JP2003096143A - Curing resin composition and laminated structure containing curing resin layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curing resin excellent in close adhesion to a base material such as a metal, etc., dried and cured easily at a low temperature, and excellent in adhesion improving effect as a primer. SOLUTION: This curing resin composition contains a crosslinking (meth) acrylic polymer having a radical-polymerizable double bond and a radical- polymerizable monomer containing as an essential component a phosphoric ester monomer having a (meth)acryloyl group.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to, for example, curing by radical polymerization which can be used as a primer composition when forming a laminate in which a mortar layer or a resin concrete layer is laminated on a metal substrate with good adhesion. The present invention relates to a curable resin composition to be obtained, and a laminated structure having a cured resin layer made of this composition.

[0002]

2. Description of the Related Art A curable resin composition capable of radical polymerization is used in a wide variety of fields, and is also widely used in the field of civil engineering and construction. In the field of civil engineering and construction, a metal has recently been used as a base material, and different materials are joined to the metal to obtain a laminated structure, which is used as a member of a building or for repairing a road or the like. There is. However, a metal and a different material (for example, a cement mortar layer or a resin concrete layer) usually have poor adhesiveness, and a primer composition may be applied to the metal in order to improve the adhesiveness.

As a main component of such a primer composition, a radical-polymerizable (curable) resin capable of undergoing radical polymerization by heat or light to form a cured product is often used. Conventionally, a phosphoric acid ester having a polymerizing property has been blended with this curable resin to improve adhesion to a metal.

However, according to the inventors of the present invention, in spite of the fact that a construction site and a repair site such as a road are required to have a fast curing property and a quick drying property at a low temperature (for example, 5 ° C.) to room temperature. The phosphoric acid ester-containing curable resin has a problem that it is slow to dry and cure, especially at low temperatures, and the work efficiency is poor.

[0005]

Therefore, in the present invention, a curable resin which has excellent adhesion to a substrate such as a metal, can be dried and cured in a short time even at a low temperature, and has an excellent effect of improving adhesion as a primer. It is an object of the present invention to provide a composition and a laminated structure containing a cured resin layer obtained from the resin composition.

[0006]

The curable resin composition of the present invention has a crosslinkable (meth) having a radically polymerizable double bond.
The gist is that it contains an acrylic polymer and a radical-polymerizable monomer containing a phosphate ester monomer having a (meth) acryloyl group as an essential component. Since the (meth) acrylic polymer, which is the main component of the curable resin composition, has a radically polymerizable double bond,
We were able to achieve quick drying and quick curing.

The phosphoric acid ester-based monomer is preferably a compound represented by the following general formula because it has good polymerizability and good adhesion to metal.

[0008]

[Chemical 3]

[Wherein R ¹ represents hydrogen or a methyl group, and R ^{2 represents}
Is an optionally branched alkylene chain having 2 to 6 carbon atoms,
Alternatively, the following formula is shown, m is an integer of 1 to 10, and n is 1 or 2. ]

[0010]

[Chemical 4]

A curable resin composition containing a polyisocyanate compound is a preferred embodiment because it exhibits excellent adhesion even when the substrate (adherend) has a wet surface. The curable resin composition of the present invention is suitable as a primer composition.

In the present invention, a cured resin layer-containing laminated structure obtained by laminating a substrate, a cured resin layer obtained from the curable resin composition, and a mortar layer or a resin concrete layer, or a substrate. And a cured resin layer-containing laminated structure having a laminated structure in which a cured resin layer obtained from the curable resin composition and a mortar layer or a resin concrete layer are laminated.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The curable resin composition of the present invention has the greatest point in using a crosslinkable (meth) acrylic polymer having a radical polymerizable double bond as a main component. As a result of various studies on the above-mentioned problem of slow drying and curing of the phosphoric acid ester-containing curable resin, the present inventors have found that the phosphoric acid group inhibits the radical polymerization reaction. Here, an attempt was made to increase the amount of the initiator for the purpose of increasing the efficiency of the initiator, but the curing acceleration effect was insufficient. Then, by introducing a double bond into the polymer used for viscosity adjustment and volume shrinkage reduction, it was found that the drying time of the coating film of the resin composition is shortened, and rapid curing is achieved. It was the invention. Hereinafter, the present invention will be described in detail.

The curable resin composition of the present invention contains a crosslinkable (meth) acrylic polymer having a radically polymerizable double bond as a main component. A crosslinkable (meth) acrylic polymer having a radical-polymerizable double bond has a unit derived from a (meth) acrylic monomer as a main constituent unit and has a radical-polymerizable double bond in the molecule (side chain). And is capable of causing a polymerization reaction in the presence of a radical polymerization initiator. Therefore, the crosslinkable (meth) acrylic polymer can be copolymerized with a phosphoric acid ester monomer having a (meth) acryloyl group and a radically polymerizable compound used in combination as necessary. By using this crosslinkable (meth) acrylic polymer, it was possible to minimize the influence of the inhibition of polymerization by the phosphoric acid ester compound and accelerate the drying and curing of the coating film.

Further, the (meth) acrylic unit is selected as the main constituent unit because the (meth) acrylic polymer has various physical properties such as weather resistance, transparency and surface gloss, and appearance and safety. This is because it has excellent characteristics. In the present invention, the term "polymer" means a copolymer and a terpolymer or higher terpolymer, and the crosslinkable polymer means a polymer that can be polymerized.

