JPS61218A - Curable composition - Google Patents

Abstract

PURPOSE:A curable composition useful in the fields of adhesives and paints, containing a polymer having a (meth)acryloyl group as a side chain and an unsaturated isocyanate having both isocyanate and (meth)acryloyl groups each in a specified amount. CONSTITUTION:A polymer having a (meth)acryloyl group as a side chain is produced from a polymerizable monomer, a polymerizable monomer having a functional group for introducing a (meth)acryloyl group into the former monomer and a polymerizable double bond and a compound having both a group reactive with said functional group and a (meth)acryloyl group. Two components of the obtained polymer and an unsaturated isocyanate having at least 0.1 equivalent of isocyanate groups and at least 0.1 equivalent of (meth)acryloyl groups (it is preferable to add a monomer such as an acrylate thereto) are mixed together to obtain the titled curable composition.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a curable composition useful mainly in the fields of adhesives and paints, which has excellent adhesion to substrates in particular, and which can be freely curable. RELATED TO CONTROLLABLE COMPOSITIONS.

[Prior art]

A wide variety of adhesives and paints have already appeared,
each for its own purpose.

As is well known, epoxy resin is the most well-established adhesive and has a good track record, but on the other hand, the hardening agent is irritating to the skin, and it is difficult to control room temperature curing. In addition, it takes time to cure, and rapid curing inevitably impairs adhesive properties, making it difficult to exhibit original physical properties.

In addition, neither polyurethane adhesives nor curable acrylic adhesives can be said to fully meet the requirements.

In particular, it is used as an adhesive for materials that can be found everywhere in everyday life, such as concrete surfaces that contain water or steel surfaces that have some rust, where the physical properties of existing adhesives do not provide reliable results. There are many. It goes without saying that the bonding process should be performed under conditions that will clean the surface to be bonded and allow the adhesive used to exhibit its best performance. In the case of gluing operations, it is difficult to find the best suitable conditions;
In many cases, it is said to be impossible.

The situation is similar in the case of paints. There are many uses for paints that require applying a highly adhesive rust-preventing paint after removing one or two types of rust.

Conventionally, oil-based or alkyd-based paints mixed with lead oxide-based rust-preventive pigments have been used in cases like this, but so-called maintenance-free heavy-duty anti-corrosion paints retain their performance for many years once applied. It is difficult to use alkyd paints.

[Structure of the invention]

The present inventors have conducted various studies on resins that serve as the base for adhesives and paints that exhibit performance that is as stable as possible even under changes in external conditions, and have found that a composition having the following structure has performance close to that described above. They discovered this and completed the present invention. That is, 5) the present invention comprises (A) a polymer having a (meth)acryloyl group in the side chain; The present invention relates to a curable composition containing an unsaturated isocyanate having at least / equivalent of isocyanate groups and at least o,i equivalents of (meth)acryloyl groups.

In this specification, "having 1 (meth)acryloyl group" means "
Contains a methacryloyl group, an acryloyl group, or both."

Although the combination of (A) and (B) above is a necessary condition for the composition of the present invention, the use of other monomers such as acrylic esters can also be said to be a sufficient condition and is practically advantageous. In addition, it is necessary to use an organic peroxide as a curing agent, especially an accelerator for curing at room temperature.

The polymer having a side chain K(meth)acryloyl group used as component (3) in the composition of the present invention includes the following polymerizable monomer (1) and a functional group (for example, an acid anhydride) for introducing a (meth)acryloyl group into the monomer. a polymerizable monomer (11) having a polymerizable double bond and a group (e.g., a hydroxyl group, an epoxy group, an NCO group) that is reactive with the functional group of the monomer (II). and a (meth)acryloyl group-containing compound (110).

The monomer (1) forming part of the polymer main chain is not particularly limited, but includes, for example, styrene, vinyltoluene, chlorostyrene, acrylic esters, methacrylic esters, acrylonitrile, vinyl chloride, vinylidene chloride, Typical examples include vinylpyrrolidone and vinyl acetate.

