JPH0297585A - Adhesive composition - Google Patents

Abstract

PURPOSE:To obtain the title composition undergoing a rapid cure reaction and improved in adhesiveness to aluminum, stainless steel, etc., by using two specified liquids as constituents one or both of which contains an acidic phosphate monomer having (meth)acrylic groups. CONSTITUTION:The title composition comprises a first liquid (A) consisting of 100 pts.wt. acrylic compound (a) selected from (meth)acrylic acid and its esters, 0.1-10 pts.wt. polymerization initiator (b) selected from peroxy esters, 0.05-7 pts.wt. organic dibasic acid (c) and, if necessary, 0.05-7 pts.wt. photopolymerization initiator (d), and a second liquid (B) containing at least 1wt.% amine/ aldehyde condensate (e) and a copper salt (f) in an amount sufficient to provide a copper concentration of 10-10,000ppm, and an acidic phosphate monomer having (meth)acrylic groups is incorporated into A or B in an amount of 0.05-10 pts.wt. based on 100 pts.wt. A or B, or into both A and B in an amount of 0.05-7 pts.wt. based on 100 pts.wt. A and B respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a two-component adhesive composition that can be used for bonding metal parts, ceramic parts, etc.

[Conventional technology]

The demand for adhesives that harden in a short time at room temperature tends to increase year by year from the viewpoint of labor saving, resource saving, and energy saving. Conventionally, well-known quick-curing adhesives at room temperature include two-component quick-curing epoxy adhesives, instant adhesives, anaerobic adhesives, and non-anaerobic acrylic adhesives.

A two-component fast-curing epoxy adhesive is used by measuring and mixing the base agent and the curing agent, and if the measuring and mixing are not carried out sufficiently, there is a risk of a significant decrease in strength. Furthermore, even if sufficient measurement and mixing are carried out, peel strength and impact strength are low.

Although instant adhesives have excellent workability, their range of use is severely limited because they generally have low peel strength, low impact strength, and poor heat resistance and moisture resistance.

Since anaerobic adhesives are adhesives that harden by pressing between the materials to be bonded and blocking air, naturally, parts that come into contact with air, such as protruding parts, do not harden.

Therefore, if the adherend is porous or the clearance between the adherends is large, the adhesive will not cure sufficiently, resulting in poor adhesion.

Non-anaerobic acrylic adhesives, commonly referred to as second generation acrylic adhesives (SGA), are two-component adhesives, but do not require precise metering of the two-component components and require very rough measuring and mixing (sometimes two-component adhesives). It has excellent workability, curing in a few minutes to several tens of minutes at room temperature (with only contact with the surface), and has high peel strength and impact strength, and cures well at protruding areas, making it widely used. It has become. However, labor saving,
From the viewpoint of saving resources and energy, there is an increasing demand for shortening the curing time of such acrylic adhesives from several minutes to several tens of minutes at room temperature.

For example, the adhesive disclosed in U.S. Pat. No. 4,348,503 is comprised of urethane acrylate, acrylate monomer, aromatic perester, organic acid, and transition metal, and cures with a set time of 45 seconds. Furthermore, the adhesive disclosed in JP-A-60-199085 uses a specific urethane acrylate and (meth)acrylic acid ester monomer (acrylic acid ester and methacrylic acid ester are collectively referred to herein as such). It is composed of an accelerator consisting of a peroxyester and a compound that forms a redox system with the peroxyester, and also cures in a quick setting time of less than 1 minute.

However, these adhesives have a problem of insufficient adhesion to aluminum, stainless steel, chromate plating, and the like.

It is known to add an acidic phosphorus compound to improve the adhesion of such acrylic adhesives to aluminum, stainless steel, chromate plating, etc.
1-132234, JP-A-58147477). However, since the phosphorus compound acts as a stabilizer for the acrylic adhesive and retards the curing speed, it has been difficult to produce the aforementioned acrylic adhesive that cures quickly and has good adhesion.

[Problem to be solved by the invention]

The present invention improves the drawbacks of the adhesive called SGA described above, and provides a fast-curing acrylic adhesive composition that has good adhesion to aluminum, stainless steel, chromate plating, etc., which was difficult to achieve using conventional techniques. The purpose is to provide.

[Means to solve the problem]

The present invention comprises: A) an acrylic compound selected from (meth)acrylic acid and its esters; B) a polymerization initiator selected from peroxy esters; C) a first liquid mainly consisting of an organic dibasic acid; and D) an amine and an aldehyde. The reaction condensate E) consists of a second liquid containing a copper salt, and is characterized by containing an acidic phosphoric acid monomer having a (meth)acrylic group in either or both of the first liquid and the second liquid. It is a two-component adhesive composition.

