JPS6268869A - Pressure-sensitive adhesive composition usable in water - Google Patents

Abstract

PURPOSE:To obtain the titled adhesive stable in air, handleable easily and useful for the bonding work of sewage, ship, etc., by compounding a poly(meth) acrylic acid, etc., with a polyfunctional epoxy compound clathrated with cyclodextrin at a specific ratio. CONSTITUTION:The objective composition is composed of (A) a poly(meth)acrylic acid and/or sodium poly(meth)acrylate and (B) a polyfunctional epoxy compound (preferably tetraglycidyl derivative of m-xylenediamine). The weight ratio of A to B (A/B) is 100/(0.01-20).

Description

[Detailed description of the invention] [Technical field to which the invention pertains] The present invention relates to an underwater adhesive composition, and more specifically,
The present invention relates to an underwater pressure-sensitive adhesive composition that is stable in the absence of water, but adheres and hardens in the presence of water.

[Conventional technologies and their problems] In recent years, various types of adhesives have been used in the fields of sewage work in spring areas, civil engineering construction vehicles such as subway construction, ships, underwater structures, etc., or anti-corrosion coating. Water-stopping agent or water-stopping agent is not used.

Such adhesives include, for example, epoxy mIl
! , those made of an organic amine, cement and a surfactant, and those made of an epoxy resin, a curing agent made of a polyamide amine, and cement are known (for example, see Japanese Patent Publication No. 54-273110 and Japanese Patent Application Laid-Open No. 54-22918). . However, the former adhesive has cement as an essential component, and therefore, the cement may absorb moisture in the air and solidify, posing a problem with its storage stability. In addition, when using the latter adhesive,
Each component must be mixed each time by a so-called "wet hand method", making the bonding work extremely complicated. Therefore, there has been a desire for an adhesive that has good adhesion in the presence of water, as well as excellent storage stability and workability.

Cyclodextrins are known to incorporate various compounds into their rings to form clathrate compounds, and the formation of clathrate compounds has been utilized in various fields. The clathrate compound of this cyclodextrin and epoxy compound is, for example, the following formula; (wherein, R is a hydrogen atom or a methyl group, and n is 1 to 10
It is known that an epoxy compound represented by (representing an integer of ) is included in cyclodextrin.
For example, see Japanese Unexamined Patent Publication No. 187-187 Eila).

However, this clathrate compound has the effect of increasing water solubility and improving clathration ability, and to date, no adhesive has been found that uses a compound that includes an epoxy compound. .

[Object of the invention] The present invention solves the above-mentioned problems.It is stable in the absence of water, increases in adhesiveness in the presence of water, has pressure-sensitive adhesive properties, and is suitable for use in the sea or underwater. The purpose of the present invention is to provide an underwater adhesive composition that can be used for adhesive work in.

[Summary of the Invention 1] As a result of intensive research to achieve the above object, the present inventors applied a crosslinking reaction by ring-opening addition reaction of epoxy groups with carboxylic acid, and developed a polyfunctional epoxy compound with cyclodextrin. Inclusion and carboxylic acid-containing polymers,
By pre-mixing, it is stable under normal conditions, but in the presence of water, the epoxy compound is liberated from the cyclodextrin and reacts with the carboxylic acid in the polymer, resulting in strong adhesion in water. They discovered this and completed the present invention.

That is, the underwater adhesive composition of the present invention comprises (A) poly(
A composition comprising meth)acrylic acid and/or sodium poly(meth)acrylate, and (B) a polyfunctional epoxy compound clathrated in cyclodextrin, wherein (A) and (B) of the composition The blending ratio is (A)/(B)=10010.01 to 20 by weight.

