JPS58179280A - Adhesive composition - Google Patents

Abstract

PURPOSE:The titled composition having improved heat resistance, retention of adhesion at high temperature, and tensile strength, containing a composition comprising a polymer having a polymerizable side chain and a dihalocyclopropane structure as a polar group and a polymerization catalyst, and an organic acid polymerizable with it. CONSTITUTION:(A) A composition having a polymerizable side chain [preferably (meth)acryloyloxy], a dihalocyclopropane structure (preferably the halogen part is chlorine or bromine) as a polar group, and >=500 molecular weight is blended with (B) preferably 4-80pts.wt. organic acid[preferably (meth)acrylic acid]having a vinyl or methacryl group, polymerizable with the component A based on 100pts.wt. total composition, and, preferably (C) a vinyl monomer such as methyl methacrylate, etc., to give the desired composition. The amount of the methacryloyloxy group is 1/100-1/5,000mol equivalent per unit weight of the polymer having a carbon-carbon unsaturated dobule bond and >=500 molecular weight.

Description

[Detailed description of the invention] The present invention relates to novel anaerobic adhesive compositions.

In recent years, remarkable progress has been made in adhesives that cure quickly at room temperature and require quantitative mixing and other complicated operations. Generation of rubber real se 1” gamma acrylic adhesive,
Second generation rubber-modified acrylic adhesives (abbreviated as SGA) have been appearing one after another.

Japanese Publication No. 1, No. 551+8 discloses that esters such as tetraethylene/glycol dimethacrylate polymerize rapidly under anaerobic conditions.
[5] Contact adhesives that polymerize and harden under anaerobic conditions are called anaerobic adhesives, and are industrially used for fitting loose 'a + I screws of I/J. Uses (・There are also things that are used.

1. Anaerobic adhesives like this are also suitable for structural applications because they have low water resistance and heat resistance, and are expensive. 2. They generally have low gap-filling properties, and the protruding parts do not harden and stick, impeding the aesthetic appearance and work. etc. It has many problems.

Furthermore, Japanese Patent Publication No. 55-111699 discloses that a composition consisting of a polymer having a chlorsulfonyl group in its side chain and a polymerizable vinyl monomer, to which a radical generating agent, an accelerator, etc. are added, cures rapidly at room temperature. Disclose that the adhesive will be
It is now available as 8GA. This adhesive cures at room temperature. It has many features such as high adhesive strength and impact resistance, without the need to secretly mix two components like many room temperature curable epoxy adhesives.

In addition, it has heat resistance, adhesive strength retention at high temperatures, and fatigue resistance.

There are some deficiencies in tensile adhesive strength, etc.

In order to obtain an anaerobic adhesive composition free from these drawbacks, the present inventors developed a composition containing at least one kind of polymerization catalyst and a polymer having a molecular weight of 500 or more and having a polymerizable side chain. The -C anaerobic adhesive contains a polymerizable organic acid or an organic acid and a vinyl monomer in a weight ratio of It has also been discovered that the protruding part of the adhesive does not stick (-) and has excellent properties.

However, especially the tensile adhesive strength of metal pieces such as aluminum and iron)
: When trying to obtain an excellent adhesive composition, it is necessary to have a functional group with high polarity in the main chain of an 11" polymer with a molecular weight of 500 or more and a polymerizable side chain. In general, highly polar polymers are difficult to dissolve in organic acids and vinyl monomers and require a step of separation and purification.

Therefore, in order to improve this drawback, the inventors conducted intensive research into υF and added polar groups to the polymer having polymerizable side chains.
1) By introducing the dino・I−+/chloropropane structure
Excellent adhesion and isolation of metal pieces.

The inventors have discovered that it is possible to obtain an adhesive composition without going through the steps of purification, and have thus arrived at the present invention.

Hereinafter, the present invention will be described in detail.

The polymer having a molecular weight of 500 or more, which has a polymerizable side chain and has a 7-baron clopropane group as a polar group, which is used in the adhesive composition of the present invention, was proposed by the present inventors in Japanese Patent Publication No. 1983- 6198. Namely.

(Here, X represents a halogen atom, A represents a carboxylic acid residue, a sulfo/acid residue, or a carbonic acid monoester,
B is a hydrogen atom,) in the presence of an N-haloamide compound represented by (representing an atom or a carboxylic acid residue),
Polymer substances with 1,500 or more molecules having polar groups and carbon-carbon unsaturated double bonds and the following general formula % formula % (where ■ (represents a hydrogen atom or a methyl group).

n is an integer selected from 2 to 5, 1m is an integer selected from 1 to L1, and l is an integer selected from 1 to 0, respectively. You can get it.

