JPS63165418A - Adhesive composition - Google Patents

Abstract

PURPOSE:To provide the titled photocurable anaerobic adhesive of high cure rate leading to high productivity, outstanding in bond strength, comprising a special modified urethane prepolymer, acrylic ester compound, organic peroxide and photopolymerization initiator. CONSTITUTION:The objective adhesive can be obtained by blending (A) a (meth) acryloyloxy-contg. polycarbonatediol-modified urethane prepolymer prepared by reaction between (i) a OH group-contg. (meth)acrylate, (ii) an organic polyisocyanate and (iii) a polycarbonatediol and/or (B) a second (meth) acryloyloxy-contg. polycarbonatediol-modified urethane prepolymer prepared by reaction between the components (i)-(iii) and (iv) a polyol, (C) a (meth) acrylic ester compound other than the component (i) [pref., 2-hydroxyethyl (meth)acrylate], (D) an organic peroxide, and (E) a photopolymerization initiator.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is a photocurable anaerobic film used for adhering metal parts, sealing, preventing loosening of fastening materials such as bolts, or fixing fitting parts. The present invention relates to adhesive compositions.

[Background of the invention]

A photocurable anaerobic adhesive composition does not cure and is stable for a long period of time when it is in contact with air or oxygen and is shielded from light. It is a curable adhesive composition that has the property of blocking and being easily polymerized and cured by irradiation with light, typically ultraviolet light.

This type of adhesive composition must cure quickly under anaerobic conditions or under light irradiation.

Needless to say, high impact strength and peel adhesion strength are required.

[Conventional technology]

Conventionally known adhesive compositions of this type are compositions containing a radically polymerizable (meth)acrylic acid ester monomer as a main component, an organic peroxide as a polymerization initiator, and a photopolymerization initiator. It is a combination of.

Such adhesive compositions are prohibited from polymerizing under aerobic conditions when in contact with oxygen, but when used, they can be applied to the surfaces of two parts to be bonded and sandwiched between them to block air. If placed under anaerobic conditions, polymerization will begin, and the outer periphery in contact with oxygen will be cured by irradiation with ultraviolet rays.

[Problem that the invention seeks to solve]

However, the above-mentioned conventional adhesive compositions have a problem in that the physical properties after curing are hard and brittle, making it impossible to obtain sufficient impact strength and peel adhesive strength.

In order to improve the hard and brittle physical properties of the cured product of the above-mentioned adhesive composition, adhesive compositions that give a cured product with some flexibility have been conventionally provided, but curing under anaerobic conditions or under light irradiation has been proposed. The slow speed is a major problem in practical application [Means for solving the problem] As a means to solve the above problem, the present invention provides a method for solving the above problem by combining a (meth)acrylate (A) having a hydroxyl group and an organic polyisocyanate (B). ) and a polycarbonate diol-modified urethane prepolymer (1) having a (meth)acryloyloxy' group, which is a reaction product with polycarbonate diol (C).
) and/or (meth)acrylate (A) having a hydroxyl group, an organic polyisocyanate (B), and a polycarbonate diol (C).

A polycarbonate diol-modified urethane prepolymer having (meth)acryloyloxy groups which is a reaction product with polyol (D) (one or more types of Ill and the above-mentioned polycarbonate diol-modified urethane prepolymer having (meth)acryloyloxy groups) One or more (meth)acrylic acid ester compounds (111) other than (1) and (II), and organic peroxide (T
V) and a photopolymerization initiator [V].

The above (meth)acrylate (A) is a general term for acrylate and methacrylate, and the above polycarbonate diol-modified urethane prepolymer (13 is a general term for a polycarbonate diol-modified urethane prepolymer having a (meth)acryloyloxy group, and (
Meth)acrylic acid ester compound (ml refers to (meth)acrylic acid ester compounds (1) to (11) described later)
One or more (meth)acrylic acid ester compounds selected from the group consisting of:

The details of each component constituting the adhesive composition of the present invention will be explained below.

Polycarbonate diol-modified urethane prepolymer [I]> The above urethane prepolymer (1) is composed of a (meth)acrylate (A) having a hydroxyl group and an organic polyisocyanate (B).
) and polycarbonate diol (C).