(A) poly(meth)acrylic acid or sodium poly(meth)acrylate which is a constituent component of the composition of the present invention,
Each can be obtained by aqueous solution polymerization of (meth)acrylic acid or sodium (meth)acrylate by a known method. Moreover, sodium poly(meth)acrylate can also be obtained by neutralizing poly(meth)acrylic acid with sodium hydroxide. Examples of such poly(meth)acrylic acid and sodium poly(meth)acrylate include Carpobol 114
1, 11140, 934 (product name; manufactured by B.F. Gutdrich Chemical Company); Julimar AC-10P, Alonbis S, M, SS, OL (product name; manufactured by Nikki Junyakusho); Hivis WAKO ( (manufactured by Wako Tsumugi Pharmaceutical ■), Rubiscoll (product name; manufactured by Yuka Padishu Co., Ltd.)
etc. can be mentioned.

In addition, when component (A) is a mixture of polyacrylic acid and sodium polyacrylate, the mixing ratio is not particularly limited, but the higher the content ratio of sodium poly(meth)acrylate, the higher the content of sodium poly(meth)acrylate. Since the curing time of the epoxy compound becomes long, the curing time can be set according to the usage conditions by adjusting the content ratio of sodium poly(meth)acrylate.

The polyfunctional epoxy compound (B) encapsulated in cyclodextrin, which is the second component of the composition of the present invention, is prepared by contacting a predetermined amount of the polyfunctional epoxy compound and cyclodextrin in a suitable molten V. It can be obtained by

The polyfunctional epoxy compound used here needs to contain two or more epoxy groups in its molecule. Examples of such epoxy compounds include triglycidyl isocyanurate, triglycidyl p-amine phenol, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1. l1l
- Compounds having a glycidyl group such as hexanediol diglycidyl ether, glycerol polyglycidyl ether, and terephthalic acid diglycidyl ester acrylate can be mentioned, among which are tetraglycidyl derivatives of metaxylene diamine, tetraglycidyl derivatives of methylene diamine, etc. is preferred.

Further, the type of cyclodextrin used here is not particularly limited, and it is usually its β form, or α, β and 7
A mixture of bodies can be used.

The mixing ratio of the epoxy compound and cyclodextrin varies depending on the type of epoxy compound and cyclodextrin used, but the weight ratio of the cyclodextrin and epoxy compound is usually 1/2 to I/+00, preferably 115 to 1/20. It is.

Suitable solvents used during inclusion include:

Any solvent may be used as long as it dissolves the epoxy compound but does not dissolve the cyclodextrin, but from the viewpoint of ease of removing the solvent in a subsequent step, it is preferable to use a solvent that does not have a high boiling point. Examples include methanol, ethanol, impropatol, acetone, methylene chloride, ethyl acetate, benzene, toluene, etc. Among them, ethanol is particularly preferred.

Inclusion of the epoxy compound and cyclodextrin is carried out by adding each to the above-mentioned solvent, heating the mixture to room temperature or 50 to 80°C, and thoroughly stirring the mixture.

Through this operation, the epoxy compound is incorporated into the voids of the cyclodextrin molecules and retained therein. This allows the composition of the present invention to remain stable during storage and handling in the absence of water.

The blending ratio of (A) and (B) in the composition of the present invention is (A) poly(meth)acrylic acid and/or poly(
For 100 parts by weight of sodium meth)acrylate, (
B) The amount of the epoxy compound is 0.01 to 20 parts by weight, preferably 0.2 to 10 parts by weight. When the blending ratio exceeds 20 parts by weight, the curing reaction proceeds excessively, making the cured product brittle and easily cracked by clamming. If the amount is less than 0.01 part by weight, the curing reaction will be insufficient and the adhesive strength will decrease.

If necessary, low molecular weight polyethylene glycol can be added to the composition of the present invention to impart initial tackiness in water, and an inorganic filler can be added to improve strength.

The composition of the present invention can be obtained by uniformly mixing the two components, for example, in powder form.

When using the composition of the present invention, the powdered composition of the present invention is uniformly sprinkled onto polyethylene, polypropylene, polyvinyl chloride, polyester, metal foil, glass cloth, etc., and then a press machine is used. It can be used as a sheet-like adhesive by pressing the adhesive. Furthermore, the powdered composition of the present invention can be used as a solid adhesive by, for example, being compressed using a tablet machine.