A dihalo/chloropropane-containing polymer (hereinafter abbreviated as D CCR) used as a polymer substance having a molecular weight of 500 or more and having a polar group and a carbon-carbon unsaturated double bond is 1.
Japanese product proposed by the present inventors, ¥f application filed in 1982-792
No. 79 or Japanese Patent Application No. 162706/1988.

In addition, a molecule having a carbon-carbon unsaturated double bond (with a dihalo/chloropropane structure) as a polar group jii5n
The O to -F polymeric material is an organic compound of the general formula H2c = c - c OOH (where R represents a hydrogen atom, atom or a methyl group) in the presence of the aforementioned alkyl hypohighlight or N-haloamide. In the case of acids.

For example, it reacts as shown in the following equation.

CH2 CH.

e 0 C=0 R-C-CH2 100H puller-OH book CH.

For the purpose of the present invention, the introduction of side chains such as acryloyloxy or methacryloyloxy groups is effective for the purpose of the present invention when the above general formulas (1) to (2 )) is an organic acid or its derivative alcohol.

It is prepared to have a molar equivalent of 1/100 to 115,000. If the molar equivalent exceeds 1/100, gelation of the polymer will occur.
Rasai 1. Moreover, if the molar equivalent is less than 115,000, the significance of introducing the side chain will be reduced. Especially 1/200~1
/000 mol is preferred.

In addition, in most cases, this reaction is used in the form of a solution in which one polymer is dissolved in an appropriate solvent, but polymeric substances normally obtained as liquid or viscous substances can be used in the reaction as they are. Needless to say.・The solvent used must be one that has good solubility for the polymer substance used.
A solvent capable of stably dissolving the realkyl hypolite or N-haloamide and the polymerizable unsaturated monomer is selected and used as a single solvent or as a mixed solvent.

Specific examples of solvents include aliphatic solvents such as pentane, hexa/pentane, and 'Actane.

/Alicyclic solvents such as Claw\kizan, benzene.

Nido['benzene, halogenated benzene, toluene/, aromatic solvents such as xylene, dioxa/l-'7-1-
Ether solvents such as Nohydro I furan, ester solvents such as ethyl acetate and methyl acetate.

Examples include ketone solvents such as methyl ethyl keto/, cyclohexanone, acet/, and methyl isobutyl ketone, and halogenated hydrocarbon solvents such as methylene chloride, chloroform, and carbon tetrachloride.

Among these, toluene, benzene, tetrahydrofuran, acetone, dichloromethane, heptane, ethyl acetate, and methyl ethyl ketone are preferred.

In addition, as a solvent for dissolving the polymer, Japanese Patent Publication No. 51-6
One or more vinyl compounds may also be used, as described in No. 198.

Concrete flL! : Styrene, α-methylstyrene.

β-methylstyrene, styrene derivatives of divinylbenzenato, methyl acrylate, methyl methacrylate, tridenyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, dimethylaminoethyl methacrylate, lauryl methacrylate, glyc/zyl methacrylate, Acrylic acid derivatives such as ethyl dimethacrylate and 1,3-butylene dimethacrylate, '! Tallylic acid, methacrylic acid, vinyl acetate.

-r, IJ low-torinol, vinylpyrin, etc. (1) Furthermore, even if the small polymer is solid, it is relatively chemically stable.
1 and is difficult to cause a gelation reaction, the polymer is treated with a polymer adjusted to an appropriate viscosity in the absence of a solvent or in the presence of one or more polymerizable vinyl monomers. The above polymer and alkyl hypohalide or N-HA can be reacted by mechanically kneading the mixture under high shear force.
Specific examples of organic acids or derivatives thereof that react in the presence of amide include acrylic acid, methacrylic acid, acrylic acid 2-
Hydroxymityl, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylolmethacrylamide or polyethylene glycoacrylate
- polyethylene glycol methacrylate.

Monoesters such as methacrylate 11 m polytetramethylene glycol, especially acrylic acid.

Methacrylic acid is preferred.

Specific examples of alkyl hypohalides or N-haloamides include alkyl hypohalides, primary alkyl hypohalites, secondary alkyl hypohalides, and tertiary alkyl hypohalides, among which stable tertiary alkyl Preferable hypohalides include monotertiary butyl hypochloride, tertiary butyl hypopromite, and tertiary amyl hypochloride.

