JPS6286073A - Adhesive composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an acrylic adhesive composition with excellent shrinkage strain and heat resistance.

[Conventional technology]

It has the advantage of having excellent chemical properties and adhesive strength because it is mainly composed of (meth)acrylic acid ester. However, it has the disadvantage of large shrinkage during curing, and when this adhesive is used to bond thin substrates such as thin metal plates, the surface of the substrate may warp or distort due to shrinkage after the adhesive cures. There is also a problem that adhesive strength is significantly reduced when the bonded base material is exposed to a high temperature atmosphere.

In addition, epoxy adhesives have little shrinkage during curing,
Adhesive distortion is less likely to occur, but in order to obtain the desired adhesive strength and fast curing speed, curing is required in a high temperature atmosphere, and like acrylic adhesives, the bonded base material must be exposed to a high temperature atmosphere. It has the disadvantage that the adhesive strength is significantly reduced when

[Problem that the invention seeks to solve]

An object of the present invention is to provide an adhesive composition that has excellent curability in a low-temperature atmosphere, has small shrinkage distortion after curing, and can be used in a low-temperature and high-temperature atmosphere.

[Means for solving problems]

The present invention provides a multilayer polymer particle component (A) in which a monomer mainly composed of an alkyl (meth)acrylate ester is graft-polymerized to an inner layer made of diene rubber or acrylic rubber as an outer layer. % and a monomer component (Bl) whose main component is (ivy) acrylic acid alkyl ester
The adhesive composition consists of a composition consisting of 20 to 95% by weight and a curing agent (C1).The diene rubber component constituting the inner layer may be composed of at least 13 of butadiene, isoprene and chloroprene, or mainly Examples include polymers obtained from monomers as components.

Monomers copolymerizable with the diene monomers constituting the diene rubber component include methyl (meth)acrylate, ethyl (meth)acrylate, globil (meth)acrylate, and (meth)acrylate. Butyl acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylate hexadecyl acid, glycidyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate,
(meth)acrylic acid-2-hydroxypropyl, (meth)acrylic acid-3-chloro-2-hydroxypropyl,
(Meth)acrylic acid alkyl esters and their derivatives such as cyanethyl (meth)acrylate; Unsaturated carboxylic acids such as (meth)acrylic acid; Unsaturated carboxylic acid amides such as (meth)acrylamide; Styrene, substituted styrene, etc. aromatic vinyl monomer; and at least one cyanated vinyl monomer such as acrylonitrile and methacrylonitrile.

The acrylic rubber component constituting the inner layer is mainly composed of an acrylic acid alkyl ester in which the alkyl group has 1 to 16 carbon atoms, a methacrylic acid alkyl ester in which the alkyl group has 4 to 16 carbon atoms, or a mixture thereof. It is a polymer obtained from monomers that

Specific examples of the alkyl group of the acrylic acid alkyl ester having 1 to 16 carbon atoms include methyl, ethyl, propyl, butyl, heptyl, hexyl, cyclohexyl, octyl, decyl, lauryl, hexadecyl, glycidyl, 2-ethylhexyl, -Hydroxyethyl, 2
-Hydroxypropyl, 3-chloro-2-hydroxypropyl, etc. Specific examples of the alkyl group of the alkyl methacrylate having 4 to 16 carbon atoms include butyl, heptyl, hexyl, octyl, lauryl, hexadecyl. , glycidyl, 2-ethylhexyl group, and the like.

Further, the above monomers can be used alone or as a mixture of two or more thereof.

Furthermore, vinyl monomers copolymerizable with the above monomers, such as cyanoalkyl (meth)acrylates such as cyanethyl merate in which the alkyl group has 3 or less carbon atoms; (meth)acrylamide; (meth)acrylic acid; At least one of aromatic vinyl monomers such as styrene and substituted styrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile can be copolymerized. The rubber polymer may be either crosslinked or uncrosslinked, but a crosslinked polymer is preferred in order to maintain the form of the inner layer polymer.