The crosslinkable (meth) acrylic polymer has a polymerizable double bond in the molecule in order to obtain high polymerization reactivity.
It is preferable to have one or more. The polymerizable double bond equivalent of the crosslinkable (meth) acrylic polymer is not particularly limited, but is preferably 500 to 20,000, for example. If it is less than 500, cracks may occur in the cured resin layer obtained from the curable resin composition of the present invention, and if it exceeds 20,000, the cured resin layer may have poor heat resistance and solvent resistance. There is a fear. A more preferred lower limit is 3000 and an even more preferred lower limit is 4000. A more preferable upper limit is 15,000, and a still more preferable upper limit is 10,000. Here, the polymerizable double bond equivalent can be determined by (weight average molecular weight of polymer) / (average number of polymerizable double bonds contained in one molecule of polymer).

The molecular weight of the crosslinkable (meth) acrylic polymer is not particularly limited, and for example, the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) is 3000 to 10000.
It is preferably 00. If it is less than 3,000, the performance of the obtained cured resin layer will be deteriorated, and if it exceeds 1,000,000, the viscosity of the curable resin composition will be high, and workability such as coating may be impaired. A more preferable lower limit is 5,000, and an even more preferable lower limit is 10,000.
A more preferable upper limit is 100,000, a still more preferable upper limit is 60,000, a particularly preferable upper limit is 40,000, and a most preferable upper limit is 30,000. To measure Mw by GPC, for example, SC-80
20 system (manufactured by Tosoh Corporation), TS as a column
KgelGMH (manufactured by Tosoh Corporation) and tetrahydrofuran as a developing solvent can be used under the conditions of a solvent flow rate of 1 ml / min.

The method for producing the crosslinkable (meth) acrylic polymer is not particularly limited, and examples thereof include (meth) acrylic monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers and glycidyl groups. A containing monomer or a monomer having another functional group such as an amino group, an oxazolinyl group, an aziridinyl group (a monomer for introducing a double bond),
If necessary, by copolymerizing with other monomers, a functional group having reactivity with a functional group such as a carboxyl group, a hydroxyl group or a glycidyl group of a side chain of the obtained polymer. And a compound having a radical-polymerizable double bond (compound for double bond introduction) may be reacted. These compounds bond to the side chain and introduce a double bond into the polymer.

As the (meth) acrylic monomer, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t- Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate and other (meth) acrylic acid alkyl esters; cyclohexyl (meth) acrylate and other (meth) acrylic acid cycloalkyl esters; dimethylaminoethyl (meth ) Acrylate, basic (meth) acrylic acid esters such as diethylaminoethyl (meth) acrylate, and the like;
(Meth) acrylamide; (meth) acrylonitrile;
(Meth) acrylates of N-alkoxy-substituted (meth) acrylamides such as N-methoxymethyl acrylamide and N-ethoxymethyl acrylamide are mentioned, and one or more kinds can be used. Of these, methyl methacrylate is preferable.

Regarding the copolymerization ratio of the (meth) acrylic monomer in the polymer, the (meth) acrylic monomer is used in an amount of 50% by mass or more, and the rest is a monomer for introducing a double bond. “Other monomer” used by The (meth) acrylic monomer is more preferably 70% by mass or more, further preferably 80% by mass or more. However,
If there are too few double bond-introducing monomers, crosslinkability (meta)
Since the amount of double bonds introduced into the acrylic polymer decreases and the solvent resistance and the like of the cured resin layer decrease, the double bond equivalent is appropriately set as described above. When the double bond-introducing monomer has a (meth) acryloyl group, it can be counted as a (meth) acrylic monomer. The “other monomer” described below is preferably less than 50% by mass, more preferably 30% by mass or less.

Among the monomers for introducing a double bond, the carboxyl group-containing monomer may be any compound having a polymerizable double bond and a carboxyl group in the molecule, and is not particularly limited. is not. Specific examples include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinylbenzoic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid; monomethyl maleate and monoethyl maleate. , Monobutyl maleate, monooctyl maleate, monomethyl fumarate,
Monoesters of unsaturated dicarboxylic acids such as monoethyl fumarate, monobutyl fumarate, monooctyl fumarate, monoethyl citracone; long acid anhydride monoesters such as succinic acid monoester, phthalic acid monoester, hexaphthalic acid monoester Chain carboxyl group-containing monomer;
Etc. These carboxyl group-containing monomers may be used alone or in combination of two or more.

With respect to the carboxyl group introduced into the polymer by the above-mentioned carboxyl group-containing monomer, allyl glycidyl ether; glycidyl (meth) acrylate, methylglycidyl (meth) acrylate; epoxy resin mono (meth) acrylate, etc. By reacting a glycidyl group-containing monomer (compound for double bond introduction),
Double bonds can be introduced into the polymer side chains. These compounds may be used alone or in combination of two or more.

The reaction between the carboxyl group and the glycidyl group is carried out in the presence of a catalyst having at least one element selected from the group consisting of Zn, Sn and Zr, or a quaternary phosphonium salt, if necessary. Good.

The above glycidyl group-containing monomer is used as a part of the monomer for obtaining the (meth) acrylic polymer, and the glycidyl group is introduced into the polymer to obtain the above carboxyl group-containing unit amount. The compound can be reacted as a compound for introducing a double bond to obtain a crosslinkable (meth) acrylic polymer.