Specific examples of the above synthetic raw materials (A), (B), and (c) are as follows.

[(Meth)acrylate (A) having a hydroxyl group] Specific examples of (meth)acrylate (A) having a hydroxyl group are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate. , hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, 2
-Hydroxy-3-phenoxypropyl (meth)acrylate, and 2-hydroxy-3-chloropropyl (
(meth)acrylate, etc.

[Organic polyisocyanate (B)]

Specific examples of the organic polyisocyanate (B) include toluene diisocyanate, 4.4'-diphenyl diisocyanate, 4.4'-diphenylmethane diisocyanate, cyanidine diisocyanate, 1°5-naphthalene diisocyanate, 4.4'-diphenyl ether diisocyanate, p- Butylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, ethylene diisocyanate, cyclohexylene diisocyanate, nonamethylene diisocyanate, octadecamethylene diisocyanate, 2-chloropropane diisocyanate, 2.
Low molecular weight organic polyisocyanates, such as 2'-diethyl ether diisocyanate, tetrachlorophenylene diisocyanate, xylene diisocyanate, and 1,4°3-heptene diisocyanate, can be used in excess amounts of these low molecular weight organic polyisocyanates, as is already known. Primary amines, secondary amines, or polyhydric alcohols such as glycerol, polyoxyethylene triol, polyoxypropylene triol, polyoxyethylene tetraol, polyoxypropylene tetraol, polypropylene glycol, polyethylene glycol, polycaprolactone, etc. There are high molecular weight organic polyisocyanates obtained by reacting polyhydric alcohols such as polyols, polytetramethylene ether glycol, and ether-type glycols obtained by adding ethylene oxide and/or propylene oxide to bisphenol A.

Particularly suitable organic polyisocyanates in the present invention are toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and hexamethylene diisocyanate.

[Polycarbonate diol (C)]

The polycarbonate diol has a C2, to C12 alkylene group, and/or a C1 to C22 alkyl group, and/or a C6 to C2□ aromatic hydrocarbon group, and/or a C6 to C72 cycloparaffinic hydrocarbon group. a carbonate ester having and a C2 to C22 alkylene group,
and/or a diol having a C1 to C72 alkyl group, and/or a CG-C2□ aromatic hydrocarbon group, and/or a C6 to C2, cycloparaffinic hydrocarbon group.

A specific example of carbonate ester is ethylene carbonate.

Dimethyl carbonate, diethyl carbonate.

Examples include diphenyl carbonate and dicyclohexyl carbonate.

Further, specific examples of the diol are 1,6-hexanediol and 1,4-cyclohexane dimetatool.

Examples include 3-methyl 1,5-bentanediol, 1,5-bentanediol, polyoxyethylene diol, polyoxypropylene diol, polyoxybutylene diol, polycaprolactone diol, trimethylhexane diol, and 1,4-butane diol. It will be done.

A particularly suitable method for producing the polycarbonate diol-modified urethane prepolymer (1) of the present invention is to combine a predetermined amount of organic polyisocyanate CB) and polycarbonate diol (C).
First, a polycarbonate diol-modified urethane prepolymer (E) containing unreacted isocyanate is produced by reacting the urethane prepolymer (E).
and (meth)acrylate (A) having a predetermined amount of hydroxyl groups.
This is a method of reacting with

(A) + (B) = (E) → (E) +
(A) = (I) Polycarbonate diol modified urethane prepolymer (1) Reaction temperature during IT production was 120°C
It is desirable that the temperature is as follows: If the reaction temperature is too high, it will increase the viscosity of the reaction product or cause gelation during the reaction.6 If the reaction temperature is too low, the viscosity of the reactant will increase, and unreacted raw materials This is because the dispersion and mixing of the substances become insufficient, making it difficult to achieve a smooth reaction.