The crosslinked polymer contains 10% of the crosslinking agent relative to the monomer for the inner layer.
It can be obtained by addition polymerization in an amount of not more than % by weight. Specific examples of crosslinking agents include ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, and propylene glycol di(meth)acrylate.
Alkylene glycol di(meth)acrylate such as meth)acrylate; polyvinylbenzene such as divinylbenzene, trivinylbenzene, etc. can be mentioned.In the above inner layer, a monomer mainly composed of an alkyl (meth)acrylic acid ester as an outer layer. To graft polymerize the
Examples include a method using a polymerization initiator having a grafting ability, or a method in which the inner layer is polymerized in the presence of a graft cross-over side, and then the outer layer is graft-bonded when polymerized. In order to control the amount of grafting, it is preferable to use the latter graft cross-agent, especially when producing acrylic rubber. Specific examples of graft cross-agents include allyl, methallyl or crotyl esters of α,β-unsaturated (di)carboxylic acids, triallyl cyanurate, triallyl isocyanurate, etc., preferably (meth) Allyl esters of acrylic acid, maleic acid or fumaric acid are particularly preferably used, allyl methacrylate. The amount of grafting agent added is 0.01 to the monomer for the inner layer of acrylic rubber.
~5% by weight. The inner layer used in the present invention does not have to be just one layer (it may have a multilayer structure of two or more layers).In this case, each layer constituting the inner layer must be graft-bonded. As the cross-agent, a graft cross-agent constituting the acrylic rubber can be used.

Each layer may be a cross-linked or non-cross-linked polymer, and to obtain a cross-linked structure, the above-mentioned cross-linking agents may be used.

In addition, the content of the inner layer in the multilayer polymer particle component report is preferably 5 to 80% by weight, particularly preferably 10 to 70% by weight, and if it is less than 5% by weight, the adhesive strength when used as the adhesive is is on the decline. Moreover, if it exceeds 80% by weight, the dispersibility in the monomer component (Bl) mainly composed of (meth)acrylic acid ester tends to decrease, which may cause problems in adhesive coating properties.

The multilayer polymer particle component (the polymer constituting the outer layer in Al is a monomer mainly composed of (meth)acrylic acid alkyl ester (dispersion solubility with Bl and hardening of the adhesive composition of the present invention) It contributes to the compatibility between the multilayer polymer particle component (Al) and the above-mentioned monomer component (Bl).

The monomer constituting the outer layer in the multilayer polymer particle component CAl is a monomer containing (meth)acrylic acid alkyl ester as a main component. The (meth)acrylic acid alkyl ester mentioned here is a (meth)acrylic acid alkyl ester monomer having a linear, branched, and alicyclic, aliphatic, or aromatic side button having 1 to 16 carbon atoms. At least one can be mentioned. Specific examples of this alkyl group include methyl,
Examples include ethyl, propyl, butyl, hexyl, cyclohexyl, benzyl, phenyl, 2-ethylhexyl, 2-hydroxyethyl, 2-hydroxypropyl, octyl, tecyl, lauryl, hexadecyl groups, and the above (meth)acrylic acid Among the alkyl esters, methyl methacrylate is preferred.

Monomers other than (meth)acrylic acid alkyl esters constituting this outer layer include ethylenically unsaturated mono- and dicarboxylic acids, ethylenically unsaturated epoxy monomers, ethylenically unsaturated carboxylic acid amides, N- Examples include alkylcarboxylic acid amide, N-methylolcarboxylic acid amide, ethylenically unsaturated polycarboxylic acid, aromatic vinyl monomer, and vinyl cyanide monomer.

For example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, glutaconic acid, 3-
Methyl glutaconic acid, muconic acid, dihydromuconic acid, methylene glutaric acid, glycidyl (meth)acrylate,
Methylglycidyl/l/(meth)acrylate, allylglycidyl ether, (meth)acrylamide, N-methyl(meth)acrylamide, N-diethylacrylamide, monoamide, diamide or esteramide such as maleic acid, fumaric acid, itaconic acid, N- Methylol (meth)acrylamide.

Methyl ether, ethyl ether, 3-oxabutyl ether, 3,6-dioxamethyl ether, 3,6.
9- Etherification N- of trioxadecyl ether, N-methylol (meth)acrylamide or ethylene oxide addition product of N-methylolmaleimide, etc.
N-vinylamide such as methylol (meth)acrylamide, N-vinylacetamide, N-vinylpyrrolidone,
Styrene, an ester condensate obtained by combining hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxymethyl (meth)acrylate, etc. with succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, etc. , aromatic vinyl monomers such as substituted styrene, and vinyl cyanide monomers such as (meth)acrylonitrile.