As the double bond-introducing monomer, a hydroxyl group-containing monomer can also be used. As a hydroxyl group-containing monomer, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate,
3-chloro-2-hydroxypropyl (meth) acrylate, 3-bromo-2-hydroxypropyl (meth) acrylate, 2-chloro-1- (hydroxymethyl) ethyl (meth) acrylate, 2-bromo-1- (hydroxy (Meth) such as methyl) ethyl (meth) acrylate
Acrylates; polyethylene glycol mono (meth)
Acrylate, polypropylene glycol mono (meth)
Mono (meth) acrylates of polyhydric alcohols having two hydroxyl groups such as acrylates; Di (meth) acrylates of tris (hydroxyethyl) isocyanuric acid, polyhydric groups having three or more hydroxyl groups such as pentaerythritol tri (meth) acrylate Partial (meth) acrylates of alcohols; ring-opening adducts of ε-caprolactone with 2-hydroxyethyl (meth) acrylate, and the like,
There is no particular limitation, and one kind or two or more kinds can be used.

The above hydroxyl group-containing monomer is (meth)
When used as a part of a monomer for obtaining an acrylic polymer and having a hydroxyl group introduced into the polymer, it has an isocyanate group and a radically polymerizable double bond as a compound for introducing a double bond. A compound may be used to introduce a double bond into the polymer by utilizing a urethane bond formation reaction.
Examples of such an isocyanate compound include m-isopropenyl-α, α-dimethylbenzyl isocyanate;
The reaction product of the above-exemplified (meth) acrylate having a hydroxyl group and a polyvalent isocyanate such as tolylene diisocyanate; isocyanatoethyl (meth) acrylate and the like, but not particularly limited, 1 type or 2 types The above can be used.

When the curable resin composition of the present invention is blended with a polyisocyanate compound described below and used as a primer composition, if the crosslinkable (meth) acrylic polymer has a hydroxyl group, the polyisocyanate is The crosslinking reaction proceeds between the compound and the crosslinkable (meth) acrylic polymer to further improve the physical properties of the cured resin layer, and further improve the adhesion to the wet substrate. Therefore, the amount of the hydroxyl group-containing monomer used in the polymerization and the amount of the above double bond-introducing compound should be adjusted so that the hydroxyl group remains in the crosslinkable (meth) acrylic polymer. Is desirable.

When synthesizing a crosslinkable (meth) acrylic polymer, in addition to the (meth) acrylic monomer and the monomer for introducing a double bond, which are essential components, other monomers are added. You may use. Examples of such monomers include styrene-based monomers such as styrene, α-methylstyrene, vinyltoluene, and chlorostyrene; vinyl esters such as vinyl acetate; allyl alcohol, ethylene glycol monoallyl ether, propylene glycol monoester. Allyl compounds such as allyl ethers; maleimide monomers such as N-phenylmaleimide, N-cyclohexylmaleimide, N-substituted maleimides such as N-isopropyl, and the like, and only one kind may be used, or 2 You may use together more than one kind.

When polymerizing the above-mentioned monomers, it is desirable to use a polymerization initiator. Specific examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, t-butyl peroxy-2-ethyl hexanoate, t-butyl peroxy octoate, t-butyl peroxybenzoate, cumene. Hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, bis (4
-T-butylcyclohexyl) peroxydicarbonate or other organic peroxide; 2,2′-azobisisobutyronitrile, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile or other azo compound; However, it is not particularly limited. These polymerization initiators may be used alone or in combination of two or more. The amount of addition of the polymerization initiator to the monomer raw material, the addition method, and the like can be appropriately set.

When the (meth) acrylic polymer is synthesized, it is desirable to add a chain transfer agent to the polymerization system in order to adjust the average molecular weight of the polymer. The chain transfer agent is not particularly limited, but a thiol compound that can extremely easily control the polymerization reaction is preferably used. Specific examples of the thiol compound include alkyl mercaptans such as t-butyl mercaptan, n-octyl mercaptan and n-dodecyl mercaptan; aromatic mercaptans such as thiophenol and thionaphthol; thioglycolic acid; octyl thioglycolate and ethylene glycol dithio. Thioglycolic acid alkyl ester such as glycolate, trimethylolpropane tris- (thioglycolate), pentaerythritol tetrakis- (thioglycolate); β-mercaptopropionic acid; octyl β-mercaptopropionic acid, 1,4-butanediol Β-mercaptopropion such as di (β-thiopropionate), trimethylolpropane tris- (β-thiopropionate), pentaerythritol tetrakis- (β-thiopropionate) Alkyl esters, and the like but is not particularly limited, may be used alone or in combination. Further, as the chain transfer agent, α-methylstyrene dimer, carbon tetrachloride or the like can be used. The amount of the chain transfer agent used may be appropriately set according to the type and combination of the monomers, and is preferably 0.1 to 15 mass% with respect to the total amount of the monomers.

