JP5296959B2 - Adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition capable of effectively bonding an adherend by roll coating, which is slow in curing speed at the roll coating, that is to say, at room temperature and curable in a short time by heating after the roll coating. <P>SOLUTION: The adhesive composition contains 100 pts.wt. of an organic polymer having a principal chain composed essentially of a polyether, and a crosslikable hydrolytic silyl group, 0.1-10 pts.wt. of a monobutyltin- or monooctyltin-based catalyst, 0.5-10 pts.wt. of a ureide silane and 0.1-20 pts.wt. of water. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to an adhesive composition capable of effectively bonding an adherend by roll coating, and more specifically, the curing rate at the time of roll coating, that is, the curing rate at room temperature is low, and roll coating is performed. The present invention relates to a modified silicone adhesive composition that cures in a short time when heated later.

  In recent years, as an adhesive used for bonding a sealing material or the like, a modified silicone adhesive having elasticity after curing has been used.

  Since the modified silicone-based adhesive has excellent curing performance, a polymer having a hydrolyzable silyl group is often included. An adhesive containing a polymer having a hydrolyzable silyl group reacts with moisture in the air in the presence of a catalyst, and is quickly cured at room temperature.

  By the way, when apply | coating an adhesive agent to a to-be-adhered body, since an adhesive agent can be apply | coated smoothly on the surface of an to-be-adhered body, it may be performed by roll coating. However, since the reaction of the hydrolyzable silyl group proceeds rapidly, the modified silicone adhesive sometimes hardens on the roll during coating. Various attempts have been made to slow the reaction rate of hydrolyzable silyl groups in order to prevent the modified silicone adhesive from curing on the roll.

In the following Patent Document 1, a polymer (A) having a main chain which is essentially a polyether and having a hydrolyzable silyl group at the terminal, and a hydrolyzable silyl group capable of crosslinking with a ureido group in the molecule are disclosed. The adhesive composition for roll coating containing the compound (B) which has is shown. If necessary, a curing catalyst such as dibutyltin dilaurate is added to the roll coating adhesive composition.
JP 2000-119625 A

  In the adhesive composition for roll coating described in Patent Document 1, the reaction rate of the hydrolyzable silyl group is delayed. Therefore, in the adhesive composition, it is difficult to be cured on the roll when performing roll coating. However, in the adhesive composition for roll coating described in Patent Document 1, it took a long time for the adhesive composition to cure after roll coating. That is, since the curing rate of the adhesive composition was slow, the adhesive composition could not be cured in a short time.

  The present invention is an adhesive composition capable of effectively bonding an adherend by roll coating, and has a slow curing rate at the time of roll coating, that is, a curing rate at room temperature, which is heated after roll coating. Then, it aims at providing the adhesive composition which hardens | cures in a short time.

  The adhesive composition according to the present invention comprises 100 parts by weight of an organic polymer having a hydrolyzable silyl group whose main chain is essentially a polyether, and a monobutyltin catalyst or monooctyltin catalyst. It contains 0.1 to 10 parts by weight, 0.5 to 10 parts by weight of ureidosilane, and 0.1 to 20 parts by weight of water.

  Details of the present invention will be described below.

  An adhesive composition according to the present invention comprises an organic polymer having a main chain essentially a polyether and a crosslinkable hydrolyzable silyl group, a monobutyltin catalyst or a monooctyltin catalyst, and a ureido Contains silane and water.

  The organic polymer is not particularly limited as long as it is an organic polymer whose main chain is essentially a polyether and has a crosslinkable hydrolyzable silyl group.

  The crosslinkable hydrolyzable silyl group is a group in which a hydrolyzable group is bonded to a silicon atom. Examples of hydrolyzable groups bonded to silicon atoms include hydrogen, halogen atoms, alkoxy groups, acyl oxide groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyl oxide groups, and the like. Is mentioned. As the hydrolyzable silyl group, an alkoxysilyl group in which an alkoxy group is bonded to a silicon atom is preferable because no harmful by-product is formed after the reaction.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, a tert-butoxy group, a phenoxy group, and a benzyloxy group. Of these, a methoxy group, an ethoxy group, and the like are preferable.