In the present invention, the outer layer may have either a crosslinked structure or a non-crosslinked structure, and the above-mentioned crosslinking agent and grafting agent may be added in the same manner as for the inner layer. However, from the viewpoint of improving the dispersibility of the multilayer polymer particle component in the monomer component (Bl) mainly composed of an alkyl (meth)acrylate ester, it is preferable that the outer layer is a non-crosslinked structure. The outer layer needs to be graft-bonded with the inner layer, and the graft efficiency of the outer layer is preferably 5% by weight or more.If it is 5% by weight or less, the main component is (meth)acrylic acid alkyl ester. The dispersion stability of the multilayer polymer particle component (Al) in the monomer component (B), and the dispersion stability of the multilayer polymer particle component (Al and the above monomer component (Bl
The compatibility with the polymer tends to decrease, and the adhesive strength tends to decrease.

In the present invention, the outer layer in the multilayer polymer particle component At is
Depending on the purpose, commonly known chain transfer agents, such as tert
-butyl mercaptan, aee-butyl mercaptan,
The molecular weight of the outer layer can be controlled by adding an alkyl mercaptan such as lauryl mercaptan.

The multilayer polymer particle component (A) can be prepared by a conventionally known multistage sequential polymerization method, for example, in the presence of preformed polymer particles.
It can be obtained by a method of multilayer emulsion polymerization by adding subsequent monomers so as not to substantially form new polymer particles. A preferred method for producing the multilayer polymer particle component (Al) is to polymerize an aqueous dispersion consisting of all or part of the monomer capable of forming the inner layer to create a latex-like polymer liquid, and then to prepare a latex-like polymer liquid. Examples include a method in which the remainder of the polymer or the monomer capable of forming the outer layer is subjected to two-layer or multilayer sequential emulsion polymerization without substantially forming new polymers.

The polymerization catalyst used in the emulsion polymerization is a conventionally known water-soluble or oil-soluble radical polymerization initiator, such as sodium persulfate, botanical persulfate, benzoyl peroxide, lauroyl peroxide, and cumene hydroperoxide. Dosodicum formaldehyde sulfoxylate, diisoprobylbenzene hydroperoxide dosodium formaldehyde sulfoxylate, tert-butyl bar acetate sodium hydrosulfite, cumene hydroperoxide dosodium formaldehyde sulfoxylate , sodium persulfate, sodium hydrosulfite, potassium persulfate, sodium formaldehyde sulfoxylate, and the like. Although the amount of the initiator added is not particularly limited, it is usually preferably about 0.001 to 2% by weight based on the amount of monomer in each polymerization step.

Furthermore, conventionally known emulsifiers can be used, such as anionic surfactants such as aliphatic salts such as sodium oleate, alkylbenzene salts such as sodium dodecylbenzenesulfonate, and sodium alkylnaphthalenesulfonate. Or naphthalene sulfonate, naphthalene sulfonate formalin condensate, dialkyl sulfosuccinate, alkyl phosphate salt, polyoxyethylene sulfate salt, etc., and as a nonionic surfactant, polyoxyethylene lauryl ether, polyoxyethylene Polyoxyethylene alkyl or phenol ether such as phenol ether, polyoxyethylene solpitan fatty acid ester, polyoxyethylene acyl ester, oxyethylene-oxypropylene block polymer, fatty acid monoglyceride, etc., and cationic interfaces. Examples of the activator include alkyl amines such as laurylamine, quaternary ammonium salts such as alkyltrimethylammonium bromide salts, and various emulsifiers such as polyoxyethylene alkyl amines. Other examples include alkyl betaines such as lauryl betaine.

The type and amount of emulsifier to be added can be arbitrarily selected depending on the type of monomer, the particle size of the resulting polymer particles, etc., but in the present invention, anionic surfactants, especially fatty acid salts, and alkylbenzenes are used as emulsifiers. Sulfonate salts, alkylnaphthalene sulfonate salts, alkyl phosphate salts, and dialkyl sulfosuccinates are preferred, and are added in an amount of about 0.1 to 6% by weight based on the multilayer polymer (Aliit).

The emulsion polymerization temperature for obtaining the multilayer polymer particle component (Al) is not particularly limited, but is preferably in the range of 30 to 90°C.

The final average particle diameter of the multilayer polymer particle component (N) obtained by sequential emulsion polymerization is usually about 100 to 500X, preferably about 150 to 4000X.

The latex polymer obtained as described above can be obtained as a powder by a conventional coagulation method or spray drying method.

Preferably it is 10 to 60% by weight. (If the amount of N component is too small, shrinkage distortion during curing tends to occur, and if it is too large, the viscosity of the adhesive composition becomes high, which causes problems in work.