The method for synthesizing the (meth) acrylic polymer is not particularly limited, and known polymerization methods such as bulk polymerization (bulk polymerization), solution polymerization, suspension polymerization and emulsion polymerization are adopted. However, bulk polymerization is particularly preferred. When suspension polymerization is adopted, the monomer may be suspended in a dispersion medium such as water using a dispersion stabilizer such as polyvinyl alcohol. Regarding the polymerization temperature, the reaction time, etc., known reaction conditions can be appropriately adopted depending on the polymerization method. Acrylic syrup (a mixture of a polymer component and a monomer component) is obtained by terminating the polymerization halfway by adding a polymerization inhibitor or rapidly cooling when synthesizing a (meth) acrylic polymer. ) Can be obtained at a stretch.

After synthesizing the (meth) acrylic polymer, the functional group of the double bond-introducing monomer used is reacted with the double bond-introducing compound as described above to obtain a side chain. A crosslinkable (meth) acrylic polymer having a double bond introduced into the chain can be obtained. When the compound for introducing a double bond is reacted, a known catalyst such as an esterification catalyst such as tetraphenylphosphonium bromide may be used, and a reaction may be carried out while optionally using a polymerization inhibitor together. The polymerization and the reaction for introducing the double bond can be simultaneously performed by selecting the conditions.

The curable resin composition of the present invention contains a phosphate ester monomer having a (meth) acryloyl group as an essential component in addition to the above-mentioned crosslinkable (meth) acrylic polymer. The phosphoric acid ester-based monomer having a (meth) acryloyl group can contribute to the polymerization and curing reaction (meth).
It is a compound having an acryloyl group and a phosphoric acid group that can contribute to the improvement of adhesion to a substrate such as a metal, and is used for introducing a phosphoric acid group into the skeleton of the cured resin layer.

The phosphoric acid ester-based monomer can be obtained by reacting phosphoric acid (orthophosphoric acid) with a hydroxyl group-containing (meth) acrylate or a glycidyl group-containing (meth) acrylate. It can also be obtained by reacting each glycidyl group of the epoxy resin with (meth) acrylic acid and phosphoric acid. As the hydroxyl group-containing (meth) acrylate and the glycidyl group-containing (meth) acrylate, any of those exemplified for the double bond-introducing monomer of the crosslinkable (meth) acrylic polymer can be used. Further, as the epoxy resin, a known bifunctional or higher functional epoxy resin can be used.

As the phosphoric acid ester-based monomer, compounds represented by the following general formula can also be preferably used.

[0036]

[Chemical 5]

[Wherein R ¹ represents hydrogen or a methyl group, R ²
Is an optionally branched alkylene chain having 2 to 6 carbon atoms,
Alternatively, the following formula is shown, m is an integer of 1 to 10, and n is 1 or 2. ]

[0038]

[Chemical 6]

Specifically, mono (2- (meth) acryloyloxyethyl) phosphate, mono (2- (meth))
Acryloyloxypropyl) phosphate, mono (2
Examples include-(meth) acryloyl polyoxyethylene glycol) phosphate, mono (2- (meth) acryloyl polyoxypropylene glycol) phosphate, bis (2- (meth) acryloyloxyethyl) phosphate, and mono (2- (meth ) Acryloyloxyethyl) phosphate, bis (2- (meth) acryloyloxyethyl) phosphate are particularly preferred. Mono (2-methacryloyloxyethyl) phosphate is, for example, "light ester P-1M" (manufactured by Kyoeisha Chemical Co., Ltd.), "Phosmer M" (manufactured by Unichemical Co., Ltd.).
Is marketed as.

The curable resin composition of the present invention comprises a crosslinkable (meth) acrylic polymer and a phosphoric acid ester monomer having a (meth) acryloyl group as essential components. In order to adjust the viscosity and the properties of the cured product,
It is preferable to add another radically polymerizable compound to obtain a crosslinkable (meth) acrylic syrup type compound.

As the radically polymerizable compound that can be used, the above-mentioned various monomers can be used as they are. Of these, methyl methacrylate and 2-hydroxyethyl (meth) acrylate are preferable. Also, a polyfunctional monomer having a plurality of double bonds can be blended.
Specific examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate and triethylene glycol di (meth).
Acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Polyfunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate; dicyclopentenyloxyethyl (meth) acrylate; epoxy acrylates; urethane acrylates; polyester acrylates; divinyl ethers A divinylbenzene, a diallyl phthalate, a diallyl isophthalate, a triallyl cyanurate, a triallyl isocyanurate and the like can be mentioned, and one kind or two or more kinds can be used. In addition,
In the present invention, oligomers are conveniently treated as "monomers". When the curable resin composition of the present invention is applied as a primer to, for example, a metal substrate, and then a mortar layer or a resin concrete layer is further laminated, dicyclopentenyloxyethyl (meta ) Acrylate is preferably used.

The curable resin composition of the present invention must contain the above-mentioned crosslinkable (meth) acrylic polymer, but other polymers may be partially used in combination. As the polymer that can be used in combination with the crosslinkable (meth) acrylic polymer, a crosslinkable polymer, if compatibility with various blending components is good,
Either a thermoplastic resin or a thermosetting resin can be used.
As such other polymerizable resin, in addition to curable resins such as unsaturated polyester resin and epoxy resin, poly (meth) acrylic polymer (PMMA) having no crosslinkability among the above-mentioned monomers is also used. Most preferred. Other than PMMA, a polymer composed of one or more kinds of the above-mentioned various monomers, a polymer of one or more kinds of monomers and methyl methacrylate, and the like are preferably mentioned. Total amount of polymer only 1
The amount of the above-mentioned crosslinkable (meth) acrylic polymer when set to 00% by mass is 20% by mass in order to effectively exhibit the characteristics of the crosslinkable (meth) acrylic polymer described above.
The above is preferable. It is more preferably 50% by mass or more, and most preferably 100% by mass.