The synthesis of polycarbonate diol-modified urethane prepolymer (13) is preferably carried out at 50°C to 120°C, more preferably at 55°C to 100°C.
GO is involved and involves its consumption, and the group -NGO
When analyzed by infrared absorption spectrum, it is 2250an''''
Because it exhibits strong absorption near 1, the progress of the 1 reaction can be easily confirmed by conducting infrared absorption spectrum analysis of the -NGO group in the reactant and tracking its consumption from changes in the intensity of the absorption characteristics. The end point of each reaction step can be set at the point when the group -NGO is consumed and the consumption of the group -NGO stops.Also, as a catalyst to make one reaction proceed smoothly, tertiary amines such as triethylenediamine, dibutyltin dilaurate, etc. For adjusting the reaction rate, the latter dibutyltin dilaurate is preferred, and its addition rate is preferably 50 to 2000 ppm per 100 parts by weight of the reactant. Preferably 100 to 1500 parts by weight per 100 parts by weight of the reactant.
It is ppm. In addition, hydroquinone monomethyl ether, phenothiazine, etc. may be added as radical polymerization inhibitors depending on the reaction conditions. Furthermore, if the viscosity of the reactant becomes too high, activated water such as toluene or acetone may be added. Organic solvents containing no active hydrogen groups or (meth)acrylates containing no active hydrogen groups may be used as reaction diluents.

Polycarbonate diol-modified urethane prepolymer [■]> The above urethane prepolymer [11] has a hydroxyl group (
It is a reaction product of meth)acrylate (A), organic polyisocyanate (B), polycarbonate diol (C), and polyol (D).

The synthetic raw materials (A), (B), and (C) are the same as the urethane prepolymer [I], and specific examples of the polyol (D) are as follows.

[Polyol (D)]

Specific examples of polyol (D) include 1,6 diol.
-hexanediol, 1,4-cyclohexane dimetatool, 3-methyl-1,5-bentanediol, 1,5
- Bentanediol, polyoxyethylene diol, polyoxypropylene diol, polyoxybutylene diol, polycaprolactone diol, trimethylhexane diol, and 1,4-butane diol, etc.
Further, trivalent or higher polyols include trimethylolethane, pentaerythritol, trimethylolpropane,
Examples include polyoxyethylene triol, polyoxypropylene triol, trishydroxyethyl isocyanurate, polyoxyethylene tetraol, polyoxypropylene tetraol, glycerin, and polyphosphoric acid.

A particularly suitable method for preparing the polycarbonate diol-modified urethane prepolymer (Tll) of the present invention is to combine a predetermined amount of an organic polyisocyanate (B) with a polycarbonate diol (C
) to produce a polycarbonate diol-modified urethane prepolymer (E) having unreacted isocyanate groups, and then react with the urethane prepolymer (E).
) and (meth)acrylate (A
) with unreacted isocyanate groups (
This is a method of producing a meth)acryloyloxy compound (F) and further reacting the (meth)acryloyloxy compound with a predetermined amount of polyol (D).

(A) + (B) = (E) → (E) ÷ (A) = (F)
→ (F) ÷ (D) = (II)
The reaction conditions in the above production method are urethane prepolymer (1
).

<(Meth)acrylic acid ester compound [■]> Above (
The meth)acrylic ester compound (nt) refers to a (meth)acrylic ester compound other than the above urethane prepolymer (1) and (T[). 1. The cohesive force and interfacial adhesive force of the adhesive of the present invention. It improves the
For example, the following (meth)acrylic acid ester compound (1
) to (11), one or more (meth)acrylic acid ester compounds may be used.

[(Meth)acrylic acid ester compound (1)] The (meth)acrylic acid ester compound (1) has the following general formula.

R,0 CH, = C-C-OR.

In the formula, R1 is hydrogen or -CM, and R2 is a substituted alkyl group in which one or more hydrogen atoms at any position of a straight chain or branched alkyl group having 2 to 4 carbon atoms are substituted with 10H and/or a halogen. Indicates the group.

The above (meth)acrylate (1) is specifically 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

1.2-dihydroxyethyl (meth)acrylate, 3
-Chloro-2-hydroxypropyl (meth)acrylate and the like.

[(Meth)acrylic acid ester compound (2)] The (meth)acrylic acid ester compound (2) has the following general formula.

In the formula, R3 is hydrogen or 10H, and R4 is hydrogen.

-CH,, -C,H,, -CH,OH, or -CH,
-0-C-C= CH,, Rs is hydrogen, chlorine, -CH5
or 10, H,, R6 is hydrogen.