The acrylic compound selected from (meth)acrylic acid and its ester as component A constituting the first liquid of the adhesive composition of the present invention may be any compound as long as it is capable of radical polymerization, and examples thereof are as follows. It is.

■ - Formation %formula% A monomer represented by

Here, A is a (meth)acryloyl group, C1,・CHC
OOCHz-CI (OR) CHt- group, or CL
・C(CHJCOOCHz-CH(OH)CHt- group, R, is H or an alkyl group having 1 to 20 carbon atoms, cycloalkyl group, benzyl group, phenyl group, tetrahydrofurfuryl group, glycidyl group, dicyclopenta Represents a nyl group, a dicyclopentenyl group, or a (meth)acryloyl group.

Specifically, such monomers include (meth)acrylic acid, (
Methyl acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycerol ( Examples include meth)acrylate and glycidyl group (meth)acrylate.

■ -Format A-0-←RZOsu++R+ ■ -Format -CsHb-, -CH2O)! --CJi- or -C
-4-DeCI.

Chyl (meth)acrylate, 2-hydroxypropyl meth)acrylate, ethoxyethyl (meth)acrylate, polyethylene glycol (meth)acrylate,
Phenomethane ethylene glycol (meth)acrylate, dicyclopentenyloxy (meth)acrylate, tripropylene glycol (meth)acrylate and 1,6
-Hexanidi/diol di(meth)acrylate and the like.

A monomer represented by

Here, A and R2 are as described above. R1 is ■4
Alternatively, it represents an alkyl group having 1 to 4 carbon atoms, and m is an integer of 0 to 8.

Specifically, such monomers include 2,2-bis(4-methacryloxyphenyl)propane, 2゜2-bis(4-methacryloxyethoxyphenyl)propane, and 2,2-bis(4-methacryloxyphenyl)propane. jetoxyphenyl)propane, 2,2-bis(4-methacryloxypropoxyphenyl)propane, and 2,2-bis(4-methacryloxytetraethoxyphenyl)propane.

■ (Meth)acrylic acid ester of polyhydric alcohol not included in the monomers of ■, ■, and ■.

Specific examples of such monomers include trimethylolpropane tri(meth)acrylate, neobentylglycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. .

■ Urethane prepolymers with (meth)acryloyloxy groups These monomers specifically have (meth)acryloyloxy groups.
It is obtained by reacting an acrylic ester with an organic polyisocyanate and a polyhydric alcohol. Specific examples of (meth)acrylic esters having hydroxyl groups are (
Examples include hydroxyethyl meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate. Specific examples of the organic polyisocyanate include toluene diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, and inphorone diisocyanate. Specific examples of polyhydric alcohols include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

One or more of the above monomers can be used, but it is preferable that one of the monomers in the adhesive composition is a urethane prepolymer having a (meth)acryloyloxy group as shown in (2). This is desirable. Among these, preferred is a urethane prepolymer having (meth)acryloyloxy groups in which the polyhydric alcohol portion is polytetramethylene glycol.

Specific examples of the polymerization initiator consisting of per-oxyester as component B include tert-butyl peroxybenzoate, tert-butyl peroxy acetate, tert-butyl peroxy isobutyrate, and tert-butyl peroxy phthalate. However, tertiary-butyl peroxybenzoate is most preferred.

Specific examples of the dibasic acid as component C include maleic acid, itaconic acid, and phthalic acid, with maleic acid being the most preferred.

The individual components contained in the first liquid have been explained above,
The preferable blending ratio is based on 1001 parts by weight of component A, and 10 parts by weight of component B po, i. Further, a photopolymerization initiator may be added to the first liquid. Examples of the photopolymerization initiator include benzyl, benzophenone, benzyl I ethyl ether, and benzyl dimethyl ketal.

The preferred amount of the photopolymerization initiator added is 0.05 to 7 parts by weight, particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the first liquid.
Parts by weight.

Ingredients A, B, and C as described above are essential components of the first liquid composition, but in addition, various antioxidants, polymerization inhibitors, etc., which are already known, are used for the purpose of improving stability. It is also possible to add additives. Furthermore, depending on the purpose, it is also possible to use plasticizers, fillers, thickeners, colorants, etc.