The crosslinkable (meth) acrylic polymer in the curable resin composition of the present invention and other polymers which can be used in combination as necessary (these are collectively referred to as a polymer component) and a phosphoric acid-based monomer. When the total amount of the monomer and other monomers used as necessary (these are collectively referred to as a monomer component) is 100% by mass, the total amount of the polymer components is 1
It is preferable to adjust the ratio of both so as to be 0 to 90 mass%. When the amount of the monomer component is too large, the volume shrinkage during curing is large, which leads to the occurrence of cracks and the like, but when the amount of the polymer component is too large, the viscosity of the curable resin composition increases and the workability decreases. Not preferable. A more preferable lower limit of the amount of the polymer component is 20% by mass, and a further preferable lower limit is 30% by mass. Further, the more preferable upper limit of the amount of the polymer component is 80% by mass, and the still more preferable upper limit thereof is 70% by mass.
Hereinafter, a mixture of the polymer component and the monomer component,
It is called crosslinkable (meth) acrylic syrup.

The curable resin composition of the present invention contains a radical polymerization initiator (curing agent) for radically polymerizing a monomer component containing a crosslinkable (meth) acrylic polymer and a phosphoric acid monomer. Is preferably added. As the curing agent, the above-mentioned polymerization initiator can be used. The curing agent is preferably blended in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the crosslinkable (meth) acrylic syrup.

The curable resin composition of the present invention also comprises
Known curing accelerators such as amines such as N, N-dimethyl-p-toluidine and organic acid metal salts may be contained.
A combination of diacyl peroxides such as benzoyl peroxide as a curing agent and amines such as the above-mentioned toluidines as a curing accelerator is preferable from the viewpoint of fast curing property and low temperature curing property. The amount of the curing accelerator used is not particularly limited, and for example, 0.01 to 10 parts by mass, more preferably 0.1 to 4 parts by mass of the accelerator is used with respect to 100 parts by mass of the crosslinkable (meth) acrylic syrup. Preferably. The amount of the curing agent or accelerator used may be appropriately changed according to the working temperature (the amount is increased when the working temperature is low) to shorten the curing time.

The above crosslinkable (meth) acrylic polymer is synthesized and, if necessary, dissolved in a monomer component together with another polymer, or as described above, the polymerization is stopped halfway to obtain the crosslinkable (meth) The curable resin composition of the present invention can be obtained by obtaining an acrylic syrup and mixing the phosphate ester-based monomer with a curing agent or the like. You may mix a hardening | curing agent etc. just before construction.

The curable resin composition of the present invention comprises paraffin, wax, thixotropic agent (thixotropic agent, thixotropic agent), ultraviolet absorber, ultraviolet stabilizer, low-contracting agent, plasticizer, thickener. , Internal release agent, coupling agent,
It may contain known additives such as a polymerization inhibitor, a filler, an aggregate and a reinforcing material. These may be used alone or in combination of two or more. The amount of the additive is preferably 0 to 50 mass% with respect to 100 mass% of the resin composition. A more preferable upper limit is 40% by mass, and a still more preferable upper limit is 30% by mass.

When the curable resin composition of the present invention to which these additives are added as necessary is applied to the substrate, a cured resin layer is quickly formed. Therefore, the curable resin composition of the present invention can be used to form a protective film on various substrates. Further, the curable resin composition of the present invention is also suitably used as a primer composition for improving the adhesion between a material to be subsequently laminated and a substrate via an obtained cured resin layer. In any of the usage forms, as the base material, in addition to metal base materials such as iron, steel, copper, aluminum and alloys thereof, wood, plastic, glass, concrete, mortar, asphalt, resin concrete, etc. What is generally used in the field of civil engineering can be adopted. Moreover, you may use as a base material what already laminated | stacked various layers. The present invention also includes a cured resin layer-containing laminated structure having a structure in which a cured resin layer obtained from the curable resin composition of the present invention is laminated on these substrates.

When the curable resin composition of the present invention is used as a primer composition, any of the materials exemplified above as the substrate can be used as the material to be laminated next. Among them, the primer composition of the present invention exhibits excellent quick-curing and quick-drying properties and good adhesion to a metal substrate, so that when the metal substrate is laminated with the mortar layer or the resin concrete layer. Is preferable as the primer composition. Therefore, the most preferred embodiment of the laminated structure of the present invention is a laminated structure in which a substrate such as a metal, a cured resin layer, a mortar layer or resin concrete is laminated, or this laminated structure is It is a laminated structure having.

As the resin for forming the resin concrete layer, known resins such as unsaturated polyester resin and epoxy resin can be used, but (meth) acrylic syrup (which may or may not be crosslinkable). When an acrylic resin concrete containing (1) is used, the effect of improving the adhesiveness by the primer layer becomes very large. Incidentally, cement when forming a mortar layer or resin concrete layer,
Known materials can be used for sand such as silica sand and aggregates such as pebbles.
Inorganic fillers, reinforcing fibers, etc. may be added.

