JPH0232304B2 - AKURIREETONOKOKASEISOSEIBUTSU - Google Patents

Description

[Detailed description of the invention]

The present invention is a so-called two-component type acrylate and/or methacrylate curable composition, in particular, containing thiourea and/or a thiourea derivative and a copper salt of an organic acid and/or a copper organic compound as a curing accelerator, and Furthermore, the present invention relates to an acrylate and/or methacrylate composition containing paraffins and/or waxes, which can be cured in a few minutes to several tens of minutes, which is convenient to handle, and which can sufficiently cure parts exposed to air. A curable composition comprising an acrylate and/or methacrylate (hereinafter often abbreviated as (meth)acrylate) monomer mixed with an organic peroxide and a curing accelerator is known. For example, British patent no.
No. 715382, U.S. Patent Nos. 3591438 and 3625930 disclose the use of a compound having a thiocarbonyl group such as thiourea as a curing accelerator;
There is a desire to further accelerate the curing of these curable compositions. In addition, as this curing accelerator, thiourea derivatives, α, α′-
The combination of dipyridyl and an organic acid salt of copper, cobalt, manganese, chromium or vanadium, and Japanese Patent Publication No. 52-24516 describes the combination of thiourea and/or thiourea derivatives with thiosalicylic acid and/or 2-mercaptobenzimidazole copper. However, these accelerators cure extremely quickly, taking several seconds to several tens of seconds. These ultra-rapid hardening accelerators were
As described in Japanese Patent Publication No. 17966 and Japanese Patent Publication No. 52-24516, hardening accelerated by dissolving a polymerizable composition containing a (meth)acrylate monomer and an organic peroxide and a curing accelerator in a solvent. In some cases, it is appropriate to coat the hardening accelerator composition in advance and then apply the polymerizable composition after drying, since instantaneous adhesion can be achieved. However, the so-called two-component base agent is composed of two components: a polymerizable composition containing a (meth)acrylate monomer and an organic peroxide, and a polymerizable composition containing a (meth)acrylate monomer and a curing accelerator. In the curable composition for molds, the two components must be sufficiently mixed in order to uniformly polymerize and harden the two components. Two-component type (meth)
When an ultra-rapid curing accelerator is used in an acrylate curable composition, the mixing time of the two components may not be sufficient and curing may be too rapid in some areas. In particular, when the composition is used as an adhesive, the time required to mix the two components is too short and sufficient mixing is not possible, resulting in failure to obtain the desired adhesive strength or inability to apply over a wide area. , or it is impossible to adjust the position of the adherend after adhesion, so it is often not practical to use. The present invention provides a (meth)acrylate curable composition containing an organic peroxide, which takes the time required for actual work, such as mixing or coating in the case of an adhesive, and adjusting the position of the adherend after adhesion. The object of the present invention is to provide a curing accelerator that can be cured as quickly as possible after a certain amount of time has elapsed. or,
In particular, the present invention is a two-component type (meth) that does not start curing during the time required for handling operations such as mixing, but quickly hardens after that time, and can sufficiently harden even the parts exposed to air. An acrylate curable composition is provided. Furthermore, the present invention provides a two-component (meth)acrylate curable composition that has little off-odor and has good adhesion to metals and the like. That is, the curing accelerator for curing (meth)acrylate monomers using an organic peroxide according to the present invention is a combination of thiourea and/or a thiourea derivative and a copper salt of an organic acid and/or a copper organic chelate compound. . A two-component (meth)acrylate composition using this curing accelerator has an appropriate curing speed. According to the present invention, a component A containing an acrylate and/or methacrylate monomer having a boiling point of 150°C or higher and an organic peroxide, an acrylate and/or methacrylate monomer having a boiling point of 150°C or higher, and curing acceleration In a two-part base type acrylate and/or methacrylate curable composition consisting of component B containing a curing accelerator, component B contains thiourea and/or a thiourea derivative and a copper salt of an organic acid and/or as a curing accelerator.
or contains a copper organic chelate compound, and one or both of component A and component B has a melting point of 35°C
The above paraffins and/or waxes are contained in an amount of 0.1 part by weight or more based on 100 parts by weight of acrylate and/or methacrylate monomers in the entire composition, and further in either or both of the A component and the B component, A curable composition of acrylate and/or methacrylate is provided, which is characterized in that it contains an acrylonitrile-butadiene rubber having a functional group. The time required for the composition of the present invention to rapidly start curing is 1 minute or more and usually several tens of minutes or less, preferably 5 minutes or less. The monomers used in the present composition are acrylates and/or methacrylates having a boiling point of 150°C or higher, and specifically include, but are not limited to, those listed below. Acrylic acid alkyl esters such as hexyl acrylate and lauryl acrylate; Methacrylic acid alkyl esters such as butyl methacrylate and lauryl methacrylate; Glycidyl acrylate; Glycidyl methacrylate; 2-hydroxyethyl acrylate and acrylic acid -2-hydroxypropyl, acrylic acid-