  Various methods for introducing the hydrolyzable silyl group into the polymer have been proposed and are not particularly limited. For example, by reacting a polyoxyalkylene having an allyl group at the terminal with a silicon hydride compound represented by the following formula (1) in the presence of a Group VIII transition metal, a hydrolyzable silyl group is converted into a polymer. Can be introduced.

RaXbHSi (1)
In the above formula (1), R is a group selected from the group consisting of a monovalent hydrocarbon group and a halogenated monovalent hydrocarbon group, and when a is 2, R is the same or different. Also good. X represents an atom or group selected from the group consisting of a halogen, an alkoxy group, an acyloxy group, and a ketoximate group. When b is 2, X may be the same or different. a and b are the same or different and represent an integer of 0 to 2; However, a + b = 3 is satisfied.

  The main chain of the polymer is essentially a polyether, and examples thereof include polyoxyethylene, polyoxypropylene, and polyoxybutylene, but the adhesive composition has good elongation and has a viscosity that is easy to handle. Polyoxypropylene is preferred.

  The number average molecular weight of the organic polymer is preferably 4,000 to 30,000. The polymer preferably has a number average molecular weight in the range of 10,000 to 30,000 and a molecular weight distribution (Mw / Mn) of 1.6 or less.

  As for the said organic polymer, only 1 type may be used and 2 or more types may be used together.

  Examples of commercial products of the organic polymer include MS polymer S-203, S-303, S-903, etc. as trade name MS polymer manufactured by Kaneka Corporation, and silylyl SAT-200, MA430 as trade name silyl polymers. , MAX447, SAT-350, SAT-400 and the like. Furthermore, as a commercial item of the said organic polymer, Exastar ESS-3620, ESS-3430, ESS-2420, ESS-2410, etc. by Asahi Glass Co., Ltd. are mentioned.

  The monobutyltin-based catalyst is not particularly limited, and examples thereof include monobutyltin tripivalate, monobutyltin trineoheptate, monobutyltin trilaurate, monobutyltin triethoxysilicate, and the like. Monobutyltin-based catalysts may be used alone or in combination of two or more.

  The monobutyltin-based catalyst is blended in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the organic polymer. When the amount of the monobutyltin catalyst is less than 0.1 parts by weight, the curing is delayed, and when it exceeds 10 parts by weight, the stability of the adhesive composition is lowered.

  Examples of the monooctyltin-based catalyst include monooctyltin tri (2-ethylhexanoate), monooctyltin tri (n-octate), monooctyltin trilaurate, and the like. The monooctyltin-based catalyst may be used alone or in combination of two or more.

  The monooctyltin-based catalyst is blended in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the organic polymer. When the amount of the monooctyl tin-based catalyst is less than 0.1 parts by weight, the curing is slow, and when it exceeds 10 parts by weight, the stability of the adhesive composition is lowered.

  Examples of the ureidosilane include 3-ureidopropyltriethoxysilane and 3-ureidotrimethoxysilane.

  The said ureidosilane is mix | blended 0.5 to 10 weight part with respect to 100 weight part of organic polymers. When the amount of ureidosilane is less than 0.5 parts by weight, the adhesiveness is inferior.

  The water is blended in an amount of 0.1 to 20 parts by weight per 100 parts by weight of the organic polymer. When the amount of water is less than 0.1 parts by weight, the curing rate is remarkably slowed, and when it is more than 20 parts by weight, the stability of the adhesive composition is lowered.

  The adhesive composition of the present invention may contain a hydrolyzable silyl group-containing epoxy compound different from the organic polymer.

  The hydrolyzable silyl group-containing epoxy compound is a compound having an epoxy group and a hydrolyzable silyl group. Examples of the hydrolyzable silyl group-containing epoxy compound include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- Examples thereof include glycidoxytriethoxysilane.

  The adhesive composition of the present invention may contain a filler, a plasticizer, an anti-sagging agent and the like as necessary.

  Examples of the filler include calcium carbonate, magnesium carbonate, hydrous silicic acid, anhydrous silicic acid, calcium silicate, silica, titanium dioxide, clay, talc, carbon black, and glass balloon. These may be used alone or in combination of two or more.