Examples of N-haloamides having carbonic acid monoester residues include N', N-dichloroethyl urethane and N, N-dichloromethyl urethane.

N, N-dichloropropyl urethane, N, N
-chlorobutyl urethane, N,N-dichloropentyl urethane, N,N-dichlorohexyl urethane7.
N, N-dibromomethylurethane, N.

N-sifuromoethyl urethane, N, N-zig mouth moprovir urethane, N, N-di10 mogropylurethane,
N,N-sifromoptylurethane.

N, N-di10mopentyl urethane, N, N-/So I+
7'\gi/) L urethane, N, N-dichloroaliurethane, N, N-dichloroinpropyl urethane, N,
N-cyclo8θC-butyl urethane, N,
N-dichlorobenzyl urethane.

N, 14-dichlorophenyl urethane, N, N
-There are dichloromethallylurethane, but there are also other N
, N, N, N-tetrachloroethylene glycerol: 1-
N, N, N, N-tetrabromoethylene glycol biscarbamate can also be used.

Typical examples containing sulfonic acid residues include N,N-dichlorobenzenesulfonamide, N-dichlorobenzenesulfonamide, and
, N-cyfromopense/sulfonamide. Other compounds having N,N-dihalosulfonamide groups include N,N-dichloromethylsulfonamide, N,
N-dibu'7methylsno1phonamide, N,N-dichlorol'ethylsulfonamide, N,-dichlorobutylsulfonamide, N,N-cycloprobilus/
L-phonamide, N,N-dibromopropylsulfonamide, N,N-dichlorobutylsulfonamide, N,N-
Dibromobutylsulfonamide, N,N-dichloropentylsulfonamide, N,N-dibromopentylsulfonamide.

N,N-dichlorohexylsulfonamide, NlN-dibromohexylsulfonamide, N,N-dichloro-p-toluenesulfonamide, N.

N-Schiffp-toluenesulfonamide.

N, N-dichloro-o-toluenesulfonamide, N,
N-dibromo-〇-toluenesulponamide, ,N,N
-dichloro-p-chlorobenzenesulfonamide, N,
N-dibromo-p-chlorobenzenesulfonamide,
N, N-cyclop-bromobenzenesulfonamide, N.

N-dibromo-p-bromobenzenesulfonamide, N
, N-dichloro-p-iodobenzenesulfonamide,
N, N-Schiff's E-p-iodobenzenesulfonamide, and more N.

N, N, N-tetrachloro-1,5-benzenedisulfonamide, N, N, N, N-tetrabromo-1゜-bencefdisulfonamide, N, N, N,
N-tetrapromo 1,5-naphthalene disulfonamide, N, N, N', N'-tetrapromo 1,5-naphthalene disulfonamide, N, N,
N', N'-tetodichlorooxybis(benzenesulfonamide), N, N, N', N'-tetrabromo-oxybis(benzenesulfonamide), N
,N.

1 inch', N'-tetrachloro-11,lI-biphenyldisulfonamide, N, N, N', 1/tetrabromo=4.11-biphenyldisulfonamide)'',
N, N.

N, N', N', N' hexachlorol, 3
．． 5-) Lisphonamide etc. can also be used.

Also, as a substance having a carboxylic acid residue, N is used.

Examples include N-di-1''roacetamide, N,N-digumoacetamide, 1)-chlorosuccinimide, and N-p-comosuccinimide.

Examples of the polymerizable vinyl monomers used in the present invention are methyl methacrylate, ethyl methacrylate, acrylonitrile, and methacrylonitrile.

Methyl acrylate, ethyl acrylate, butyl methacrylate, cyclohexyl methacrylate.

Hexyl methacrylate, 2-ethylexyl methacrylate, lauryl methacrylate, butyl acrylate, cyclohexyl acrylate, hexyl acrylate, 2-ethylexyl acrylate.

Tridecyl methacrylate, tetrahydrofurfuryl methacrylate, dimethylamine ethyl methacrylate, diethylaminoethyl methacrylate.

Stearyl methacrylate, glycidyl methacrylate, ethyl dimethacrylate, 1,u-butyl dimethacrylate, benzyl methacrylate, 2-hydroxypropyl methacrylate, trimethylolpropane trimethacrylate,
Pentaerythritol tetramethacrylate, 1-nibutyl methacrylate, isobutyl methacrylate, 2-hydroxyethyl methacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylol triacrylate or methacrylic acid, acrylic Condensates of acids with bisphenol A diglycidyl, diisocyazole 1, epichlorohydrin, etc., styrene derivatives such as styrene, α-methylstyrene, β-methylstyrene, divinylbenzenato, vinyl acetate, vinylpyridine, acrylamide, methacrylamide, etc. There it is.