-0H1 or -CH, -0-C-C: CH.

, m is an integer of 1 to 8, n is an integer of 1 to 20, and p is 0 or 1.

Specifically, the above (meth)acrylate (2) is diethylene glycol di(meth)acrylate.

Triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,2
-Propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, diglycerol di(meth)acrylate, glycerin tri(meth)acrylate
Acrylate, trimethylolpropane tri(meth)
Examples include acrylate, di-glycerol tetra(meth)acrylate, and the like.

[(Meth)acrylic acid ester compound (3)] The (meth)acrylic acid ester compound (3) has the following general formula.

In the formula, R7 is hydrogen or -CH, R1 is hydrogen or a straight chain or branched alkyl group having 1 to 4 carbon atoms, and R1 is C
2 to C4 linear or branched alkylene group, m is 1
Indicates an integer between ~10.

Specifically, the above (meth)acrylate (3) is 2.2
-Bis(4-methacryloxyjethoxyphenyl)propane, 2,2-bis(4-allyloxyjethoxyphenyl)propane, 2,2-bis(4-methacryloxytriethoxyphenyl)propane, 2,2-bis (4-Acryloxypentaethoxyphenyl)propane, 2-2bis(4-methacryloxyhexaethoxyphenyl)propane, 2,2-bis(4-acryloxyhexaethoxyphenyl)propane, 2,2-bis(4- methacryloxyoctaethoxyphenyl)propane, 2,2-bis(
4-Acryloxydipropoxyphenyl)propane, 2
, 2-bis(4-methacryloxytripropoxyphenyl)propane, 2゜2-bis(4-acryloxydibutoxyphenyl)propane, 2,2-bis(4-methacryloxyoctabutodixyphenyl)propane, 2 -(4
-methacryloxyjethoxyphenyl)-2-(4-methacryloxytriethoxyphenyl)propane, 2-
(4-acryloxydipropoxyphenyl)-2-(4
-acryloxytriethoxyphenyl)propane, etc.

[(Meth)acrylic acid ester compound (4)] The (meth)acrylic acid ester compound (4) has the following general formula.

In the formula R,. represents hydrogen or -CH, R11 represents hydrogen or a straight chain or branched alkyl group having 1 to 4 carbon atoms, and n
represents O or an integer from 1 to 10.

Specifically, the above (meth)acrylate (4) is dicyclopentenyl (meth)acrylate, dicyclopentenyloxymethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyloxyprobyl (meth)acrylate, ) acrylate, etc.

[(Meth)acrylic acid ester compound (5)] The (meth)acrylic acid ester compound (5) has the following general formula.

oO 1M CH,=C-C-0R13 In the formula, R12 is hydrogen or -CH, R13 is hydrogen or a straight chain or branched alkyl group having 1 to 18 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, phenyl group, a tetrahydrofurfuryl group, or a straight-chain or branched alkyl group having 5 to 20 carbon atoms.

Specifically, the above (meth)acrylate (5) is methacrylic acid, acrylic acid, methyl (meth)acrylate, cyclohexyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.

2-ethylhexyl (meth)acrylate, phenyl (
Examples include meth)acrylate and benzyl(meth)acrylate.

[(Meth)acrylic acid ester compound (6)] The (meth)acrylic acid ester compound (6) has the following general formula.

R,,O I CHz =C-C-0-R1m-0-R□In the formula, R1 is hydrogen or -CH3,R,, is any position of a straight chain or branched alkyl group having 3 or 4 carbon atoms A substituted alkylene group in which hydrogen is replaced with -OH, R1, represents a straight chain or branched alkyl group having 1 to 18 carbon atoms.

Specifically, the (meth)acrylate (6) is as follows.

2-hydroxy-3-fexipropyl (meth)acrylate, cyclohexanoxy-β-hydroxypropyl (meth)acrylate, tetrahydrofurfuroxy-β
-hydroxypropyl (meth)acrylate, nonyloxy-β-hydroxypropyl (meth)acrylate, and the like.

[(Meth)acrylic acid ester compound (7)] The (meth)acrylic acid ester compound (7) has the following general formula.