Next, the D component and E component constituting the second liquid will be explained.

The reaction condensate of an amine and an aldehyde as component D is prepared in the presence of a carboxylic acid such as acetic acid and propionic acid or an inorganic acid such as phosphoric acid or sulfuric acid in an amount of at least 1 mole, preferably 1.5 to 3 moles per mole of the amine. 4 moles of aldehyde
It is obtained by reacting at 0 to 70°C. Specific examples of the reaction condensate of amine and aldehyde include butylamine and reaction condensate of aniline and butyraldehyde.

Component D is desirably in liquid form, and it is better to dissolve or disperse it in a volatile melting liquid to form the second liquid, which has better workability as an accelerator. Suitable solvents include methylene chloride, trichloroethane, acetone, methyl ethyl ketone, ethyl acetate, toluene, methanol and ethanol.

The concentration of component D in the second liquid is preferably 1% by weight or more.

The copper salt of component E is an organic or inorganic salt, and examples thereof include copper acetate, copper naphthenate, copper octenoate, and copper acetylacetone complex.

The preferred blending amount of component E is 10 to 110,000 pp, particularly preferably 50 to lo
00 ppm.

As described above, the component E and the component E are essential components of the second liquid, but other materials such as a plasticizer, filler, thickener, colorant, etc. may be used depending on the purpose.

The adhesive composition of the present invention is a two-part adhesive composition consisting of a first part and a second part, and either or both of the first part and the second part has a (meth)acrylic group. Contains acidic phosphoric acid monomer. The acidic phosphoric acid monomer having a (meth)acrylic group has the general formula [However, Cocote Rz is -Cz fl a--C3Hb
--CH2Cl--CJ8- or -c, n, ! −
and k represents CH,1 1 to 10. R4 represents H or CH3, R3
is H or N OH3CgH40H, or is C1-1
, or C2HS. ], specifically acid phosphooxyethyl (meth)acrylate, acid phosphooxyethyl (meth)acrylate, acid phosphooxyethyl (meth)acrylate monoethanolamine salt, acid phosphooxyethyl (meth)acrylate
Acrylates include diethylaminoethyl (meth)acrylate salt and bis(2-hydroxyethyl (meth)acrylate) acid phosphate. These acidic phosphoric acid monomers having a (meth)acrylic group can be used alone or in combination of two or more.

The preferred blending amount of the acidic phosphoric acid monomer having a (meth)acrylic group is 0 parts by weight per 100 parts by weight of the first solution or the second solution when it is blended in either the first solution or the second solution.
．． 0.5 to 10 parts by weight, particularly preferably 0.5 to 7 parts by weight. When blended into both the first and second liquids, 0.05 parts by weight per 100 parts by weight of each of the first and second liquids.
~7 parts by weight is preferred, and 0.5 to 5 parts by weight is particularly preferred.

[Effect]

The adhesive composition of the present invention is rapidly cured in a short time by bringing the first liquid into contact with the second liquid, and has good adhesion to chromate plating, aluminum, stainless steel, and the like.

When using the adhesive composition of the present invention, since the curing speed is fast, the first liquid is applied to one adherend, the second liquid is applied to the other adherend, and the second liquid is volatile. If a solvent is contained, it is desirable to volatilize the solvent and then bond the coated surfaces of each adherend together.

If this method produces protruding areas where the first and second liquids did not come into contact, it is possible to add a photoinitiator to the first liquid and cure the protruding areas by irradiating them with ultraviolet rays, if necessary. can.

〔Example〕

Hereinafter, the adhesive composition of the present invention will be further explained by Examples.

Reference M: Charge about 50 g of tolylene diisocyanate and about 0.03 g of dibutyltin dilaurate in a reactor, keep the reaction temperature at 60 to 70°C, and gradually add about 145 g of polytetramethylene glycol with a molecular diameter of about 1000 while stirring. Added. The temperature was maintained at 60 to 70°C and the reaction was allowed to proceed for about 1 hour, and about 75 g of 2-hydroxyethyl methacrylate was gradually added thereto, followed by stirring for 3 hours. Temperature about 80℃
After stirring for 1 hour, 236 in the IR spectrum
After confirming that no NGO signal near 0 cm-' was observed, the mixture was cooled to room temperature to obtain urethane prepolymer UA-1 having meth)acryloyloxy groups.

