JPH0258583A - Bonding - Google Patents

Abstract

PURPOSE:To adhere materials to be bonded in good workability and extremely in a short time by coating the surface of the material to be bonded with a treating agent containing glyoxal, drying the treating agent, applying an adhesive containing an imide compound, etc., to the coated face and sticking another material to be bonded to the adhesive coated material. CONSTITUTION:The surface of one material to be bonded is coated with (A) a treating agent comprising an aqueous solution containing (i) 5-25wt.% glyoxal and (ii) 1-10wt.% hexamethylenetetramine and the treating agent is dried. Then the applied face is coated with (B) an adhesive comprising an aqueous composition containing (i) 20-40 pts.wt. imide compound prepared by making an isobutylene-maleic anhydride copolymer having 8-9(X)10<4> molecular weight into 30-50mol.% imide modification ratio, (ii) 60-80 pts.wt. calculated as solid content of a carboxy modified styrene-butadiene latex and optionally (iii) a polyfunctional epoxy compound and another material to be bonded is stuck to the adhesive coated material and compressed.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for bonding wood materials, inorganic boards, paper, etc. in an extremely short time.

(Prior Art) Conventionally, as means for instant bonding, cyanoacrylate adhesives and acrylic adhesives based on separate application have been used. These adhesives are expensive, have many restrictions in handling, and are suitable for bonding small areas, but cannot be used for large-scale bonding operations.

Furthermore, according to JP-A No. 56-90867, an aqueous solution of a natural or synthetic polymer having an amide bond or an imide group in the molecule and an aqueous solution of a dialdehyde compound are applied to both surfaces of the adherend in a fast-curing manner. It has been proposed to be used as an adhesive. There is no problem with this method when the bonding area and shape of the adherend materials are the same, but when manufacturing a flash panel where the frame material and crosspiece are combined as a frame material and the surface material is bonded, Applying amide bonds or imide groups in the molecules to the entire surface of the material is economically disadvantageous as the parts other than the bonded areas are completely wasted, and the facing material also warps due to the supplied moisture. This is undesirable because it tends to cause peeling due to the stress when the pressure is released. Further, it is quite complicated to carry out the same work on the face material in accordance with the bonding part with the frame material, and the work cost increases, leading to an increase in the cost.

(Problems to be Solved by the Invention) In the production of adhesive products, there is a widespread desire to shorten the time required for adhesion and simplify the process as a means of improving productivity. The method is complicated and involves applying adhesive components separately to both surfaces of the materials to be bonded;
There has been a long-awaited development of a bonding method that does not require an uneconomical process, but requires a process of treating and applying only one side of the adherend, which is easy to work with and uses an inexpensive adhesive. The adhesion process includes a process of applying an adhesive to the adherend and subsequent pressing. In this case, it is an important property of the adhesive to allow sufficient deposition time after application until sufficient pressure is applied for adhesion. The inventors of the present invention have carried out intensive research into solutions for this bonding process, and have found that by using the processing agent (a) and adhesive (b), sufficient deposition time can be secured for the work. We have completed a method of bonding in an extremely short time.

The present invention relates to an extremely short-time bonding method that is particularly suitable for manufacturing so-called flash panels, in which a panel is bonded to a frame material that is a combination of a frame material and a crosspiece.

(Means for Solving the Problem) As a result of intensive research to achieve the above object, the present inventors have developed a treatment agent (a) which is an aqueous solution containing glyoxal and hexamethylenetetramine at a specific concentration, and a specific An adhesive that is an aqueous composition consisting of an isobutylene-maleic anhydride-modified compound having a molecular weight range and a specific amount of imide groups in the molecule, a carboxy-modified styrene-butadiene latex, and optionally a polyfunctional epoxy compound. It has been discovered that good workability and strong adhesive strength can be achieved by using a combination of (b) and applying the adhesive to only one side of the adherend, thereby completing the present invention. That is, in the present invention, the treatment agent (a) for coagulating the adhesive (b) is applied to one adherend in advance, and after drying, the adhesive (b) is then overlaid and applied to the treated adherend. The present invention relates to a method for bonding in an extremely short period of time, which comprises the steps of overlapping and bonding the other adherend.

The treatment agent (a) according to the present invention is an aqueous solution comprising glyoxal and hexamethylenetetramine.