The monomer (1) that forms part of the polymer main chain and has a functional group for introducing a side chain (meth)acryloyl group into the main chain is, for example, acrylic acid, methacrylic acid; maleic anhydride, itaconic anhydride: unsaturated alcohol. Examples include co-hydroxyethyl acrylate, co-hydroxybrobyl acrylate, co-hydroxyethyl methacrylate, -monohydroxyglobyl methacrylate; methylol acrylamide.

In addition, the compound (ili) that introduces a (meth)acryloyl group in a side chain into a polymer is the compound (1) above that introduces a (meth)acryloyl group into a side chain by reacting with an acid anhydride group in the polymer.
Unsaturated alcohols described in 1), such as unsaturated epoxy compounds that react with side chain carboxyl groups of polymers to introduce (meth)acryloyl groups, such as glycidyl (
meth)acrylate, especially glycidyl methacrylate, or an unsaturated isocyanate that initially reacts with, for example, a side chain ○H group of a polymer [hereinafter, this unsaturated isocyanate will be referred to as unsaturated isocyanate to distinguish it from the unsaturated isocyanate of component (B) of the present invention. (C)].

The above unsaturated incyanae) (C) is seven months (II)
It can be obtained by the reaction of the unsaturated alcohol having a (meth)acryloyl group described in 1 with a polyhydric isocyanate.

In this case, it is necessary to react one mole or more of unsaturated alcohol per mole of polyvalent isocyanate. For example, 1 mole of diisocyanate to 1 mole of unsaturated alcohol. 1
It is necessary to react in the range of mol to g mol to leave an NCO group, and this remaining NCO group is used as a monomer (
+) and the hydroxyl group of the polymer raw button obtained in (11).

The unsaturated isocyanate (C) is therefore, for example, a mixture of the monomers listed below.

In this case, a heptadmer (+) with a hydroxyl group in the side chain
The reaction with the polymer obtained from (11) is only the unsaturated isocyanate (C) of (a) (8ka1,...
. 9()l)a24. . The urethane produced by A2 is useful for improving physical properties including improving curability. (Free polyvalent isocyanate compound is unsaturated isocyanate)
If it remains in (C), it will cause gelation during the reaction, so the molar ratio of the unsaturated alcohol should be greater than 1 mole per mole of polyhydric alcohol.

(Meth)acryloyl group-containing unsaturated isocyanate for introducing a (meth)acryloyl group into the side chain of the polymer of the present invention) Examples of polyvalent isocyanates that can be used in (C) include the following types: J, # -) lylene diisocyanate, J, 4'-
A mixture of tolylene diisocyanate and 2.6-)lylene diisocyanate, phenylene diisocyanate, diphenylmethane isocyanate, xylylene diisocyanate, inphorone diisocyanate), /, A-hexamethylene diisocyanate, polyisocyanate synthesized from novolac, and /,! - Naphthylene diisocyanate.

Thus, in the composition of the present invention, the polymer (A) having a (meth)acryloyl group in its side chain can be produced, for example, as follows: (a) A polymer having an acid anhydride structure in its structure, (meth) Reacting an alcohol having an acryloyl group: (b) Reacting an epoxy compound having a (meth)acryloyl group with a polymer having a carboxyl group in its structure: C,H.

Catalyst H (iii) A polymer having a hydroxyl group in its structure is reacted with an unsaturated isocyanate (yF-) compound containing an isocyanate group and a (meth)acryloyl group in the molecule: H,C2C-CH.

Among the water-side polymers mentioned above, a polymer (having a (meth)acryloyl group in the Illi chain through a urethane bond) is obtained by reacting a polymer having a hydroxyl group () and ) with an unsaturated isocyanate (C). Polymer (A) is most preferred.

In the type (b) in which an unsaturated epoxy compound is reacted with a carboxyl group-containing polymer, the hydroxyl group generated by the reaction reacts with the unsaturated isocyanate (B), so the polymer (A) and unsaturated isocyanate are separated immediately before use. Since (B) is mixed, even if 9 is present, if both are mixed, it cannot be stored for a long time.