Acrylic acid hydroxyalkyl esters such as 3-chloro-2-hydroxypropyl; 2-hydroxyethyl methacrylate; 2-hydroxypropyl methacrylate; methacrylic acid such as 3-chloro-2-hydroxypropyl methacrylate Acid hydroxyalkyl ester; 2-acetoxyethyl (meth)acrylate, for example, acetoxyalkyl (meth)acrylate having an alkyl group having 1 to 3 carbon atoms; Polyethylene glycol mono(meth)acrylate represented by the following formula; Propylene glycol mono(meth)acrylate represented by the following formula; Mono- or polyethylene glycol diacrylates such as ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate; ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol Mono- or polyethylene glycol diacrylates such as dimethacrylate; Mono- or polypropylene glycol diacrylates such as propylene glycol diacrylate and tripropylene glycol diacrylate; Mono- or polypropylene glycol diacrylates such as propylene glycol dimethacrylate and tripropylene glycol dimethacrylate Methacrylates; Polyacrylates such as trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethanetetraacrylate; Polymethacrylates such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, and tetramethylolmethanetetramethacrylate ; Polyester acrylate obtained by the reaction of acrylic acid, glycols, and polybasic acid; Polyester methacrylate obtained by the reaction of methacrylic acid, glycols, and polybasic acid; Obtained by the reaction of epoxy compound and acrylic acid Epoxy acrylate; Epoxy methacrylate obtained by reacting an epoxy compound with methacrylic acid; Amide acrylate obtained by reacting a polybasic acid with an amino alcohol and then reacting with acrylic acid; Amide methacrylate obtained by reacting hydroxyalkyl acrylate and then reacting with methacrylic acid; Urethane acrylate obtained by reacting hydroxyalkyl acrylate with a polyisocyanate compound; Urethane obtained by reacting hydroxyalkyl acrylate with a polyisocyanate compound Methacrylate; liquid NBR, liquid SBR, liquid polybutadiene,
Examples include reactive oligomers in which one or both ends of liquid 1,2-polybutadiene or liquid polychloroprene are acrylated or methacrylated. In this invention, (meth) having a boiling point of 150℃ or higher is used.
Although acrylate monomers are used, such high-boiling (meth)acrylates are almost odorless, so curable compositions using them do not degrade the environment during coating operations. When the curable composition is used as an adhesive, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-acetoxyethyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, epoxy mono(meth)acrylate obtained by reaction of an epoxy compound and (meth)acrylic acid , an amide mono(meth) obtained by reacting a reaction product of an organic acid and an amino alcohol with (meth)acrylic acid.
Particularly preferred are mono(meth)acrylate monomers such as urethane mono(meth)acrylates obtained by reacting acrylates, hydroxyalkyl(meth)acrylates, and isocyanate compounds.
These mono(meth)acrylate monomers are
In a composition containing an elastomer such as NBR, it exhibits high impact strength and high shear strength as adhesive properties, and is also excellent in that there is little deterioration in adhesive properties when exposed to high temperatures. In the composition of the present invention, one type or a combination of two or more types of (meth)acrylate monomers having a boiling point of 150°C or higher can be used. And if necessary, vinyl monomers other than (meth)acrylate monomers with a boiling point of 150°C or higher, such as methyl acrylate, ethyl acrylate, propyl acrylate,
(meth)acrylates with boiling points below 150°C, such as butyl acrylate, methyl methacrylate, ethyl methacrylate, and propyl methacrylate;
Addition of styrene, α-methylstyrene, vinyl acetate, vinyl propionate, acrylic amide, methacrylic amide, maleic acid or maleic anhydride, fumaric acid, chlorostyrene, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, etc. You can also. It is preferable that these vinyl monomers be limited to a maximum of 50% by weight based on the total monomers. Adding more than that may impair the characteristics of the compositions of the invention. Generally, in a composition consisting of a (meth)acrylate monomer, an organic peroxide, and a curing accelerator, if the monomer has a boiling point of 150°C or higher at normal pressure,
It is anaerobic, meaning it does not harden in the presence of air. In the case of (meth)acrylate with a boiling point of 150° C. or lower, it can be cured in the presence of air with or without the addition of a wax such as paraffin. However, it is known from Japanese Patent Publication No. 43-6545 that (meth)acrylate compositions having a high boiling point, such as 2-hydroxyethyl methacrylate (boiling point 95 DEG C./10 mmHg), do not harden in the presence of air. Furthermore, it is known from JP-A-53-2543 that the surface of a composition containing a monomer containing 90% by weight of 2-hydroxyethyl methacrylate, an organic hydroperoxide, thiourea, and paraffin will not harden in air. ing. However, (meth)acrylate, which has a high boiling point, has little negative impact on the environment such as odor, so it can be used as a monomer component to create compositions that harden at a suitably fast rate in the air, such as adhesives, paints, and sealants. It is highly anticipated in a wide range of fields. In the composition of the present invention containing a (meth)acrylate monomer, an organic peroxide, and a thiourea derivative and/or a copper salt of an organic acid and/or a copper organic chelate compound as a curing accelerator, Even when the polymer is a (meth)acrylate with a boiling point of 150°C or higher, surface hardening can be made possible in air by adding paraffins and/or waxes such as carnauba wax with a melting point of 35°C or higher. The boiling point of (meth)acrylate monomer is
Even if the temperature is below 150°C, use thiourea and/or a thiourea derivative and a copper salt of an organic acid and/or a copper organic chelate compound as a curing accelerator, and add paraffins and/or waxes with a melting point of 35°C or higher. This accelerates the surface hardening rate in air compared to compositions that do not contain paraffins and/or waxes. Examples of paraffins include paraffin and microcrystalline wax, and examples of waxes include carnavaloi, beeswax, lanolin, spermaceti wax, ceresin, and candelilla wax. The content of paraffins and/or waxes in the composition is 0.1 part by weight or more based on 100 parts by weight of all (meth)acrylate monomers, and if it is less than 0.1 part by weight, stickiness remains in the air contact area. The amount is preferably up to 5 parts by weight, and may exceed 5 parts by weight, but the effect of improving surface curability will no longer be achieved. Paraffins and/or waxes can be added to either or both of component A and component B of the composition, but it is preferable to add them to both. Examples of organic peroxides include hydroperoxide, benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, and t-