Compatibility with the polymer having a polymerizable side chain, which is the first component.One or more types are selected in consideration of the performance of the composition and the like.

As the polymerizable organic acid used in the present invention, acrylic acid and methacrylic acid are used, and when the total final composition containing the organic acid is 100 parts by weight, 11 to 80 parts by weight are used. If the amount is less than 4 parts or more than 14 parts by weight, satisfactory results in both durability and adhesion cannot be obtained.

Known organic peroxides and hydroperoxides are preferably used as the undercarriage curing catalyst for the present composition. The amount of the polymerization curing catalyst to be added per 100 parts of the composition is 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight. Addition of less than 0.005 parts by weight increases the polymerization curing time, and addition of more than 10 parts by weight usually does not produce any beneficial effects, significantly reduces shelf life, and is undesirable from the standpoint of increased costs. Specific examples of organic peroxides and hydroperoxides include ketone peroxides such as methyl ethyl ketone peroxide, hydroperoxides such as t-butyl nohydrobor oxide and cumenohydrobor oxide, and dialkyl peroxides such as dicumyl peroxide.

Sial peroxides such as acetyl peroxide,
Examples include peroxy esters such as t-butyl peroxide benzoate. In order to promote the reaction of such a radical generating agent, N,N-dimethylaniline, N.

N-dimethyltoluidine, N,N-diethylaniline,
Tertiary amine compounds such as guanidine, N,N-diisopropyl (p-toluidine), naphthinates such as cobalt, nickel, manganese, iron, iron propionate, copper ofsanoate, iron hexonate, aldehyde amine condensates, tetrahydro Many known compounds such as quinoline, vanadium compounds, acetyl ahidone, acetoacetate, and dimedone can be used alone or in combination. These reaction accelerators can be applied alone or dissolved in a suitable solvent as a primer to one or both of the adherends, or
Alternatively, the adhesive composition is divided into two parts at 10°C and a radical generator is added to one part. A reaction accelerator is added to the other, and the two are mixed together in an equal force method for use. It can also be added to the adhesive composition if the shelf life of the adhesive is not a particular problem. Further, the present adhesive composition may contain a small amount of a known conjugation inhibitor to improve its shelf life. Examples include 1 + quinones such as p-benzoquinone, hydroquinone monomethyl ether, 2゜ (phenols such as 6-di-t-butyl p-cresol + 2 + 5 polyvalents such as j-butylhydroquinone) J
Examples include nols and the like.

The present adhesive composition may contain a known silane coupling agent to improve adhesion to glass, etc., and may further include /silica, clay, carbon blank, inorganic and organic short fibers, and carbonaceous materials.

It may also contain an appropriate amount of a coloring agent or the like.

The adhesive composition of the present invention is particularly useful for bonding pieces of metal such as aluminum and iron, but also for bonding pieces of metal such as aluminum and iron.
It is also useful for bonding FRP, glass, etc.

Next, the present invention will be explained in more detail with reference to Examples.

(Example 1~U) fJo crystal-100p was placed in a three-necked flask equipped with a stirrer and a dropping funnel and dissolved in a mixture of methacrylate, methyl norate, etc. having the composition shown in Table 1. Next, t- Butyl hypochloride 362 was placed in a dropping funnel, and the polymer solution was gradually added dropwise while stirring.

The flask was cooled with water so that the reaction solution was kept below room temperature during the dropwise addition. A catalyst and a stabilizer were further added to this mixture to prepare an adhesive. Adjusted adhesive to '50jIm thickness, 1
The adhesive was placed between test pieces measuring 00xx x 25 mm (251 m width x 12.5 n + length) using paper clips and cured.

The surface of the pure aluminum piece C was previously polished with #100 abrasive paper, degreased with acetone, and coated with the primer shown in Table IK.

The test piece was left at room temperature for more than 21 hours and then tested using an I/Stron type tensile tester at a crosshead speed of 5 mm/m.

Tensile shear force was measured at room temperature of 20°C.

(Comparative Examples 1 to 5) After masticating Polymer 1009 with a roll mill, it was placed in a three-bottle flask equipped with a stirrer and a dropping funnel, and 1 of methyl keto/
The solution was adjusted to have a zero coefficient.