The concentration of glyoxal ranges from 5 to 25% by weight, preferably from 10 to 20% by weight. When glyoxal is less than 5% by weight, the adhesive (b) coagulates slowly;
The desired effect cannot be obtained. Moreover, if the concentration of glyoxal exceeds 25% by weight, the coagulation of the treatment agent (a) on the coated surface is too slow, which tends to cause poor adhesion, which is not preferable. On the other hand, the concentration of hexamethylenetetramine is 1 to 101
i amount%, preferably 2 to 8% by weight. An appropriate amount of hexamethylenetetramine has the effect of keeping the treatment agent (a) in a neutral range and controlling the coagulation rate of the imide compound, as well as improving the water-resistant adhesive strength. When hexamethylenetetramine is not blended, the acidity of the treatment agent (a) is strong and tends to damage the wood, which is not preferable. In addition, if the concentration is high, the pH of the treatment agent (a) will increase and coagulation of the adhesive will be delayed, resulting in unfavorable short-term adhesion. The treatment agent (a) may be mixed with a water-soluble solvent such as an alcohol, ketone, or ester solvent in order to improve its applicability. Surfactants can also be mixed for the same purpose. The amount of treatment agent (a) applied is adjusted as appropriate depending on the type of adherend.

The adhesive (b) used in the present invention is (1) an imide compound, (2) a carboxy-modified styrene-butadiene latex, and optionally (3) for imparting water resistance.
Consists of a polyfunctional epoxy compound with two or more epoxy groups in one molecule.

The imide compound (]) and the carboxy-modified styrene-butadiene latex 2) are (1) of 20 to 40 overlapping parts.
(2) is used in a ratio of 60 to 80 parts by weight as a solid content, but a ratio of 25 to 35 parts by weight and 65 to 75 parts by weight is suitable. If the amount of the imide compound is less than 20 parts by weight, coagulation by the geographical agent (a) will be weak and good adhesive strength cannot be obtained, and if it is more than 40 parts by weight, water resistance will be low and the size liquid This is not desirable for work as it increases the viscosity.

If necessary, a filler may be added to the adhesive (b) for the purpose of adjusting fluidity, reinforcing adhesive strength, and increasing the amount.

The blending amounts are the above imide compound (1) and the above latex (2).
) is desirably 100% by weight or less based on the total amount of solid content. Fillers used in adhesive (b) include calcium carbonate, barium carbonate, limestone, clay, talc, wood flour, and the like.

These may be used alone or in combination of two or more.

The imide compound (1) used in the adhesive (b) has a molecular weight of 8 to 9 x 1 of the isobutylene-maleic anhydride copolymer.
04 is limited to 5.5 to 6.5XI, which has a low molecular weight.
Water resistance and strength at depressurization are not sufficient near OL,
Furthermore, if a high molecular weight material with a molecular weight of around 16 to 17 x 10' is used, the adhesive will thicken, and in order to make an adhesive that can be used for practical purposes, it must have a low imidization rate, resulting in low water resistance and degradation. The strength under pressure also decreases.

The imide compound (1) used in the present invention is isobutylene-
It is obtained by imide-modifying a maleic anhydride copolymer. The modification rate is preferably 30 to 50 mol%, more preferably 35 to 45 mol%. Modification rate is 30 mol%
If it is less than 1, the coagulation by the treatment agent (a) becomes weak and adhesive strength cannot be obtained by pressing for a short time. In addition, if the modification rate exceeds 50 mol%, the size liquid exhibits strong stringiness, and the coagulation by the processing agent (a) is too strong, and when the adhesive (b) is applied and pressed in layers, it becomes difficult to coat the adhesive. Leakage into the material is poor and the desired strength cannot be obtained.

The term "denaturation rate" as used herein is defined as follows. The reaction of modifying the ammonia adduct of the isobutylene-maleic anhydride copolymer into the imide compound (1) is a deammonization/dehydration reaction, and the water produced by the reaction is distilled out of the reaction system. That is, by measuring the amount of water distilled off, the modification rate (mol %) of the imide reaction can be determined using the following equation.

[In the formula, A is the dehydration fk (g), W is the amount of isobutylene-maleic anhydride copolymer collected (g), and 154 (g) is the molecular weight of the repeating unit of the inbutylene-maleic anhydride copolymer (g). ). ] The imide compound (1) is used as an aqueous solution prepared by dissolving basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium phosphate, ammonium hydroxide, and amines alone or in combination of two or more.

The water-based latex used for adhesive (b) was specifically limited to carboxy-modified styrene-butadiene latex (2) because it has high strength when decompressed and has high water resistance due to the polyfunctional epoxy compound used as a crosslinking agent. This is because it gives you sex.