Organic peroxides such as butyl peroxyacetate are used, but hydroperoxides are preferred. Examples of preferred organic peroxides include cumene hydroperoxide, diisopropylbenzene hydroperoxide, diisopropylbenzene dihydroperoxide, paramenthane hydroperoxide, and t-butyl hydroperoxide. The amount of organic peroxide is usually 0.1 to 15 parts by weight per 100 parts by weight of the total monomer components.
Parts by weight are used, preferably 1 to 10 parts by weight. The curing accelerator according to the present invention is a combination of thiourea and/or a thiourea derivative and a copper salt of an organic acid and/or a copper organic compound. As the thiourea derivative, thioamide compounds such as diethylthiourea, dibutylthiourea, ethylenethiourea, trimethylthiourea, diphenylthiourea, ditolylthiourea, and mercaptobenzimidazole are used. Thiourea and/or
Or, the amount of the thiourea derivative is 0.01 parts by weight or more per 100 parts by weight of the total monomer components, and curing is possible.
The range is preferably 0.01 to 15 parts by weight, particularly 0.1 to 10 parts by weight. Copper salts of organic acids include copper naphthenate, copper acetate,
Preferred are copper salts of carboxylic acids such as copper maleate, copper organic sulfonates, and the like. Preferred examples of the copper organic chelate compound include copper acetylacetonate, copper dimethylglyoxime, and copper dithizone. The amount of the organic acid copper salt and/or copper organic chelate compound used is 0.001 to 1 part by weight based on 100 parts by weight of all monomer components. The curable composition of the present invention is a two-component (meth)acrylate composition consisting of component A and component B. The weight ratio of the monomers of component A and component B is approximately 1
It is possible to cure from about 10 to about 10 to about 1, but 1
A ratio of 3:3 to 3:1 is preferable since there is little variation in cured physical properties. The essential components of this composition include a (meth)acrylate monomer with a boiling point of 150° C. or higher, an organic peroxide, and a specific curing accelerator. In order to further enhance the performance of this curable composition, other additives may be added as desired. For example, various polymers or plasticizers can be dissolved or dispersed in the composition, and various inorganic or organic powders can be dissolved or dispersed in order to adjust the viscosity or change the properties of the cured product. NBR, SBR, styrene
butadiene block copolymer, polychloroprene, polybutadiene, carboxylated modified polymers of these polymers, chlorosulfonated polyethylene, butadiene as essential components, and at least one of acrylonitrile, styrene and methyl methacrylate as a component Addition of a graft polymer or the like is very effective in improving adhesive properties, especially impact strength and peel strength. The present inventor has discovered that the above (meth)acrylate monomer, organic peroxide and specific curing accelerator and melting point
In the composition of the present invention, which contains paraffins and/or waxes having a temperature of 35°C or higher as an essential component, and optionally contains other additives, one or both of the A component and the B component is particularly functional. Compositions containing acrylonitrile-butadiene rubber (abbreviated as NBR) having groups are particularly useful when used as adhesives due to their high adhesive strength. Functionalized NBR is made by copolymerizing butadiene with acrylonitrile and up to about 5% by weight of a functional monomer. Suitable functional monomers include acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, methyl methacrylate, and chlorostyrene. The amount of NBR modified with a functional group added is preferably in the range of 5 to 30% by weight based on component A, component B, and the entire composition. A copper salt of an organic acid and/or a copper organic chelate compound is used as one component of the curing accelerator according to the present invention, but a salt and/or chelate compound of a metal other than copper is used, and functional group-modified NBR is used as the B component. If added, it may cause problems such as gelation before curing or increase in viscosity during storage of component B. Examples and comparative examples will be explained below. Parts and percentages herein are by weight unless otherwise specified. Various physical properties were measured using the following measurement methods. Adhesive strength Adhesive test piece: Iron (mild steel) 〃 Surface treatment: 150 mesh sandblasting followed by acetone degreasing, Tensile shear strength: ASTM D1002-64 Impact strength: ASTM D950-54 Peel strength: Conforms to ASTM 1876-6T, Drop impact strength : The ferrite magnet (60φ) of the speaker field part was glued to the plate and yoke, and the magnet was dropped from a 1 m long slide table at an angle of 70 degrees, and the number of times until it broke was measured. Fixing time One end of a 25.4 m/m x 100 m/m iron specimen with a smooth surface was wrapped at a 20°C atmosphere with a lap length of 12.7 m/m.
The time required for bonding was determined as the time required for the bond to stop moving when touched with the finger after bonding. Example 1 44.5 parts of methyl methacrylate and 44.5 parts of 2-hydroxyethyl methacrylate were mixed and dissolved with 11 parts of polymethyl methacrylate (Acricon, Mitsubishi Rayon Co., Ltd.) and 1.0 part of paraffin wax (MP47°C), and after dissolving, this solution was mixed and dissolved. Divide into two liquids, add 8 parts of cumene hydroperoxide to one liquid,
Solution A is made by adding 0.2 parts of 2,2'-methylenebis(6.t-butyl 4-methylphenol (Sumilyzer MDP)), and the other solution is made by adding 1.2 parts of ethylene thiourea and 0.12 parts of copper naphthenate. Liquid B was prepared.The two liquids A and B prepared in this way were mixed and cured, and the surface hardness after 1 day and the iron/iron test piece were adhered.The shear strength after 10 minutes, the shear strength after 1 day, and the time of adhesion The fixation time at ambient temperature was measured.For comparison, a solution containing only copper naphthenate was prepared as solution B', and the physical properties were simultaneously measured when it was combined with solution A.The results are summarized in Section 1.
Shown in the table.