  Examples of the plasticizer include phosphate esters such as tributyl phosphate and tricresyl phosphate, phthalate esters such as dioctyl phthalate, fatty acid monobasic esters such as glycerol monooleate, dibutyl adipate, dioctyl adipate, and the like. And fatty acid dibasic acid esters, polypropylene glycols and the like. These may be used alone or in combination of two or more.

  Examples of the anti-sagging agent include hydrogenated castor oil, fatty acid bisamide, fumed silica, and the like.

  If necessary, the adhesive composition may further contain an antioxidant, an antioxidant, an ultraviolet absorber, a pigment, a solvent, a fragrance and the like.

  In the present invention, the main chain is essentially a polyether and 100 parts by weight of an organic polymer having a crosslinkable hydrolyzable silyl group and a monobutyltin catalyst or a monooctyltin catalyst 0.1 to 10 weight Part, 0.5 to 10 parts by weight of ureidosilane, and 0.1 to 20 parts by weight of water, it is excellent in storage stability and adhesiveness. Furthermore, the adhesive composition of the present invention has a slow curing rate at the time of roll coating at the time of adhesion of the adherend, that is, a slow curing rate at room temperature, and is difficult to cure on the roll. It is cured in a short time by being heated later.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to a following example.

Example 1
100 parts by weight of silyl SAT400 (manufactured by Kaneka Co., Ltd.) as an organic polymer having a principal chain of polyether and having a crosslinkable hydrolyzable silyl group, and Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as an antioxidant ) 1 part by weight, 40 parts by weight of colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd.), 2 parts by weight of monooctyltin trilaurate (manufactured by Nitto Kasei Co., Ltd.), 3-ureidopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 5 1 part by weight, 4 parts by weight of 3-glycidoxypropyltrimethoxylane (manufactured by Shin-Etsu Chemical Co., Ltd.), and 3 parts by weight of water are blended and vacuum kneaded for 60 minutes using a planetary mixer to obtain an adhesive composition It was.

(Example 2)
An adhesive composition was obtained in the same manner as in Example 1 except that 2 parts by weight of monooctyltin trilaurate (manufactured by Nitto Kasei) was changed to 2 parts by weight of monobutyltin trilaurate (manufactured by Nitto Kasei).

(Comparative Example 1)
Example 1 was repeated except that 5 parts by weight of 3-ureidopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 5 parts by weight of 3-aminoethylaminopropyltrimethoxylane (manufactured by Shin-Etsu Chemical Co., Ltd.). Thus, an adhesive composition was obtained.

(Comparative Example 2)
An adhesive composition was obtained in the same manner as in Example 1 except that 2 parts by weight of monooctyltin trilaurate (manufactured by Nitto Kasei) was changed to 2 parts by weight of dibutyltin dilaurate (manufactured by Nitto Kasei).

(Evaluation of adhesive composition)
(1) Roll stability 100 g of the obtained adhesive composition was placed on a spreader roll manufactured by Sekisui Chemical Co., Ltd., and run idle for 20 minutes. Changes in the adhesive composition before and after the 20-minute idling operation were evaluated according to the following evaluation criteria.
○: No gelation confirmed after 20 minutes idling, viscosity after 20 min idling less than 1.5 times viscosity before running Δ: No gelation confirmed after 20 min idling, 20 min idling After viscosity exceeds 1.5 times the viscosity before operation ×: Gelation was confirmed after 20 minutes idling

(2) Heat-curing property The obtained adhesive composition was applied on a galvanized steel sheet (0.5 mm × 50 mm × 50 mm) so as to have a thickness of 0.2 mm. Thereafter, two galvanized steel sheets were joined through the adhesive composition application surface and cured at 120 ° C. for 20 minutes. It was evaluated whether two bonded galvanized steel sheets could be peeled off by hand.

○: The adhesive composition is cured and cannot be peeled off by hand. ×: The adhesive composition is not sufficiently cured and can be easily peeled off by hand.

Claims (1)

100 parts by weight of an organic polymer whose main chain is essentially a polyether and has a crosslinkable hydrolyzable silyl group, 0.1 to 10 parts by weight of a monobutyltin catalyst or a monooctyltin catalyst, and ureido An adhesive composition comprising 0.5 to 10 parts by weight of silane and 0.1 to 20 parts by weight of water.