When the curable resin composition of the present invention is applied to a wet base material, it is preferable to use a polyisocyanate compound in combination. The polyisocyanate compound reacts with moisture in the air or on the surface of the base material, and the isocyanate group forms a urethane bond and is crosslinked and cured.
This improves the drying property of the base material and forms a barrier layer against the air on the surface of the coating film, which inhibits polymerization by oxygen when the crosslinkable (meth) acrylic syrup polymerizes and cures in the coating film. The action is suppressed and the curability is improved. The polyisocyanate compound also has the function of improving the adhesion of the cured resin layer to various base materials.

As the above polyisocyanate compound,
It is not particularly limited as long as it is a compound having two or more isocyanate groups, and for example, tolylene diisocyanate (80 / 20TD with an isomer ratio of 2,4 / 2,6 = 80/20).
I), 65/35 TDI, 2,4-100 TDI, diphenylmethane-4,4'-diisocyanate (pure or monomeric MDI) and its isomers, polymeric MDI, hexamethylene diisocyanate (HDI),
Trans-cyclohexa-1,4-diisocyanate (CHDI), isophorone diisocyanate (IPD
I), xylylene diisocyanate (XDI), naphthalene diisocyanate (NDI), p-phenylene diisocyanate (PPDI), 4,4'-diphenylmethane triisocyanate, triethylene diisocyanate, ethylene diisocyanate, 1,2-diisocyanate propane, 1,3 -Diisocyanate propane,
1,1'-methylenebis (4-isocyanatocyclohexane), tetramethylxylylene diisocyanate,
Lysine diisocyanate, 4,4'-methylenebis (cyclohexyl) isocyanate, methylcyclohexane-2,6-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, dimer acid diisocyanate, 2-isocyanatoethyl-2,6-diisocyanate hexaenol And other polyisocyanate monomers, and dimers and trimers thereof.
These may be used alone or in combination of two or more. A polymerizable polyisocyanate compound such as m-isopropenyl-α, α-dimethylbenzyl isocyanate and 2-isocyanatoethyl (meth) acrylate may be used.

Further, for example, an isocyanate group-containing prepolymer obtained by subjecting a compound having a hydroxyl group to an urethanization reaction with an excess polyisocyanate compound can also be used as the polyisocyanate compound. This urethanization reaction is preferably performed so that the NCO group / OH group ratio becomes 1.5 to 10. In this way, a polyisocyanate compound having a terminal isocyanate group or the like can be obtained.

The compound having a hydroxyl group is not particularly limited, and examples thereof include known polyols such as polyols and polyol polyesters; hydroxyl groups such as acrylic compounds having an hydroxyl group and allyl ether compounds, and a polymerizable double bond. And the like. These may be used alone or in combination of two or more.

In the curable resin composition, the crosslinkable (meth) acrylic syrup and the polyisocyanate compound may be blended so that the polyisocyanate compound is contained in an amount of 10% by mass or more based on 100% by mass. preferable. If it is less than this range, the effect of addition becomes insufficient. However, when it is more than 90% by mass, the amount of the crosslinkable (meth) acrylic syrup becomes too small and the adhesion to metal may not be sufficiently exhibited. Therefore, the polyisocyanate compound is preferably 90% by mass or less. The more preferable upper limit of the polyisocyanate compound is 70% by mass,
A more preferable upper limit is 50% by mass. When using the polyisocyanate compound, it may be dissolved in a solvent or the like and blended into the resin composition, if necessary.

[0056]

The present invention will be described in more detail with reference to the following examples, but the following examples do not limit the present invention.
All modifications and implementations that do not depart from the spirit of the description below are included in the technical scope of the present invention. In Examples and Comparative Examples, "part" means "part by mass", and "%" means "% by mass" unless otherwise specified.

Synthesis Example 1 Synthesis of methacryl syrup (1) A reactor equipped with a thermometer, a cooling pipe, a gas introduction pipe and a stirrer was charged with 96.5 parts of methyl methacrylate and 3.5 parts of methacrylic acid, and the reactor was prepared. The inside was replaced with nitrogen gas. Next, the temperature of this mixture is raised to 80 ° C. while stirring,
After 0.1 part of azobisisobutyronitrile (polymerization initiator) and 1.4 parts of mercaptopropionic acid (chain transfer agent) were added and a copolymerization reaction was carried out for 4 hours, air was introduced into the reaction system. Hydroquinone (polymerization inhibitor) at the same time as blowing
Polymerization was stopped by adding 0.01 part. Then, 4.0 parts of glycidyl methacrylate and tetraphenylphosphonium bromide (esterification catalyst: hereinafter TPP
After adding 0.1 part (referred to as B), the temperature was raised to 100 ° C., and the esterification reaction was carried out for 2.0 hours in an air atmosphere. A methacryl syrup having a solid content concentration of 42% and a viscosity of 1.8 Pa · s (25 ° C.) was obtained. This was designated as methacryl syrup (1).

When the weight average molecular weight (Mw) of the polymer in methacryl syrup (1) was measured by gel permeation chromatography (GPC), Mw was 17,000 in terms of polystyrene. For the measurement by GPC, SC-8020 system (manufactured by Tosoh Corporation) was used, TSKgelGMH (manufactured by Tosoh Corporation) as a column, and tetrahydrofuran as a developing solvent, and a solvent flow rate of 1 m.
It was performed at 1 / min.