In the present invention, ((meta) which is the main component in the Bl component)
Examples of acrylic esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, and (meth)acrylate. ) lauryl acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, etc. (
meth)acrylic acid alkyl ester or derivative thereof;
Mono- or di(meth)acrylic acid esters of polyalkylene glycols such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyallene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc. Poly(meth)acrylates such as trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethanetri(meth)acrylate, and tetramethylolmethanetetra(meth)acrylate; Polyester (meth) Polyester (meth)acrylate obtained by adding acrylic acid; Epoxy (meth)acrylic L'-) obtained by adding (meth)acrylic acid to an epoxy compound;
Amide (meth)acrylate obtained by adding (meth)acrylic acid to the reaction product of polybasic acid and amino alcohol; Urethane (meth)acrylate and Examples include reactive oligomers in which one or both ends are (meth)acrylated, such as liquid NBR, liquid 5BR1, liquid polybutadiene, liquid 1,2-polybutadiene, and liquid polychloroprene.

In the present invention, the above (meth)acrylic acid esters can be used alone or in combination of two or more.

Furthermore, other types of monomers may be combined with the above-mentioned acrylic ester. Specifically, ethylenically unsaturated mono- and dicarboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, glutaconic acid, 3-methylglutaconic acid, muconic acid, dihydromuconic acid , methylenemalonic acid, citraconic acid, mesanic acid, methylglutaric acid, etc.; ethylenically unsaturated carboxylic acid amides such as (meth)acrylamide; N-alkylcarboxylic acid amides such as N-methylacrylamide, N-diethylacrylamide or maleic monoamides, diamides and esteramides of ethylenically unsaturated dicarboxylic acids such as acid, fumaric acid and itaconic acid; N-methylolcarboxylic acid amides such as N-methylol(meth)acrylamide; methyl ether, ethyl ether, 3-oxabutyl ether ,3,
6-dioxahebutyl ether and 3,6,9-t!
Etherified N-methylol (meth)acrylamide such as J oxadecyl ether, N-methylol (meth)acrylamide or ethylene oxide addition product of N-methylolmaleimide; N-vinylamide, such as N-vinylacetamide, N-vinylpyrrolidone, etc. ;
Other vinyl monomers, such as aromatic vinyl monomers such as styrene and substituted styrene, cyanated vinyl monomers such as (meth)acrylonitrile, and the like can be used.

It is 2% of the country.

The monomer (Bl) may have a polymerization stopper added thereto for the purpose of improving storage stability as the case may be.

The curing agent (C) used in the present invention includes initiators commonly used in radical polymerization, such as ketone peroxide, perester, cyanyl peroxide, dialkyl peroxide, hydroperoxide, etc.
Hydroperoxide is preferred because it has excellent adhesive strength and curing speed. The amount of the curing agent (C1) used is preferably 0.1% by weight or more based on the monomer (Bl), particularly preferably 0.5 to 10% by weight, from the viewpoint of contact strength, curing speed, etc.

Further, in the present invention, when curing is performed at a low temperature, a commonly known curing accelerator can be used in combination with the curing agent (C). Specific examples of curing accelerators include metal soaps such as cobalt naphthenate, amines such as diethyl p-toluidine, p-tolyldiethanolamine, and p-tolyldibrobanolamine, thiourea, acetylthiourea, and tetramethylthio Thioureas such as urea and ethylenethiourea; thioamides such as mercaptobenzimidazole; and the like.

The method of adding the curing accelerator is not particularly limited (
For example, a curing accelerator is added to a part of the monomer (Bl), and the remaining monomer (tBl), a curing agent (C1), and a mixture consisting of a multilayer polymer particle component (Al) are mixed and cured at the time of use. The amount of the curing accelerator added is preferably 0.01 to 15% by weight, particularly preferably 0.1 to 10% by weight, based on the monomer (Bl).

〔Example〕

The present invention will be explained below with reference to Examples.

In the examples, % and % indicate parts by weight and % by weight, respectively.

Various evaluation methods for bacteria were performed using the methods shown below.

1) Tensile shear strength of adhesive Measured according to JIS K-6850.

The material to be bonded is steel (JIS G-4051 S
-10C), and the adhesive surface was JIS R-6252 (
Polish with No. 240 abrasive paper until it has a metallic luster, JIS
The material was thoroughly washed with K-1508 (trichlorethylene) and dried.

The testing machine used was Tensilon Model 3 (manufactured by Toyo Baldwin Co., Ltd.), which had a capacity of 15 to 85% of the capacity of the testing machine, and the loading rate was 500 kgf per minute or less.

2) Impact strength Measured according to JIS K-6855.

The above-mentioned steel material was used as the material to be bonded.

The test machine has a capacity of 30 ports and 300 k! 9 brocade, 900k
A gα pendulum impact tester was used.