The polyfunctional Evoquin compound (3) having two or more epoxy groups in one molecule used in the adhesive (b) is preferably a low viscosity liquid, such as N,N,N',N'-tetraglycidyl- 1,3-xylylenediamine, 1,3-bis(N
- Tetrafunctional poxy compounds such as diglycidylaminomethyl)cyclohexane, trifunctional poxy compounds such as glycerol triglycidyl ether, 0-7 triglycidyl ester, ethylene glycol -
Difunctional poxy compounds such as diglycidyl ether, glycerol-diglycidyl ether, 1,6-hexanethiol-diglycidyl ether, and neobentyl glycol-diglycidyl ether are used. These may be used alone or in combination of two or more. The mixing ratio of these polyfunctional epoxy compounds (3) is not particularly specified, but usually the imide compound (1) and the latex (
The amount is 1 to 30% by weight based on the total amount including the solid content of 2). If it is less than 1% by weight, the effect of improving water resistance will be small;
If it exceeds 0% by weight, high strength upon decompression cannot be expected for the very short-time bonding method that is the object of the present invention, and the viscosity of the adhesive (b) will change significantly, making the work difficult. I don't like it because there is.

When the treatment agent (a) and adhesive (b) used in the present invention are intentionally mixed, they coagulate instantaneously. This coagulation is caused by the processing agent (
It is presumed that this is due to hydrogen bonding between the aldehyde group contained in a) and the imide group contained in the adhesive (b) due to active hydrogen. This instantaneous solidification phenomenon is expressed as strength upon decompression.

Next, the present invention will be explained with reference to examples, and all parts and percentages in the examples and comparative examples are parts by weight and percentages by weight.

(1) Preparation of processing agent (a) Using a 40% concentration glyoxal aqueous solution and hexamethylenetetramine, processing agent (a) solutions having different amounts of glyoxal and hexamethylenetetramine were prepared.

(2) Preparation of imide compound aqueous solution Isobutylene-maleic anhydride copolymer [manufactured by Kuraray Co., Ltd.: trade name Isopan 04, molecular weight 5.5-6.5×10
4; Isopane 06, molecular weight 8-9X10'; Isopane I
1150 g of O1 molecular weight 16-17XlO' was stirred 6
The mixture was heated to 0°C and ammonia gas was blown into it to form an ammonia adduct, then heated to 180°C with stirring to perform an imidization reaction in a nitrogen stream, resulting in different modification rates as shown in the table below. An imide compound was obtained. This imide compound was dissolved in sodium hydroxide, solid content 40%, pH 7.2 (pH
An aqueous solution of test paper (cresol red).

(3) Preparation of adhesive (b) a) Imide compound aqueous solution, carboquine-modified styrene-butadiene latex as shown in the table below [manufactured by Japan Synthetic Rubber Co., Ltd.: product name J]
SR○668, solid content 48%; Nippon Zeon Co., Ltd.'s:
Product name: 2-ball LZ-430, solid content 49%; produced by Sumitomo Nogatatsuta Co., Ltd.: 5N-307, solid content 48% J; as a comparative example, non-carboxy modified styrene-butadiene latex [produced by Asahi Kasei Industries, Ltd.] Name DL-[312
, solid content 48%1, c) carbonic acid runium E manufactured by Nichizuka Funka Kogyo Co., Ltd.: trade name N5-fool, and 2) tetrafunctional poxy compound [manufactured by Mitsubishi Gas Chemical Co., Ltd.:
TETRAD-X, TETRAD-C], trifunctional poxy compounds [manufactured by Nagase Kasei Co., Ltd., trade name Bunacol EX-313], bifunctional poxy compounds [manufactured by Nagase Kasei Co., Ltd., trade name Denacol E, etc.] and mixed well to prepare adhesive (b).

(4) Measurement of Splitting Adhesive Strength Stainless steel material with a specific gravity of 0.45 ± 0.02 and a water content of 10 ± 1% was cut into 40 x 40 x IO mm pieces as an adherend, and 50 g of treatment agent (a) was applied to this adherend. The adhesive (b) is then applied to the treated surface in an overlapping layer of 350 g/m". A 40 x 50 x 5.5 mm lauan plywood having a specific gravity of 0.45±0.02 and a moisture content of IO±1% is bonded to this coated surface so that the fiber direction of the plywood surface and the fiber direction of the Stainless Steel material are orthogonal. Deposition time 3 molecules i, °IO
Press at kg/cm2 for 1 minute. Immediately after depressurization, the splitting strength was measured using a tensile tester manufactured by Toyo Baudouin Co., Ltd. at a tensile rate of 5') 100 mm.

The above test was conducted at 20°C. The unit is kg.