When the sheet-like or solid underwater adhesive pressure-sensitive adhesive thus obtained is used in water, it becomes an adhesive component (A
) The viscosity of the component increases, and it can be easily attached to an object by pressing it lightly. Furthermore, although it varies depending on the conditions of use, etc., after about several minutes to several tens of minutes, the epoxy compound clathrated in the cyclodextrin is liberated by the action of water and hardens by reacting with component (A). , it is possible to more firmly adhere to the adherend.

[Embodiments of the invention] Hereinafter, the present invention will be explained in further detail with reference to Examples.

Examples 1 to 5 Epoxy cyclodextrin phrase 0710g of β-cyclodext, N, NI N-1°, N
"BB Tetraglycidyl Taxylene Diamine (manufactured by Mitsubishi Gas Chemical ■, trade name PGA-X) Ig was added to 100 g of ethanol and thoroughly stirred at room temperature. Then, about 1
The mixture was boiled for an hour to volatilize the ethanol.

In this way, component (B) in the composition of the present invention,
A cyclodextrin inclusion product of an epoxy compound was obtained.

The composition of the present invention was obtained by powder-mixing Carpobol 841, which is the component (A), and (B) f&min, which was produced by the method described above, at the blending ratio shown in the table below. This composition 8h
g using a tablet molding machine (KT-2 type powder molding press machine;
(manufactured by Nichiei Seiko ■) at a pressure of 2 tons/C12 to obtain a button-shaped adhesive with a diameter of 10 mm. This adhesive became sticky when placed in water, and when it was sandwiched between two glass plates and strongly pressed from both sides, it immediately bonded firmly.

In addition, this adhesive was sandwiched between two stainless steel plates, and
After standing in water for an hour, the lap joint adhesion strength was measured at a pull-off rate of lO layers/min. The results are shown in the table.

Example 6 A 25 mm x 100 mm polyester adhesive tape (substrate thickness 2511 mm) using an acrylic adhesive was placed on a 20 ton press-1 with the adhesive side facing up, and about 1.5 g was placed on the l-. The composition of the present invention of Example 1 was uniformly applied to #*
After that, it was pressed at a pressure of 10) tons/C112.

When this tape is placed in water, the adhesive becomes viscous and
It also became soft, making it easy to wind and adhere to adherends. When this tape was wound around a 1 inch diameter iron pipe in water, it was firmly adhered to the pipe after 1 hour.

Example 7 The clathrate tg produced in Example 1 was added to a mixture of 94,190 g of Carpo Ball and 10 g of Aronbis S to obtain a powder mixture. Next, this mixture of ElOmg was molded using a tablet molding machine at a pressure of 2 tons/C- to give a diameter of 1
A 0 mm button-shaped adhesive was obtained.

When this adhesive was put into water, it became sticky, and when it was sandwiched between steel plates and pressed from both sides, it bonded firmly. After leaving it as it was for about 20 hours, the lap joint adhesive strength was measured at a peeling speed of Ih 17 minutes. The adhesive strength was approximately 1.5 kg.

[Effects of the Invention] As explained above, the composition of the present invention is stable in the absence of water (in the air) and has excellent storage stability.
It is also easy to handle. In addition, the composition of the present invention increases its adhesiveness in water, and furthermore, due to the curing reaction between the epoxy compound released from the cyclodextrin and poly(meth)acrylic acid, etc., it firmly adheres to the adhered material for a long period of time. Its industrial value is extremely large.

Claims (1)

[Claims] A composition comprising (A) poly(meth)acrylic acid and/or sodium poly(meth)acrylate, and (B) a polyfunctional epoxy compound clathrated in cyclodextrin, the composition comprising (A) ) and (B) in a weight ratio of (A)/(B)=100/0.01
-20.