3) Peel strength Measured according to JIS K-6854.

The above-mentioned steel material was used as the material to be bonded.

Measurements were made using the T-peel method, and the test machine was operated at a cutting rate of 50 ± 5 mrx per minute.

+) 300°C heat treatment Tensile shear strength After holding the adherend in a 300°C constant temperature heater for 3 hours and cooling to room temperature, JIS K-6 as shown in 1) above.
Measured according to 850.

5) Adhesive Distortion After applying an adhesive composition to the entire adhesive surface of the steel material of a door with a thickness of 1 mm, a width of 50 mm, and a length of 550 mm, the adhesive surface of another steel material similar to the above was bonded and cured. Next, after holding at room temperature for one day, the amount of strain in the longitudinal direction was measured on a horizontal plate. That is, one side of the steel material was brought into contact with the plate, and the height of warpage (h) mm of the other side on the plate was determined. (55o x 100
<%) was taken as the adhesive strain. ) 6) Measurement of grafting efficiency: Accurately weigh 2 Pr of the obtained multilayer polymer particle component (Al),
After dispersing and dissolving in 100-methyl ethyl ketone, the mixture was heated under reflux at 75°C for 24 hours. After refluxing, cool to room temperature, filter the insoluble matter through a glass filter, concentrate the filtrate, reprecipitate with hexane, collect the polymer component, dry it, and precisely weigh it (Wl).
Shita.

Multilayer polymer particle component of outer layer monomer component (A12 J'r
The amount inside is W. Then, the grafting efficiency was calculated from the following formula.

Example 1 250 parts of ion-exchanged water, 2 parts of sodium salt of sulfosuccinic acid dioctyl ester, and 0.05 part of sodium aldehyde sulfoxylate were added to a polymerization container equipped with a cooler, and after stirring under a nitrogen atmosphere, A mixture consisting of 5 parts of methyl methacrylate, 35 parts of butyl acrylate, 1 part of 1,3-butylene dimethacrylate, 0.3 part of allyl methacrylate and 0.05 part of cumene hydroperoxide was added. Next, the temperature was raised to 70° C. without stirring, and the reaction was continued for 60 minutes to form a multilayer polymer particle component (an inner layer of Al).

Subsequently, in the presence of the inner layer, a mixture consisting of 56 parts of methyl methacrylate, 1 part of methacrylic acid, 3 parts of butyl acrylate, 0.3 part of n-octyl mercaptan and 0.05 part of cumene hydroperoxide is added over 60 minutes, The polymerization was completed by stirring for an additional 60 minutes to obtain a multilayer polymer particle component (Al) in the form of a latex.The average particle diameter of the polymer (Al) was 2000A.

This latex was salted out using 5% calcium chloride based on the solid content of the polymer, thoroughly washed with water and dried.

The grafting efficiency of this multilayer polymer particle component (Al) was measured and was 45%.

The thus obtained multilayer polymer particle component (A140
55 parts of methyl methacrylate and 1 carbon number of the alkyl group
Acryester SL (manufactured by Mitsubishi Rayon Co., Ltd.), which is a 1:1 mixture of methacrylic acid alkyl ester of No. 2 and methacrylic acid alkyl ester of which the alkyl group has 13 carbon atoms.
A dispersion liquid P) was prepared by mixing 5 parts of Composition (1) was prepared by adding and dissolving 10 parts of methacrylic acid and 6 parts of benzoyl peroxide to 100 parts of this dispersion (a).

A composition (b) was prepared by adding and dissolving 8 parts of p-)lyldiethanolamine to 100 parts of the above solution (a).

Next, approximately equal weights of the compositions (1) and (1) were separately applied to two adherends, and the two were overlapped and fixed with clips, and cured and bonded about 15 minutes after application. After the adhesive was left at room temperature for 24 hours, the adhesiveness was evaluated.

The results obtained are shown in Table-1.

Example 2 In a 401-volume autoclave, 101 parts of water, 0.4 kg of Diplozin-25 (manufactured by Toho Chemical Industry Co., Ltd.), 0.2 kg of Nonsal TK-1 (manufactured by Nippon Oil & Fats Co., Ltd.), and cyinbropyrpenzene Baroxide 0.025! ? , sodium birophosphate 0.02 hours, dextrose 0.04 hours
kl? , tart-dodecyl mercaptan 0.05 k
10 kg of 9- and 1,3-butadiene monomers were added to 0.03 g of sodium sulfate, and the mixture was heated and stirred at 70° C. for 10 hours. A latex liquid with a reaction conversion rate of 99% was obtained. This was used as an inner layer polymer. After adding 100 parts of this latex (polybutadiene solid content 50%) into a separately prepared polymerization vessel equipped with a cooler, 100 parts of ion-exchanged water were added, followed by 1 part of dioctyl ester soda salt of sulfosuccinic acid and 1 part of sulfosuccinic acid dioctyl ester soda salt and After adding 0.05 part of xylene and stirring under nitrogen atmosphere,
The temperature was raised to 0°C.