(5) Measurement of compression shear adhesive strength A cover material having a specific gravity of 0.65±0.05 and a water content of 11±1% was cut into a size of 150×200×IO mm and used as an adherend. Apply treatment agent (a) at 50 g/m2 to one side of the adherend and dry. Next, apply adhesive (b) in layers of 350 g/m" to the treated surface, and immediately attach the other adherend to 12 kg of adhesive.
/cm" for 24 hours. After curing for 3 days at 20℃, J
A test piece was prepared in accordance with the IS・K-6852r Adhesive Pressure Shear Adhesive Strength Test Method, and was tested at a loading rate of 900 per minute using an Amsler type testing machine manufactured by Mori Shikenki Seisakusho Co., Ltd.
Compressive shear strength was measured in kg. The unit is kg/
cm”, the value within 0 is the wood breakage percentage.The treatment of the test piece was J.
IS-N-6801R urea resin wood adhesive” and J
Is-ni-6802 [phenolic resin wood adhesive].

Examples 1 to 7 and Comparative Examples 1 to 6 are shown in Table 1, Examples 8 to 1
0, Comparative Examples 7-8 are in Table 2, Examples 11-13, Comparative Examples 9-1O are in Table 2, Example 14, Comparative Example ll-13
are shown in Table 4, and Examples 15 to 21 are shown in Table 5.

Adhesive (b): Imide compound aqueous solution (isopane 06, imide modification rate 42%, solid content 40%) 31 parts 0668 30 parts LX-43023 parts MS-10016 parts TETRAD-X 5 parts Treatment agent (a): Glyoxal 15 g /Hexamethylenetetramine 5 parts/Water 80 parts Imide compound aqueous solution: Isopane 06, imide modification rate 42
%, solid content 40% Treatment agent (a) Adhesive (b): Glyoxal 15 parts/Hexamylenetetramine 5 parts/Water 80 parts: Imide compound aqueous solution (isopane 06 solid content 40%) 28 parts 5N-30758 parts NS-100 16 parts TETRAD-X 2.5 parts TETRAD-C2, 5 parts Treatment agent (a): Adhesive (b): Glyoxal 15 parts/hexamethylenetetramine 5 parts/water 80 parts Imide compound aqueous solution (isopane 06 solid content 40%) 28 parts SBR (r0668J or r61:2+) 56 parts NS-10016 parts TETRAD-X 5 parts (Effects of the invention) The present invention mainly relates to adhesion of wood materials, and its purpose is to achieve economical It is an extremely short-time bonding method that is advantageous for
This is largely due to the unique adhesive composition. It can be said that the adhesion method of the present invention has extremely high practical value, particularly in the field of adhesion of flash panels that require a high degree of water resistance.

Procedural amendment entry (1) "Coating an imide group" on page 3, line 2 of the specification, 10/6, 1985, Director General of the Patent Office, Yoshi 1) Written by Mr. N. 1, Indication of the case, 1988 Patent Application No. 209461 No. 2, Invention name adhesion method 3, Relationship with the case of the person making the amendment Patent applicant name Misawa Ceraminck Chemical Co., Ltd. 4, Agent 107 5, No date of amendment order As shown in the attached document, r-imide group "Applying an aqueous solution of a natural or synthetic polymer or an aqueous solution of a dialdehyde compound having a

(2) “Process to only one side” on page 3, line 15 of the specification, Correct it to "processing for only one side".

(3) Specification ring 5 times! Correct "slow" in line 17 to "fast".

(4) On page 6, line 6 of the specification, ``J in case'' is corrected to ``in case''.

(5) "r-samethylene" at the end of page 11 of the specification is corrected to "sameethylene."

(6) rLZJ on page 13, line 2 of the specification is corrected to rLXJ.

(7) "rlo in Table 2" on page 15, line 1 O of the specification is corrected to "10 in Table 3."

Claims (1)

[Claims] After applying the treatment agent (a) to the surface of one adherend and drying it, apply the adhesive (b) on the applied surface, and bond the other adherend to this and press it. The treatment agent (a) contains 5 to 25% by weight of glyoxal and 1
It is an aqueous solution containing ~10% by weight of hexamethylenetetramine, and the adhesive (b) has (1) a molecular weight of 8 to 9 x 10^
20 to 40 parts by weight of an imide compound in which the isobutylene-maleic anhydride copolymer of 4 has an imide modification rate of 30 to 50 mol%, and (2) 60 to 80 parts by weight of carboxy-modified styrene-butadiene latex solid content, and as necessary. Accordingly, the imide compound (1) and the latex (2)
) from 1 to 30% by weight based on the total amount of solids (3)
A method for bonding adherends with good workability and in an extremely short time, characterized in that the composition is an aqueous composition containing a polyfunctional epoxidized food.