[Table] Example 2 50 parts of 2-hydroxyethyl methacrylate, polyester acrylate which is a condensate of glycidyl phenol and acrylic acid (manufactured by Kyoei Yushi Co., Ltd., M-
600A), 50 parts of methyl methacrylate/butadiene/acrylonitrile/styrene graft copolymer (trade name MBAS of Denki Kagaku Kogyo Co., Ltd.)
BL-20) 20 copies and paraffin wax (mp57
After dissolving and dispersing the solution, it was divided into two parts, and 5 parts of diisopropylbenzene dihydroperoxide was dissolved in 100 parts of one solution to obtain Solution A. To 100 parts of the other liquid, 5 parts of O-tolylthiourea and predetermined amounts of various metal compounds were added to prepare a B liquid. Apply the adhesive liquid created in this way on a steel plate.
Table 2 shows the results of mixing equal amounts of liquids A and B and examining the curing properties and surface tack after 10 minutes and 1 day. From this table, in the case of compositions using non-volatile monomers, the effect of addition of copper organic acid salts and chelate compounds on surface curing properties (non-anaerobic) is noticeable.

[Table] The criteria for judgment are as follows. (Similar criteria apply hereafter) ○: No surface tack △: Slight tack (slightly tacked) ×: tacked Example 3 The same composition as Example 2 was used, but the amount of the ring element component of liquid B was changed. Hardenability on iron piece as in Example 2,
Table 3 shows the results of measuring the adhesion time on iron/iron test pieces.