Subsequently, a mixed solution consisting of 47 parts of methyl methacrylate, 3 parts of butyl acrylate, 0.3 parts of n-octyl mercaptan, and 0.05 parts of cumene hydroperoxide was added over a period of 60 minutes, and maintained for an additional 60 minutes. Polymerization was completed. This layer was used as the outer layer. The final particle size was 3000A.

The grafting efficiency of this outer layer was 65%.

The polymer latex obtained in this way was converted into polymer 10
After coagulating with 10 parts of concentrated sulfuric acid to obtain a polymer component, the multilayer polymer particle component (Al
I got it.

An adhesive composition was prepared in the same manner as in Example 1 except that the above polymer component (Al) was used, and adhesion was evaluated.

The obtained results are summarized in Table-1.

Example 3 250 parts of ion-exchanged water, 3 parts of sodium salt of dioctyl sulfosuccinate, and 0.05 part of indium formaldehyde sulfoxylate were added to a polymerization vessel equipped with a cooler, and after stirring under nitrogen atmosphere, methyl methacrylate was added. 3
A mixture of 32 parts of butyl acrylate, 0.8 parts of 1,3-butylene dimethacrylate, 0.3 parts of allyl methacrylate and 0.05 parts of cumene hydroperoxide was added. Next, the reaction was continued for 60 minutes after raising the temperature to 70°C at () to form the first inner layer of the multilayer polymer (At. Butyl 8 parts, allyl methacrylate 0.1
and 0.02 parts of cumene hydroperoxide were added over 30 minutes, and the mixture was stirred and maintained for an additional 30 minutes to complete polymerization and form the second inner layer. Subsequently, in the presence of the second inner layer, a mixture consisting of 8 parts of methyl methacrylate, 2 parts of butyl acrylate, 0.1 part of allyl methacrylate, and 0.02 parts of cumene hydroperoxide was added with vinegar over 30 minutes, and the mixture was heated for another 30 minutes. Polymerization was carried out while stirring to form a multilayer polymer particle component (inner layer of Al) consisting of three layers.

Subsequently, in the presence of the inner layer, 42 parts of methyl methacrylate, 3 parts of butyl acrylate, and 0 parts of n-octyl mercaptan were added.
．． A mixture consisting of 3 parts of cumene hydroperoxide and 0.05 parts of cumene hydroperoxide was added over 60 minutes, and the polymerization was completed by holding for an additional 60 minutes to obtain a polymer (AI latex). was 4000i.

This latex was salted out with 5% calcium chloride, washed with water, and then dried. The grafting efficiency (including this polymer) was 37%.

60 parts of this multilayer polymer (A), 3 parts of methyl methacrylate
A mixed dispersion consisting of 7 parts and 3 parts of Acryester SL (
b) was adjusted. Composition (1) was prepared by adding and dissolving 10 parts of methacrylic acid and 6 parts of tert-butyl hydroperoxide to 1100 parts of the dispersion ((1).

Further, a composition (n) was prepared by adding and dissolving 8 parts of p-tolylgetanolamine in 100 parts of the above solution (a).

The above compositions (1) and ([1) were evaluated in the same manner as in Example 1, and the results are summarized in Table 1.

Example 4 In a 40 J autoclave, 101 ml of water was added. Diplozin - 25o, 3 - 9, Nonsal TK-10, 4kli
,') Isopropylbenzene hydroperoxide 0.0
24X? , 0.02 kg of sodium pyrophosphate, 0.04 kg of dextrose, 0.05 kg of tart-dodecyl mercaptan, 0.03 kg of sodium sulfate, 9 kg of butadiene, and 1 cup of styrene were added, and the mixture was heated and stirred at 70°C for 10 hours. . Inner layer 1 with reaction conversion rate of 99%
A step polymer was obtained in the form of latex (solid content 50%).