Further, an appropriate amount of methacryl syrup (1) was sampled, dissolved in the same amount of acetone, and then dropped into 20 times the amount of methanol to separate the polymer, which was separated by filtration, drying and filtration. Using a nuclear magnetic resonance apparatus UNITY-plus (manufactured by Varian Japan), the separated polymer is subjected to proton nuclear magnetic resonance under the conditions of a resonance frequency of 400 MHz, a solvent of chloroform-d, a reference substance of tetramethylsilane, and an integration number of 10 times. Resonance analysis was performed to confirm that the double bond was introduced into the polymer. The polymerizable double bond equivalent of the polymer was 3600.

Synthesis Example 2 Synthesis of methacryl syrup for comparison A container equipped with a thermometer, a cooling pipe, a gas introduction pipe and a stirrer was charged with 100 parts of methyl methacrylate, and the inside of the reactor was replaced with nitrogen gas. Then, the temperature was raised to 80 ° C. with stirring, 0.1 part of azoisobutyronitrile and 1.4 parts of n-dodecyl mercaptan (chain transfer agent) were added, and 3.
Polymerized for 5 hours. At the same time as blowing air into the reactor, 0.01 part of hydroquinone was added to terminate the polymerization.
Comparative methacryl syrup 2 having a solid content concentration of 46% was obtained. The viscosity of this methacryl syrup 2 is 3.0 Pa.
-S and Mw were 26000.

Synthesis Example 3 194.8 parts of a bisphenol A type epoxy resin having an epoxy equivalent of 181 and 0.73 of triethylamine were placed in a synthesis reactor of a phosphoric acid ester-based monomer solution.
And 0.03 part of hydroquinone were charged, the temperature was raised to 104 ° C., and 38.7 parts of acrylic acid was added over 40 minutes. The esterification reaction was carried out for 1.5 hours while maintaining the temperature at about 101 ° C. A reaction product having an acid value of 0 and an epoxy equivalent of 489 was obtained. Charge 24.9 parts of this reaction product to another reactor,
Heated to 49 ° C. Then, 85% phosphoric acid aqueous solution 6.6
The aqueous phosphoric acid solution prepared by adding 2.1 parts of water to the parts was added dropwise over 30 minutes. Since the temperature increased to about 107 ° C, the temperature was maintained at 107 ° C for 1 hour. Solid content concentration 9
An acryloyl group-containing phosphoric acid ester aqueous solution having an acid value of 202 and 0.1% was obtained.

Synthesis Example 4 Synthesis of Polyisocyanate Compound In a reactor equipped with a thermometer, a cooling pipe, a gas introduction pipe and a stirrer, diphenylmethane-4,4′-diisocyanate (MDI, isocyanate group concentration 8.00 eq./k) was added.
g) 58.1 parts, 41.9 parts of polypropylene glycol having a weight average molecular weight of 1000, and 0.1 part of dibutyltin dilaurate (catalyst) were charged and reacted at 60 ° C. for 2 hours to react 100% of hydroxyl groups. It was Solid content concentration 100%, isocyanate group concentration 3.81e
q. A polyisocyanate compound having a viscosity of 5 kg / kg and a viscosity of 5 Pa · s was obtained.

Examples 1 to 4 and Comparative Examples 1 to 3 Curable resin compositions having the compounding ratios shown in Table 1 were prepared. The curing agent (niper FF; benzoyl peroxide; powder product; purity 50%; manufactured by NOF CORPORATION) was used at 2.0 parts in the evaluation at 25 ° C. and 6.0 parts in the evaluation at 5 ° C. . After the composition was prepared, the concrete panel had 0.
3 kg / m ^2, the steel sheet so that the coating weight of 0.1 kg / m ^2, the curable resin composition was applied with a roller, to cure the resin layer. Before applying the resin composition, the concrete panel, the steel plate and the curable resin composition are adjusted to 25 ° C. in the evaluation at 25 ° C., and the concrete panel, the steel plate and the curable resin composition are evaluated in the evaluation at 5 ° C. Was adjusted to 5 ° C. As a concrete panel, JIS concrete pavement board (300 × 300 × 60 mm; manufactured by Nippon Test Panel Co., Ltd.)
Was dried at room temperature to clean the surface before use. As the steel plate, a surface sandblasted product of SS400 (JISG 3101) (manufactured by Nippon Test Panel Co., Ltd.) was used after being degreased with acetone.

After applying the curable resin composition to the steel sheet, it was left at each measurement temperature, the degree of curing and drying of the resin layer was confirmed by touching with a finger, and the time until drying was measured. The results are also shown in Table 1.

Separately, 60 parts of methacryl syrup (1),
Methyl methacrylate 40 parts, the Niper FF2.0
Parts, curing accelerator (N, N-dimethyl-p-toluidine;
Wako Pure Chemical Industries, Ltd.) 0.2 parts, paraffin wax 140
(Paraffin wax; manufactured by Nippon Seiro Co., Ltd.) 0.5 part was mixed, and 100 parts of silica sand No. 8 and 50 parts of silica stone powder (both silica sand and silica stone powder were manufactured by Sanei Mining Co., Ltd.) were added as an aggregate to prepare resin concrete. It was adjusted.