Examples 1 to 8 and ' 1 to 5 In addition to the (meth)acryloyloxy group-containing urethane prepolymer IJA-1 obtained in Reference Example as the A component,
The acrylic compound shown in the table, the polymerization initiator shown in Table 1 as the B component, maleic acid as the C component, and an acidic phosphoric acid monomer having a (meth)acrylic group were mixed in the proportions shown in Table 1. , was used as the first liquid.

Tsukusera 8 (trade name: manufactured by Irunai Shinko Kagaku Kogyo Co., Ltd.; n-butyraldehyde aniline) as the D component, copper naphthenate (copper concentration 5%) as the E component, and acidic phosphoric acid having a (meth)acrylic group. The monomer and the solvent were mixed in the proportions shown in Table 1 to prepare a second liquid.

The properties of the adhesive compositions of Examples and Comparative Examples were measured by the following method and are shown in Table 1.

■ 5l pruning and 2m as adherend according to ASTM D-1,002
A cFE aluminum test piece (A-5052) was glued and tested using an Instron 1123 type tensile tester (tensile speed 1).
0ss/min).

Compliance level for second construction: 0.31m on the adherend according to ASTM D-1876
A thick stainless steel test piece (SUS304) was glued and tested using an Instron 1123 type tensile tester (tensile speed 501/
Measured in minutes).

Iron on the adherend according to ASTM D-950 (Sanded products: 44X25X19mm and 25X25X
9mm) was adhered and measured using an Izod impact tester.

Apply the first liquid to one side of the test piece for measuring tensile shear strength.
After applying the second liquid to the other test piece and volatilizing the volatile solvent of the second liquid, the coated surfaces of each adherend are brought together and glued together.
The adhesion time was defined as the time until it could not be removed even when a load of kg was applied.

〔Effect of the invention〕

The adhesive composition of the present invention has an extremely fast curing reaction at room temperature.
It also has excellent adhesion to metals such as aluminum, stainless steel, and chromate plating, making it possible to shorten and rationalize production lines, and its industrial applicability is extremely large.

Nif continued Main City iE Book November 7, 1988 Patent Application No. 249143 of 1988 2 Name of invention Adhesive composition 3 Relationship with the case of the person making the amendment Patent applicant address Chiyoda, Tokyo 100 Yurakucho 1-4-1, Ward Yurakucho, 1-4-1 Specification, claims column, detailed description of the invention column 5, contents of amendment (11 claims are corrected as shown in the attached sheet.

(2) On page 4, line 10 of the specification, ``j to raise'' is corrected to ``raise.''

(3) [Tuesday!] on page 17, line 2 of the specification. (4J1-8 and p) and corrected Kushikushi II 1-5 J to "Daishi ■ Uni-ko and Comparative Examples 1-4."

(4) The following statement is inserted between lines 18 and 19 on page 18 of the specification.

1 part by weight of henzyl dimethyl ketal was added as a photopolymerization initiator to the first liquid of the composition of Example 1 and dissolved to prepare the first liquid. Aluminum for tensile shear strength measurement Apply the second liquid of Example 1 to the adhesive surface of the test piece so that it does not protrude, and apply the first liquid described above to the other test piece, and adhere so that the composition of the first liquid does not protrude. When this protruding portion was irradiated with ultraviolet light (Toscure 400 manufactured by Toshiba Corporation, lamp output 80 W/IJ, irradiation distance 15 cm) for 10 seconds, the tank was completely gone even when the surface of the cured product was touched with a finger.

When a similar test piece was not irradiated with ultraviolet rays, the protruding portion remained tacky or uncured even after one day. ” Claims A) An acrylic compound selected from (meth)acrylic acid and its esters B) A polymerization initiator selected from peroxy esters C) A first liquid mainly consisting of an organic dibasic acid; D) An amine. Aldehyde reaction condensate E) Consists of a second liquid containing a copper salt, and either or both of the first liquid and the second liquid contains an acidic phosphoric acid monomer having a (meth)acrylic group. A two-component adhesive composition with special features.

(2) Claim No. 1 (2) in which the first liquid contains a photopolymerization initiator
The adhesive composition described in item 1).

Claims (1)

[Claims] (1) A) an acrylic compound selected from (meth)acrylic acid and its esters; B) a polymerization initiator selected from peroxy esters; C) a first liquid mainly consisting of an organic dibasic acid; and D) a mixture of an amine and an aldehyde. Reaction condensate E) Consisting of a second liquid containing a copper salt, characterized in that either or both of the first liquid and the second liquid contains an acidic phosphoric acid monomer having a (meth)acrylic group. Two-component adhesive composition.