CH, = C-C-0-CH, -C-0-R1II where R17 is hydrogen or 10H, Im is a straight or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aryl group, It represents an aralkyl group or a straight-chain or branched alkoxyalkyl group.

Specifically, the above (meth)acrylate (7) is methoxycarbonylmethyl (meth)acrylate and ethoxycarbonylmethyl (meth)acrylate.

Examples include heptoxycarbonylmethyl (meth)acrylate, isopropoxycarbonylmethyl (meth)acrylate, and the like.

[(meth)acrylic acid ester compound (8)] In the formula, R
1 is hydrogen or -CH, R11l represents a straight chain or branched alkylene group having 2 to 4 carbon atoms, m is an integer of 1 to 10, and n is 1 or 2.

[(Meth)acrylic acid ester compound (9)] The (meth)acrylic acid ester compound (9) has the following general formula.

In the formula, R21 is hydrogen or 10H, m is an integer of 1 to 10, and n is 1 or 2.

Specifically, the above (meth)acrylates (8) and (9) include acid phosphoxyethyl (meth)acrylate, 3-chloro-2-acid phosphooxypropyl (meth)acrylate, and acid phosphooxypropyl (meth)acrylate. etc. can be mentioned.

[(Meth)acrylic acid ester compound (10)] It is a reaction product of a (meth)acrylate (A) having hydroxyl gas and an organic polyisocyanate (B).

[(Meth)acrylic acid ester compound (11)] A (meth)acrylate (A) having a hydroxyl group.

It is a reaction product of an organic polyisocyanate (B) and a trivalent or higher valent polyol and/or diol (D).

(meth)acrylate (A) having a hydroxyl group in the above (meth)acrylic acid ester compounds (10) and (11), organic polyisocyanate (B) polyol (
D) is the same raw material as the urethane prepolymers (1) and (n).

The above (meth)acrylic acid ester compounds (1) to (1)
Among 1), the most preferable compounds as the adhesive of the present invention are as follows.

(1): 2-hydroxyethyl (meth)acrylate (2): trimethylolpropane tri(meth)acrylate (3): 2.2-bis(4-(meth)acryloxyjethoxyphenyl)propane (4): Dicyclopentenyl (meth)acrylate (5): Methyl (meth)acrylate (6):
2-Hydroxy-3-phenoxypropyl (meth)
Acrylate (7): Ethoxycarbonylmethyl (meth)acrylate (8): Acid phosphooxypropyl (meth)acrylate (9)': 3-chloro2 acid phosphooxypropyl (meth)acrylate (10): 2-Hydroxyethyl ( Reaction product (11) of meth)acrylate and tolylene diisocyanate modified bisphenol A ethylene oxide: Reaction product of the two components of (10) and trimethylolpropane (organic peroxide [■]) This invention The organic peroxide to be incorporated into the composition (
Specific examples of IV) include benzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, cyclohexanone peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, diisopropylbenzene hydroperoxide, lauroyl peroxide, and Examples include dicumyl peroxide. As is already well known, the type and amount of the compound to be added may be such that it functions as a polymerization initiator and is sufficient to impart anaerobic curing properties to the composition. It's enough.

<Photopolymerization initiator [■]) Photopolymerization initiator (■) to be blended into the composition in the present invention
Specific examples of V) include benzyl, benzophenone, Michler's ketone, 2-chlorothioxysanthone, 2
, 4-diethylthioxysanthone, benzoin, benzoin ethyl ether, benzoin isobutyl ether,
Benzoin octyl ether, jetoxyacetophenone, benzyl methyl ketal, 1-hydroxycyclohexylphenyl ketone, diacetyl, methylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, anthraquinone, and 3.3', 4
．． Examples include 4'-tetra-(tert-butylperoxycarbonyl)benzophenone.

The mixing ratio of each component described above is as follows.

Polycarbonate diol modified urethane prepolymer (
1) and/or ([1 is the adhesive composition 10 of the present invention
It is preferably from 10 to 80 parts by weight, more preferably from 20 to 65 parts by weight.

The (meth)acrylic acid ester compound (III) is preferably 20 to 90 parts by weight, more preferably 35 to 80 parts by weight, based on 100 parts by weight of the adhesive composition of the present invention.

The photopolymerization initiator (V) is preferably used in an amount of 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the adhesive composition of the present invention.