Methacrylic acid 1157 was added to 1-17 SoX and thoroughly stirred.Next, 36 g of t-butylhypochloride was added dropwise to a volume of t, and the polymer solution was gradually added dropwise while stirring well. The flask was cooled with water so that the reaction solution was kept below room temperature during the dropwise addition. After the dropwise addition was completed, the reaction solution was poured into a large excess of methanol to recover the modified poly. The modified polymer was repeatedly purified by dissolving it in methyl ethyl ketone and pouring it into methanol, and then air-dried to form a mixture of methyl methacrylate, methacrylic acid, 2-hydroxyethyl methacrylate, ethylene dimethacrylate, etc., with the composition shown in Table 1. Dissolve in.

Furthermore, a catalyst and stabilizer were added to create an adhesive.

Apply the prepared adhesive between 5.0mm thick, 100mm x 25mm pure aluminum pieces to a 25inch wide x 12mm glued area.
51111+l length) was held between paper clips and hardened.

The surface of the steel piece was polished with #100 abrasive paper in advance.

Degrease with acetone and apply the primer shown in Table 1.

The test piece was left at room temperature for 211 days or more and then tested with an Instron type tensile tester at a crosshead speed of 5mi/dragon.

Tensile shear force was measured at room temperature of 20°C.

The dichlorocyclopropane structure in the li-hitament was 80% and the -7 moiety was 20.

-2; Kutsutoy A' N-206 was used. Denaturation rate 1. ,'3ooo0)5;I+Heather''-Nos [Made by Marr1. Denaturation rate: 11500°・manufactured by Electrochemistry +l.
Denaturation rate l/100G.

) 5;/1-ノ [Changed Zeng 1 unit. Bisphenol A
Type epoxy resin (1', 4 mm x 25 mm
100mm't; Bani ζ-111! ,(,+nmX 2
5111MX 1001i + 8; Low yield shoes 1 volume”HP
26I1mX25mxX100su+9; Asahi Fiberglass High Modulus FRP2, 611111
X 25mm
+X 25m++mx100+am(?'E1);Nursing 6
．． The primer for Boku 7 is a butyraldehyde-aniline condensate, the primer for ``L'' 9 is a 50% methyl ethyl ketone solution of dimethylaniline: Napha/cobalt acid = 1:l, and the primer for commercially available SGA is the manufacturer's specified Ply-7-. there was.

(Set 2) Modified with the formulation of Example 1 to Wu (Table 1).

1-11 was used as an adhesive. In addition, Comparative Examples 1 to 3 are edges isolated by modifying the polymer.

An adhesive prepared with the formulation shown in Table 1 was used.

Claims (1)

[Claims] (1) Having a polymerizable side chain and serving as a polar group. A composition consisting of a polymer having a molecular weight of 500 or more having a dihalocyclopan structure and at least one kind of polymerization catalyst, containing an organic acid having a vinyl group or a methacrylic group and polymerizable with the above composition. An anaerobic adhesive composition made of (2) Having a polymerizable side chain and as a polar group. For a composition comprising a polymer having a molecular weight of 500 or more having a propane structure and at least one kind of polymerization catalyst, an organic acid having a vinyl group or a methacrylic group and capable of polymerizing with the above composition, and a vinyl monomer. An anaerobic adhesive composition (3+) in which the amount of polymerizable organic acid is 1+ to 100 when the final composition containing the organic acid is 100 parts
Claims (1) and (2) which are 80 parts by weight
Anaerobic adhesive composition (14) according to item ), wherein the polymerizable organic acid is methacrylic acid and. The anaerobic adhesive composition (5) according to claims (1) and (2), which is at least one type selected from acrylic acid; a polymerizable side chain of a polymer having a molecular weight of 500 or more; The anaerobic adhesive composition (6) according to claims (1) and (2), wherein is a methacryloylloki7 group or an acryloyloxy group; v100-11500 per unit weight of polymer having carbon-carbon unsaturated double bonds
Anaerobic adhesive composition (7) according to claims (1) and (2), preferably having a molar equivalent of 1/200 to 1/'5000. The no-rogen part of the dihalo/chloropropane structure is a polar group. The anaerobic adhesive composition (8) according to claims (1) and (2), which is at least one selected from chlorine and bromine; the amount of dihalo/chloropropane structure as a polar group; is 10% of all segments of the polymer with a molecular weight of 500 or more
The anaerobic adhesive composition according to claims (1) and (2), which is 90% preferably between 60 and 85 inches.