The unsaturated isocyanate (B), which is another component of the present invention, has a slightly different component ratio from the unsaturated isocyanate (C). That is, the molar ratio of the polyvalent isocyanate compound and the (meth)acryloyl group-containing unsaturated alcohol is of the type obtained by reacting 1 to 1 mole of unsaturated N alcohol O per 1 mole of the polyvalent isocyanate. Therefore, the unsaturated isocyanate (B) used as a monomer component is, for example, a mixture of the following three components: However, depending on the molar ratio of the unsaturated alcohol and the isocyanate compound in the unsaturated alcohol (B), it may also be a co-component.

The constituent components of the unsaturated isocyanate (B) are the same as those of the unsaturated isocyanate (C).

It goes without saying that the blending ratio of the polymer (A) of the present invention, that is, the side button non-h1 bond type polymer and the unsaturated isocyanate (B), can be changed depending on the purpose of use, but in general, the unsaturated isocyanate CB) is Of the whole composition! ;-93
It is possible to place it with a heavy view%.

A suitable proportion of the unsaturated isocyanate (B) is within the range of 20 to 70% by weight of the total composition.

It is of course possible to dissolve the polymer (A) and the unsaturated isocyanate (B) in a solvent, but it is practically preferable to dissolve them in a monomer. The monomer used here can be any type that can be copolymerized with a (meth)acryloyl group, such as styrene, vinyltoluene, methacrylic esters, acrylic esters,
Examples include acrylonitrile, vinylpyrrolidone, and vinyl acetate.

Further, in order to cure the composition of the present invention, a curing agent is used, and for curing at room temperature or by heating, an organic peroxide and an accelerator as necessary are used, and for photocuring, a photosensitizer such as benzyl is used. Dimethyl ketal, hydroxyacetophenone, benzoin isobutyl ether, etc. are used.

The composition of the present invention can be used in combination with a fibrous reinforcing material, a filler, a coloring agent, etc., if necessary.

[Embodiments of the invention]

Examples are provided below to aid in understanding the invention.

Example 1 Synthesis of fixed one-phase bonded polymer A In one flask, ethyl acetate J 00 ti, azobisisobutylene were added. 1 g of lonitrile, lauryl mercaptan o, a I! are charged, and a mixed monomer mixture of gtylated acrylate/'10 g, acrylonitrile, and 10 il of λ-hydroxypropyl methacrylate is added dropwise at room temperature in a nitrogen stream.

After completion of the dropwise addition, keep the mixture under reflux for 71 hours. The temperature was lowered to 60C and hydroquinone o and ig were added to complete the reaction.

Next, 1 mole of 2-hydroxypropyl methacrylate and 2
．． A reaction product of /:1 mole of Hiro-tolylene diisocyanate, an unsaturated isocyanate f with a substantially zero hydroxyl value and with a substantially /equivalent amount of isocyanate groups remaining.
Add 3011 parts of I) and heat and stir with BOC for 3 hours.

As a result of infrared analysis, it was confirmed that the hydroxyl groups had almost completely disappeared. Furthermore, 700 g of ethyl acetate was added, and unsaturated polymer (A) was obtained in the form of a slightly cloudy pale yellowish brown liquid.

An adhesive was fabricated using the following formulation.

Unsaturated polymer (A) / 00 parts Saturated isocyanate FII J 0 parts Benzoyl peroxide paste (SO%BPO) / Old Is glass flakes (average particle size approximately goμ) aO parts (... *7
)9(,&□ゎao+T available,,.

isow×2! ；■Make the end of a 3x copper plate 13m long. Apply it with a percoater to a thickness of 0.2 on a test piece cleaned with /, z, z, and trichloroethane with boo abrasive paper. After leaving it for 20 minutes at room temperature to volatilize the ethyl acetate, it was pressed and left overnight.