(Desired Added Components) In addition to the components described above, various substances may be added to the composition of the present invention for various purposes. For example, an appropriate amount of a polymerization accelerator may be added and mixed, and examples of the polymerization accelerator include 1,2,3,4-tetrahydroquinoline, saccharin, triethylamine, N,N-dimethylaniline, etc. The amount added varies depending on the type of polymerization accelerator, etc., and cannot be generalized, but an example is: [(meth)acrylic acid ester compound (m) , 0.1 to 5 parts by weight of 3,4-tetrahehydroquinoline, 0.1 to 3 parts by weight of saccharin, and 0.1 to 1 part by weight of triethylamine.

Furthermore, oxalic acid, dinitrosoresorcinol, and quinones are added for the purpose of improving stability, dyes and pigments are used for coloring purposes, thixotropic agents such as silica are added for the purpose of imparting thixotropic properties, and thixotropic agents such as silica are used for thickening and thickening purposes. Acrylic resin, urethane resin, epoxy resin, silica, etc. can be blended for different purposes.

The adhesive composition according to the present invention can be easily prepared by mixing and dissolving the components as described above at room temperature or under heating.

[Curing means]

The adhesive composition according to the present invention can be used in the same manner as conventional photocurable anaerobic adhesive compositions.

(Photocuring) Polymerization and curing can be easily achieved by irradiating the photocurable anaerobic adhesive composition with ultraviolet light.

(-Liquid anaerobic curing) When the adherend material is metal, the photocurable anaerobic adhesive composition of the present invention is sandwiched between two adjacent surfaces of the adherend material.

By blocking air, polymerization and curing can be easily coupled.

(Anaerobic curing in combination with curing accelerating primer) When you want to increase the adhesion speed from several seconds to several minutes, or when you want to bond plastics or ceramics.

Apply a primer to accelerate curing to one of the adherends.

Polymerization and curing can be easily achieved by applying the photocurable anaerobic adhesive composition of the present invention to the other adherend, pasting them together, and blocking air. The curing accelerating primer used in this case includes cobalt naphthenate, copper naphthenate, metal organic acid salts described in Japanese Patent Publication No. 5.3-24231, dimethylpara-toluidine, dimethylaniline, 1,2 .3. Tertiary amines such as 4-tetrahydroquinoline, ethylenethiourea,
Examples include thioamide compounds such as tetramethylthiourea.

Example 1 About 12.7 parts by weight of toluene diisocyanate as organic polyisocyanate (B) and about 200 ppm of dibutyltin dilaurate were placed in a reactor, and the reaction temperature was set to about 7
Polycarbonate diol (C) while maintaining at 0°C
Polycarbonate diol with a molecular weight of about 2000 (
Manufactured by Toagosei Chemical Industry Co., Ltd.: Ethylene carbonate and
About 77.8 parts by weight of 1,6-hexanediol (reactant) was gradually added under stirring and stirred for about 1 hour to react.
Add about 200 ppm of dibutyltin dilaurate, and
As a (meth)acrylate (A) having a hydroxyl group, 2-
Approximately 9.5 parts by weight of hydroxyethyl methacrylate was gradually added and reacted while stirring and maintaining the reaction temperature at 70°C, and the reaction solution was analyzed using an infrared absorption spectrum.
The reaction was continued until it was confirmed that the characteristic absorption of the group -NC◯ (near 2250Cn-'') disappeared.

As a result, 100 parts by weight of polycarbonate diol-modified urethane prepolymer (1), which was a rubbery solid at room temperature, was obtained. Further, as a result of analyzing the polycarbonate diol-modified urethane prepolymer (1) by infrared absorption spectrum, the following main peaks were confirmed.