Then, in a polymerization container equipped with a cooler, 80 parts of the latex,
80 parts of ion-exchanged water, 0.8 part of sodium salt of dioctyl sulfosuccinate, and 0.04 part of sodium formaldehyde sulfoxylate were added, and after stirring under nitrogen atmosphere, the temperature was raised to 70°C, and methyl methacrylate was added. 2 parts, butyl acrylate 8 parts, allyl methacrylate 0.1
and 0.02 parts of cumene hydroperoxide were added over 30 minutes, and the mixture was stirred and maintained for 30 minutes to polymerize the second stage of the inner layer, thereby creating an inner layer within the multilayer polymer particle component.

Then, in the presence of the inner layer, methyl methacrylate 4
A mixture consisting of 8 parts of butyl acrylate, 2 parts of n-octyl mercaptan, 0.3 parts of n-octyl mercaptan, and 0.04 parts of cumene hydroperoxide was added over 60 minutes, and the mixture was stirred and maintained for an additional 60 minutes to complete the polymerization. In this way, a latex within the multilayer polymer particle component was obtained. The average particle size of this latex was 800A. This latex was salted out in the same manner as in Example 1 to obtain a multilayer polymer [A]. The grafting efficiency of this multilayer polymer (Al) was 83%.

An adhesive composition was prepared and evaluated in the same manner as in Example 1 except that the above multilayer polymer matrix was used.

The results are summarized in Table-1.

Example 5 Emulsion polymerization of butadiene monomer was carried out in the same manner as in Example 2,
An inner layer polymer latex was obtained. Latex was charged so that the resulting butadiene polymer was 70 parts, 30 parts of methyl methacrylate, 0.2 parts of n-octyl mercaptan,
A mixture consisting of 0.05 parts of cumene hydroperoxide was added over a period of 60 minutes and held for 60 minutes to complete the polymerization. This layer was used as the outer layer. The final particle size was 4000A. The grafting efficiency of this outer layer was 85%.

Polymer latex polymer 10 obtained in this way
A polymer component was obtained by aggregation using 10 parts of concentrated sulfuric acid per 0 parts, and then washed and dried to obtain a multilayer polymer particle component.

An adhesive composition was prepared in the same manner as in Example 1 except that the above polymer component (Al) was used, and adhesion was evaluated.

The obtained results are summarized in Table-1.

Example 6 Into a polymerization vessel equipped with a cooler, 250 parts of ion-exchanged water, 3 parts of dioctyl sulfosuccinate IJium salt, and 0.05 part of sodium formaldehyde sulfoxylate were added, and after stirring under nitrogen atmosphere. , 2 parts of methyl methacrylate, 48 parts of butyl acrylate, 2 parts of 1,3-butylene dimethacrylate, 0.7 part of allyl methacrylate, and 0.07 part of cumene hydroperoxide were added, and the temperature was raised to 70°C. The reaction was continued for another 60 minutes to form the first layer within the multilayer polymer. Subsequently, in the presence of the first inner layer, a mixture consisting of 1 part of methyl methacrylate, 4 parts of butyl acrylate, 0.1 part of allyl methacrylate, and 0.02 part of cumene hydroperoxide was added over 15 minutes, The mixture was stirred and maintained for an additional 15 minutes to complete polymerization and form a second inner layer. Subsequently, in the presence of the second inner layer, a mixture consisting of 5 parts of methyl methacrylate, 5 parts of butyl acrylate, 0.1 part of 7-bylyl methacrylate, and 0.02 part of cumene hydroperoxide was added over a period of 30 minutes; The polymerization was completed by stirring and holding for a minute, and the third inner layer was formed. Subsequently, in the presence of the third inner layer, a mixture consisting of 4 parts of methyl methacrylate, 1 part of butyl acrylate, 0.1 part of allyl methacrylate, and 0.02 part of hicumene hydroperoxide was added over 15 minutes, and then for another 15 minutes. The polymerization was completed by stirring and holding, and a fourth inner layer was formed, and a multilayer polymer particle component (an inner layer of Al) consisting of four layers was formed.

Subsequently, in the presence of the inner layer, 30 parts of methyl methacrylate, n
~ A mixture consisting of 0.2 parts of octyl mercaptan and 0.03 parts of cumene hydroperoxide was added over 60 minutes and held for an additional 60 minutes to complete the polymerization.
A latex of At was obtained. The average particle diameter of the polymer (A) was 1,000 yen.

This latex was salted out with 5% calcium chloride, washed with water, and then dried. The grafting efficiency of this polymer (Al) was 70%.

Using the thus obtained multilayer polymer (At), an adhesive composition was prepared in the same manner as in Example 1 at °C, and its adhesion was evaluated.