Adhesive strength by tensile shear is /S da~79-kg7cm
” and was useful as an adhesive.Also, even when using a rusted test piece of the same size (however, the floating mackerel parts were removed with sandpaper) The adhesive strength by shearing of □ffi was shown at ~/70, which was at the same level.

Example Synthesis of side chain unsaturated condensation polymer (B) Methyl ethyl ketone aoo1. Azobissuitronitrile Q, ZI,
Laurylmercazotane O. While refluxing toluene under a nitrogen stream, add nonyl acrylate ibog.
, 10 g of styrene, and a mixed solvent of maleic anhydride OP were added dropwise. After completion of the dropwise addition, refluxing was continued for 16 hours, the temperature was lowered to 60C, and hydroquinone O0θgg was added to stop the reaction.

Then co-hydroxyethyl methacrylate 30I! ,
Add diptyltin oxide o and bl, and further heat for S hours at the boiling point of toluene.

Based on the acid value (in terms of solid content) qy, S, it was estimated that most of the acid anhydride groups had become monoesters of unsaturated alcohols. After cooling to room temperature, add methyl ethyl keto 7300
g was added to obtain I+ii g unsaturated bond type resin (B) in the form of a pale yellowish brown liquid.

Synthesis of unsaturated isocyanate (11) /l separable flask with stirrer, reflux condenser, dropping funnel, thermometer with gas inlet hole, isophorone diisocyanate cococoy (l soru), rosebenzoquinone o, o! r11. Prepare diptyltin dilaurezilaurate 0, co-hydroxyethyl methacrylate/4
14I! (hecomole) is added dropwise.

As the temperature rises as it drops, once it reaches the AOC, cool it down.
After drying and reacting in air for 3 hours with AOC, infrared analysis revealed that the absorption of hydroxyl groups, although somewhat difficult to judge, had almost completely disappeared, and unsaturated isocyanate (
(2) was obtained in the form of a pale yellowish brown liquid.

Side chain unsaturated bond type polymer (B) 100 parts unsaturated isocyanate (II) J o part para-menthane peroxide 1 part dimethyl para-toluidine A mixture of OJ part was added to the same steel plate end as in Example 1 to a thickness of O. Paint it accordingly.

After the solvent evaporates, the coating film is sticky, but when steel plates are placed on top of each other, it gels and stops moving after about an hour, and the adhesive strength by tensile shearing after being left overnight is 1/3 hi ~
/9/kg/cm" and could be used as an adhesive.

Furthermore, when using a test piece of the same size with a film of water on it after wetting the steel plate and scraping off the excess water, the bond strength was on the order of 1SO~-0Ky, indicating an improvement in strength. Ta.

Example 3 Synthesis of polymer (C) with unsaturated side chains
1.7 Zobisisobutyronitrile Hiro I, lauryl mercaptan/Elk were prepared, polymerized for S hours at the boiling point of methyl ethyl ketone in a nitrogen gas stream, and then cooled to 60C.
~Add 0.2 g of hydroquinone to terminate the reaction.

Next, triphenylphosphine cog and acrylic acid JOI were added, the temperature was raised, and the reaction was carried out for one hour under the boiling point of methyl ethyl ketone and a nitrogen stream. The acid value became almost zero, and the reaction was judged to have been completed.

This includes phenoxyethyl acrylate 370)
Add I and reflux °7de71-replaced with fractional distillation ``'de''- and approx.! Methyl ethyl ketone was distilled off under a reduced pressure of 0.00 mall, to obtain a yellowish brown, sill-like unsaturated bond type polymer (C).

Synthesis of unsaturated isocyanate) (II[) In a cellar equipped with a stirrer, a dropping funnel, a reflux condenser, and a thermometer with a gas inlet hole, /, 6-hexamethylene diisocyanate /+<<g (1 mol) , phenoxyethyl methacrylate/l, by diptyltin dilaurate co11 Hydroquinone 00-g was charged, t, o'
After raising the temperature to c, 2-hydroxyethyl acrylate)
Add dropwise g o ff (o, g moles).