-NHCOO- absorption; 1520-1550an-1, 1720-1740aa
″″1CH,= Absorption of C-CO2-; 930-960
B-1 Example 2 About 13.1 parts by weight of toluene diisocyanate and about 200 ppm of dibutyltin dilaurate were placed as organic polyisocyanate (B) in a reactor, and while maintaining the reaction temperature at about 70'C, polycarbonate diol (
As C), about 80.3 parts of polycarbonate diol (manufactured by Toagosei Kagaku Kogyo Co., Ltd.: a reaction product of ethylene carbonate and 1,6-hexanediol) with a molecular weight of about 2000 was gradually added under stirring for about 1 hour. After stirring and reacting, about 200 ppm of dibutyltin dilaurylate was added, and further, about 4.9 parts by weight of 2-hydroxyethyl methacrylate as (meth)acrylate (A) having a hydroxyl method was added while stirring and at a reaction temperature of 70. The mixture was gradually added while maintaining the temperature at 70°C, and after reacting for about 2 hours, about 1.7 parts by weight of trimethylolpropane as polyol (D) was gradually added while maintaining the reaction temperature at 70°C. The reaction solution was analyzed by infrared absorption spectroscopy to determine the group -NGO.
(7) Characteristic absorption (near 2250an-1) The reaction was continued until it was confirmed that the absorption had disappeared.

As a result, 100 layers of polycarbonate diol-modified urethane prepolymer [■], which is a rubbery solid at room temperature, was coated. Further, as a result of analyzing the polycarbonate diol-modified urethane prepolymer (If) by infrared absorption spectrum, a primary peak was confirmed.

-NHCOO- absorption: 1520-1550an-1, 1720-1740a1
″″1CH,= Absorption of C-COO-; 930~
960aa-1 Example 3 Using the polycarbonate diol-modified urethane prepolymers (t) and (n) obtained in Examples 1 and 2, photocurable anaerobic adhesive composition No. 1 having the composition shown in Table 1 was prepared. ~No,
6 was adjusted. For anaerobic curing adhesive performance, carbon steel adherends were used, and a curing accelerating primer (AT, Quicka V3, manufactured by Toagosei Chemical Industry Co., Ltd.) was applied to one of the adherends.

Apply photocurable anaerobic adhesive compositions No. 6 to No. 6 shown in Table 1 to the other adherend, and paste both together.
By blocking air, the adhesive is anaerobically cured and J
Tensile shear adhesive strength according to IS K-6850, impact adhesive strength according to JIS K-6855,
Further, T-peel adhesive strength was measured according to JIS K-6854. The anaerobic curing adhesive curing time was 3 days at room temperature.

In addition, No. 1 shown in Table 1 was applied on the photocuring performance cormorant glass plate.
～No. 6 photocurable anaerobic adhesive composition with a film thickness of about 50
It was coated with μ and irradiated with ultraviolet light, and the time until the surface tack disappeared was measured.

Table 2 shows the investigation results of photocuring performance and anaerobic curing performance.

means tanprepolymer.

Photo-curing conditions; (Ultraviolet irradiation bag used? 1); Manufactured by Ushio Electric Co., Ltd. System model: UVC-183
3/INJA-2DI> (high-pressure mercury lamp); semi-concentrating type, lamp output = 80 W/am (illuminance [365 nm]);
140 mv/ffl [Effects of the Invention] When the composition according to the present invention is used as a photocurable anaerobic adhesive composition for adhering metal parts, sealing, preventing loosening, fixing fitting parts, etc. It is an excellent product that exhibits high impact adhesive strength and peel adhesive strength, and because it has a fast photocuring speed, it is also an excellent product that can improve the speed of the photocuring process. This is a photocurable anaerobic adhesive composition that is significantly improved in terms of adhesive strength reliability and productivity compared to the conventional anaerobic adhesive composition.

Claims (1)

Scope of Claims: A polycarbonate diol-modified urethane preform having a (meth)acryloyloxy group, which is a reaction product of a (meth)acrylate (A) having a hydroxyl group, an organic polyisocyanate (B), and a polycarbonate diol (C). one or more polymers [I] and/or
Polycarbonate diol-modified urethane having a (meth)acryloyloxy group, which is a reaction product of a (meth)acrylate (A) having a hydroxyl group, an organic polyisocyanate (B), a polycarbonate diol (C), and a polyol (D) One or more types of prepolymer [II] and a polycarbonate diol-modified urethane prepolymer having the above (meth)acryloyloxy group [
An adhesive composition comprising one or more (meth)acrylic acid ester compounds [III] other than [I] and [II], an organic peroxide [IV], and a photopolymerization initiator [V]