The obtained results are summarized in Table-1.

Example 7 250 parts of ion-exchanged water, 3 parts of sodium salt of dioctyl sulfosuccinate, and 0.05 part of sodium formaldehyde sulfoxylate were added to a polymerization vessel equipped with a cooler, and after stirring under a nitrogen atmosphere, methyl methacrylate was added. 5 parts of allyl methacrylate, 0.1 part of allyl methacrylate and 0.05 part of cumene hydroperoxide. then 7
After raising the temperature to 0°C, the reaction was continued for 60 minutes to form a multilayer polymer (A
The first inner layer of 1 was formed. Subsequently, in the presence of the first inner layer, a mixture consisting of 25 parts of butyl acrylate, 1 part of 1,3-butylene dimethacrylate, 0.2 part of allyl methacrylate and 0.05 part of cumene hydroperoxide was added for 60 minutes. The polymerization was completed by further holding for 60 minutes, and a second inner layer was formed. Subsequently, in the presence of the second inner layer, a mixture consisting of 6 parts of methyl methacrylate, 4 parts of butyl acrylate, 0.1 part of allyl methacrylate, and 0.05 part of hicumene hydroperoxide was added over 30 minutes. Then, the mixture was stirred and held for an additional 30 minutes for polymerization to form a multilayer polymer particle component consisting of three layers (an inner layer of Al).

Subsequently, in the presence of an inner layer, 55 parts of methyl methacrylate, 5 parts of butyl acrylate, and 0.3 parts of n-octyl mercaptan were added.
A mixture of 0.05 parts of cumene hydroperoxide and 0.05 parts of cumene hydroperoxide was added over 60 minutes and maintained for an additional 60 minutes to complete the polymerization to obtain a polymer (Al latex). It was 1200A.

This latex was salted out with 5% calcium chloride, washed with water, and then dried. The grafting efficiency of this polymer (At) was 80%.

An adhesive composition was prepared in the same manner as in Example 1 using the thus obtained multilayer single unit (Al), and the adhesion was evaluated.

The obtained results are summarized in Table-1.

Comparative Example 1 95 parts of methyl methacrylate, methacrylic acid alkyl ester with 12 carbon atoms in the alkyl group, and 1 carbon number in the alkyl group
5 parts of Acryester SL (manufactured by Mitsubishi Rayon Co., Ltd.), which is a 1=1 mixture of the methacrylic alkyl esters of No. 3, were mixed to prepare a mixed solution a). This mixed solution ((11
A composition (1) was prepared by adding and dissolving 10 parts of methacrylic acid and 6 parts of benzoyl peroxide to 00 parts.

A composition (■) was prepared by adding and dissolving 8 parts of p-tolylgetanolamine in 100 parts of the above mixed solution (A).

It was bonded to a steel adhesive base material in the same manner as in Example 1, but
The viscosity tended to be too low.

The adhesive performance evaluation results are summarized in Table-1.

Comparative Example 2 250 parts of ion-exchanged water, 2 parts of sodium salt of sulfosuccinic acid dioctyl ester, and 0.05 part of indium sulfoxylate were added to a polymerization container equipped with a cooler, and after stirring under a nitrogen atmosphere, The temperature was raised to ℃.

After the system temperature reaches 70℃, methyl methacrylate 60
1 part of butyl acrylate, 0.3 part of n-octyl mercaptan, and 0.1 part of cumene hydroperoxide were added at 0.degree. C. over 120 minutes, and the polymerization was completed by stirring for 120 minutes.

This latex was salted out using 5% calcium chloride based on the polymer, thoroughly washed with water and dried.

The thus obtained copolymer of methyl methacrylate/butyl acrylate = 60/40 was used in place of the polymer particle component (Al) of Example 1 to prepare an adhesive composition, and the adhesion was evaluated. .

The obtained results are summarized in Table-1.

Table 1 [Effects of the Invention] As described above, the adhesive composition of the present invention has excellent low-temperature curability, small shrinkage distortion after curing, and excellent heat resistance, and is effective against deafness, deafness, It can exhibit excellent effects in a variety of fields, such as personal training.

Claims (1)

[Claims] 1. 5 to 80% by weight of a multilayer polymer particle component (A) in which a monomer mainly composed of (meth)acrylic acid alkyl ester is graft-polymerized to an inner layer made of diene rubber or acrylic rubber as an outer layer. Monomer component (B) mainly composed of (meth)acrylic acid alkyl ester 20-95
An adhesive composition consisting of a composition consisting of % by weight and a curing agent (C).