Rather, it is cooled and maintained around boc during dropping.

After the dropwise addition, the mixture was heated and stirred at bOc for 3 hours, and as a result of infrared analysis, it was determined that the hydroxyl groups had completely disappeared, and unsaturated isocyanate (■) was obtained in the form of a pale yellowish brown liquid.

Side chain unsaturated bond type polymer (C) 100 parts unsaturated isocyanate 100 parts Irgacure manufactured by Ciba Corporation ÷ 6 st q parts (trade name, photosensitizer) were mixed and immediately mixed with a width of tso+, a length of 130 wm, and a thickness of 3 vam. After polishing, apply it to a length of 00ttsg with a knife coater on a steel plate that has been cleaned with trichlene, and then press a polyester film of the same size (thickness L) to give an output of ? OKw's UV irradiation device bottom oc
m at a speed of /OW15+ and cured. After curing, a T-peel test was performed on the device at -k.
y/cm 2 or higher, and could be used as an adhesive.

Example DA A photocurable resin having the same composition as that used in Example 3 was used with /jθ
A bonderite-treated steel plate of 10×10 OIII×/1 was coated with a bar coater to a thickness of 23μ, and 20cm was coated at 3m/3 under an ultraviolet irradiation device with an output of j OKw.
Passed it in minutes.

The hardness of the resulting coating film was C~JH, and the roughness test was "'"
/loo has excellent adhesion, and swmφ /ff 0
Even in the 0-bending test, no cracks or peeling of the coating film was observed.

Example 3 Synthesis of side chain unsaturated bond type resin (D) Styrene I
O'llJ, methyl methacrylate 1oop, co-hydroxyethyl methacrylate t, sg, ethyl acetate/, 3
/i, lauryl mercaptan/17. Charge azobisisobutyronitrile/17, raise the temperature in a nitrogen gas stream,
React under reflux of ethyl acetate for 6 hours.

After finishing, add hydroquinone o and tg. Especially.

Diphenylmethane diisocyanate ssog (1 mol)
Unsaturated isocyanate (IV) obtained by heating tetraxyethyl methacrylate/36g (hecomole) in boc for 6 hours without catalyst and confirming the disappearance of the hydroxyl group by infrared analysis. tin dilaurate ly
was added and reacted for 3 hours at 60C under a stream of dry air, and as a result of infrared analysis, it was confirmed that the free isocyanate groups had completely disappeared.

Add styrene 3309, about II! r Omall
Ethyl acetate is distilled off.

A side chain unsaturated bond type resin (D) of styrene solution was obtained in the form of a pale yellowish brown liquid.

Side chain unsaturated bond type resin (D) 700 parts unsaturated isocyanate (TV) so part styrene
20 parts cumene hydroperoxide
3 parts cobalt naphthenate, 0 parts talc were uniformly kneaded and immediately wetted with water/s.

WXko! The end of the slate board of WI4X4 Castle was covered with a tube cloth, crimped and left overnight.

3゜kg/cm2 in adhesive strength test by tensile shear
As a result, the slate broke.

Separately, the hardness of a putty applied to a 3-inch thickness on a water-wetted steel plate of 150III 11 x 10 O x J and hardened was 3-keH, and in a tensile adhesion test using an Elcometer, it was over g Okg/cm". The dolly was broken on the 11th side (epoxy resin adhesive side).

However, for a sample with the same composition except for unsaturated isocyanate (mV) &
The peeling occurred between the steel plate surface and the cured resin.

〔Effect of the invention〕

It exhibits strong adhesion even when applied to rusted or water-wet materials.

Claims (1)

[Scope of Claims] (A) A polymer having a (meth)acryloyl group in a side chain; (B) 0.1 equivalent or more of an isocyanate group and 0.1 equivalent or more of a (meth)acryloyl group in one molecule. and an unsaturated isocyanate having the following.