[Table] Example 4 As a monomer with low volatility, 2-hydroxyethyl methacrylate and a condensate of bisphenol A, ethylene glycol, and acrylic acid [trade name A-BPE-4, manufactured by Shin Nakamura Chemical Co., Ltd., from the condensation composition] The estimated molecular formula of 2,2′bis(4-acryloxydiethoxyphenol)propane] 40:60 monomer mixture, carboxylated NBR
Rubber (Hycar1072) was dissolved at 12%. This 2
The mixture was divided into equal parts to form liquid A and liquid B. Part A contains 5 parts of diisopropylbenzene dihydroperoxide,
Solution B contains 1.2 parts of ethylene thiourea and copper naphthenate.
0.12 part was added. Various waxes or paraffins were added to liquids A and B, and the surface drying properties under air contact were examined. The results are shown in Table 4.

【table】

[Table] Example 5 Various rubbers and polymers were dissolved in 50 parts of 2-hydroxyethyl methacrylate and 50 parts of polyethylene glycol monomethacrylate (PE-90 manufactured by NOF Corporation), and the influence on adhesive strength, particularly impact strength, was investigated. Add 1 part of paraffin wax (mp57℃) as wax to this solution, divide it into 2 parts, add 5 parts of diisopropylbenzene dihydroperoxide to part A, 1 part of ethylene thiourea, and 0.1 part of copper acetylacetonate to part B. Adhesives were prepared by adding parts of The results are shown in Table 5.

[Table] * Iron - Iron test piece ** Solution A, gelling in a few days Example 6 50 parts of polyethylene glycol monomethacrylate (trade name: Bremmer PE-90 manufactured by NOF Co., Ltd.) and 2
- 15 parts of carboxylated NBR (Hycar1072) and 1 part of paraffin (mp57°) were dissolved in 50 parts of hydroxyethyl methacrylate to prepare a rubber stock solution.
To prepare liquid B, 1,3-
When 5 parts of dicyclohexylthiourea and various metal salts were added, those to which metals other than copper salt were added thickened or gelled, and could not be used as adhesives. The viscosity of the rubber stock solution is 3500cps.
(at 23℃).

[Table] Example 7 100 parts of various monomers and carboxylated NBR
(Hycar1072) 12 parts and paraffin (mp57゜) 1 part were dissolved to make a rubber stock solution, which was divided into two parts.For part A, 100 parts of rubber stock solution and 5 parts of diisopropylbenzene dihydroperoxide were added, and for part B, It was adjusted by adding 1.2 parts of ethylene thiourea and 0.12 parts of copper naphthenate. For each monomer composition, the shear strength and impact strength of iron/iron test pieces were measured, and the ferrite magnet (60φ) of the speaker field part was bonded to the yoke and plate. The drop impact strength was measured. Drop impact tests were also conducted on the strength one day after bonding and on the bonded test pieces after one day of curing and heat treatment at 150°C for 2 hours. 7th result
Shown in the table.

【table】

【table】

【table】

Claims (1)

[Claims] 1 A containing an acrylate and/or methacrylate monomer and an organic peroxide with a boiling point of 150°C or higher
In a two-component base type acrylate and/or methacrylate curable composition consisting of a component B having a boiling point of 150°C or higher, an acrylate and/or methacrylate monomer, and a curing accelerator, the B component has a curing accelerator. contains thiourea and/or a thiourea derivative and a copper salt of an organic acid and/or a copper organic chelate compound as an agent, and component A and B.
One or both of the components contains paraffins and/or waxes with a melting point of 35° C. or higher based on 100 parts by weight of the entire acrylate and/or methacrylate monomer in the composition, and further contains A An acrylate and/or an acrylate characterized by containing an acrylonitrile-butadiene rubber having a functional group in either or both of the component and the B component.
or a curable composition of methacrylate.