For each sample for evaluation at 25 ° C., 0.7 kg of the resin concrete was placed on the cured resin layer after the layer of the cured resin composition was dried and cured (after the drying time shown in Table 1). / M ² applied and cured. After standing for 4 days at 25 ° C., a laminated structure composed of concrete-cured resin layer (primer layer) -resin concrete layer and a laminated structure composed of steel plate-cured resin layer (primer layer) -resin concrete layer were constructed. Ken-type adhesive strength measurement was performed. In the case of the laminated structure in which the base material is concrete, when the adhesive strength was 30 kg / cm ² or more, the base material was broken, so that it was shown as> 30 in the table.

[0067]

[Table 1]

The examples of the present invention are not limited to 25 ° C. but 5 ° C.
Also in the case of the above, the drying time was short, and quick drying and quick curing could be achieved. In Comparative Example 1, since the phosphoric acid ester-based monomer is not used, the drying time is short, but when the steel plate is used as the base material, the adhesion is low. In Comparative Example 2, since methacryl syrup that is not crosslinkable was used, it was found that the drying time was prolonged due to the polymerization inhibitory action of the phosphoric acid ester monomer. In Comparative Example 3, since only the monomer was used instead of the syrup, it took a long time to dry and cure.

Example 5 As a base material, wet concrete was used in which the concrete panel was immersed in water for 24 hours and lightly wiped off with water.
A curable resin composition having the same composition as in Example 2 was added to Synthesis Example 4
30 parts of the polyisocyanate compound obtained in 1 was added and mixed, and in the same manner as in Example 1, 0.3 kg / m ² was applied to the concrete panel (dry product) and 0.1 kg / m ^{2 was applied to} the steel plate.
m ^2, was 0.3kg / m ² applied to the wet concrete surface. The coating film on the surface of the steel sheet was dried at 25 ° C for 25 minutes and at 5 ° C for 30 minutes. Further, in the same manner as in the first embodiment,
Concrete using resin concrete (dry product)
-Cured resin layer (primer layer) -Laminated structure composed of resin concrete layer, steel plate-Cured resin layer (primer layer) -Laminated structure composed of resin concrete layer and wet concrete layer-Cured resin layer (primer layer) -Resin A laminated structure consisting of concrete layers was manufactured and the Kenken-type adhesive strength measurement was performed. The laminated structure composed of concrete (dry product) -cured resin layer (primer layer) -resin concrete layer and the wet concrete layer-cured resin layer (primer layer) -resin concrete layer both have adhesive strength. More than 30 kg / cm ² ,
Substrate destruction occurred. Further, the laminated structure composed of the steel plate-cured resin layer (primer layer) -resin concrete layer had cohesive failure at 40 kg / cm ² .

[0070]

The curable resin composition of the present invention essentially contains a crosslinkable (meth) acrylic polymer and a phosphate ester monomer having an effect of improving adhesion to a metal substrate. Since the polymerization inhibitory action of the phosphoric acid ester-based monomer is compensated by the high reactivity of the crosslinkable (meth) acrylic polymer, the coating film can be quickly dried and cured. Further, since the phosphoric acid group is introduced into the polymer skeleton of the cured resin layer, the adhesion to a metal substrate is particularly good. Furthermore, when a polyisocyanate compound is used in combination,
The base material adhered well even in a wet state.

Therefore, the curable resin composition of the present invention is useful as a composition for forming a cured resin layer on the surface of a base material or for forming a primer layer in various fields including the field of civil engineering and construction. Is.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 4/00 C09D 4/00 5/00 5/00 DF term (reference) 4F100 AB02 AE01C AE11C AK01A AK01C AK25A AK51A AL05A AT00B BA03 BA07 BA10A BA10C CA02 EH46 EH462 EJ05A EJ08 EJ08A EJ082 EJ34 EJ341 GB07 JL11 JM02A 4J027 AA02 AC02 AE01 BA07 BA20 BA22 BA26 BA28 BA29 CB03 PA02 PA12 PA12 NA12 NA12 NA02 NA12 NA12 NA12 NA02 NA11 FA02 NA11 FA02 NA11 FA02 NA11 PC04 PC06 PC08

Claims (6)

[Claims] 1. A crosslinkable (meth) acrylic polymer having a radical polymerizable double bond, and a radical polymerizable monomer containing a phosphate ester monomer having a (meth) acryloyl group as an essential component. A curable resin composition comprising: 2. The curable resin composition according to claim 1, wherein the phosphoric acid ester-based monomer is a compound represented by the following general formula. [Chemical 1] [In the formula, R ¹ represents hydrogen or a methyl group, R ² represents an optionally branched alkylene chain having 2 to 6 carbon atoms, or the following formula, m is an integer of 1 to 10, and n is 1 Or represents 2. ] [Chemical 2] 3. The curable resin composition according to claim 1, further comprising a polyisocyanate compound. 4. The curable resin composition according to claim 1, which is used as a primer composition. 5. A laminate comprising a base material, a cured resin layer obtained from the curable resin composition according to any one of claims 1 to 4, and a mortar layer or a resin concrete layer. And a cured resin layer-containing laminated structure. 6. A laminate structure in which a substrate, a cured resin layer obtained from the curable resin composition according to any one of claims 1 to 4, and a mortar layer or a resin concrete layer are laminated. A characteristic cured resin layer-containing laminated structure.