydrating agent, the reaction between the moisture curable resin composition and moisture during storage can be suppressed. Examples thereof include vinyltrimethoxysilane and ethyl orthoformate. It is added in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the moisture curable resin.

  The coupling agent can be used for the purpose of improving the adhesion to the adherend, and the reaction of the silane coupling agent, the titanate coupling agent, the silane or titanate coupling agent and the polyisocyanate compound. Products and the like can be used. These can be used alone or in combination of two or more.

  Fillers are blended for the purpose of viscosity adjustment, viscosity adjustment, solid content adjustment, and as specific examples, for reinforcing inorganic fillers such as calcium carbonate, cinnabar, talc, carbon black, titanium oxide, kaolin, and cured resin Examples include reinforcing materials such as glass fibers, hollow bodies such as shirasu balloons and glass balloons for weight reduction and viscosity adjustment.

  Anti-aging agents include phosphite, naphthylamine, p-phenylenediamine, quinoline, hydroquinone, bisphenol, trisphenol, polyphenol, thiobisphenol, hindered phenol, etc. You may use individually and can also use 2 or more types together.

  The present invention will be further described below with reference to examples and comparative examples. Of course, the present invention is not limited to the examples.

  As a moisture-curing resin having a reactive silicon group, Kaneka Silyl EST 280 (trade name, manufactured by Kaneka Corporation) which is a modified silicone resin, and 30 parts by weight as Adeka Resin EP-4100 (trade name, manufactured by ADEKA Corporation) as an epoxy resin. , 240 parts by weight of P-3000 (trade name, manufactured by ADEKA Co., Ltd.) as polypropylene glycol, 400 parts by weight of Shiraka Hana CCR-B (trade name, manufactured by Shiraishi Kogyo Co., Ltd.) which is a surface-treated calcium carbonate as a filler, untreated surface 400 parts by weight of white carbonate SB (trade name) manufactured by Calcium Carbonate, 10 parts by weight of DYNASYLAN VTMO (vinyl trimethoxysilane, product name of Evonik Degussa Japan Co., Ltd.) as a silane coupling agent, SH-6040 (Guri Doxypropyltrimethoxysilane, manufactured by Toray Dow Corning Co., Ltd., 15 parts by weight, Eponit K-100 (manufactured by Nitto Kasei Co., Ltd., trade name) as a ketimine compound, Neostan U-130 as a curing catalyst (1,1,3,3-Tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, manufactured by Nitto Kasei Co., Ltd., trade name) 3 parts by weight of the mixture was stirred and mixed under reduced pressure, and the moisture curability of Example 1 A resin composition was obtained.

In addition to the compounding materials used in Example 1, PMLS1004F (trade name, manufactured by Asahi Glass Co., Ltd.) which is polypropylene glycol, diisononyl adipate (DINP) as diluent, U-220H (Nitto Kasei Co., Ltd.) which is dibutyltin diacetylacetonate The product is manufactured in the same manner as in Example 1 with the formulation shown in Table 1 using the company name, product name), and the adhesive compositions of Examples 3 to 5, Comparative Examples 1 to 6, and Reference Example 1 are obtained. It was.

<Bleed resistance test method>
After the prepared adhesive composition is thickly applied to a SUS plate, modern art (made by Kikusui Chemical Co., Ltd., trade name, thickness of about 3 mm), which is a sheet-like decoration material, is attached. The coating thickness is adjusted using a spacer or the like so that the thickness of the adhesive composition is about 5 mm. After curing for 7 days in a 23 ° C. atmosphere, the plate was further left in an 80 ° C. atmosphere for 4 weeks, and the discoloration of the surface of the sheet-like decorative material was visually observed and evaluated as follows.
○: Almost no discoloration and excellent bleed resistance △: Discoloration is slightly observed and bleed resistance is slightly insufficient ×: Significant discoloration is observed and bleed resistance is not recognized

<Adhesive strength test method>
After the prepared adhesive composition was applied to a JIS mortar whose surface was polished using a 5 mm pitch comb iron, the sheet-shaped decorative material having a 4 cm square was filled with the adhesive on the entire back surface. Crimp and create a test specimen. The specimen was cured for 7 days in an atmosphere of 23 ° C., and then subjected to a plane tensile strength test.
○: Adhesive strength of 0.2 N / mm ² or more or material destruction of sheet-like decoration material ×: Adhesion strength of less than 0.2 N / mm ² and no occurrence of material destruction of sheet-like decoration material

  When each adhesive composition of the Example was used, there was almost no discoloration of a to-be-adhered body and it was excellent also in adhesive performance. On the other hand, when each adhesive composition of the comparative example was used, discoloration of the adherend was observed.

Claims (1)

An adhesive composition comprising a moisture curable resin having a reactive silicon group, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, and polypropylene glycol.