JPH09227639A - Curable composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable compsn. which forms a waterproof layer usable for a pavement structure, etc., and forms a film having a cure rate little dependent on the ambient temp. and excellent in characteristics such as weatherability, low-temp. flexibility, resistances to abrasion and fatigue, balance between tensile strength and elongation, etc. SOLUTION: This compsn. at least contains a reactive acrylic polyurethane- modified composite oligomer, at least one alkyl (meth)acrylate, a petroleum wax having an m.p. of 40 deg.C or higher, and a polymn. inhibitor. Pref. the compsn. further contains a high-molecular compd. which has a wt.-average mol.wt. of 500,000 or lower and is sol. in the alkyl (meth)acrylate. The reactive oligomer is obtd. by reacting a diisocyanate compd., a polyoxyalkylene glycol or polyol having a mol.wt. of 600-3,000, and if necessary, a chain extender and at least one (meth)acrylic ester having at least one active hydrogen group.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable composition that can be used as a waterproof layer formed on a base substrate in a pavement structure or the like that requires waterproofness. Specifically, it can be used as a bridge pier on a road, a floor or a slope of a multi-storey parking lot, a factory, a warehouse, a stand portion of a stadium, or a waterproof layer for a veranda or a corridor. Furthermore, the curable composition of the present invention can also be used as a binder for the surface coating of the above facilities.

[0002]

2. Description of the Related Art Conventionally, as a material used for a waterproof layer of a waterproof pavement structure, epoxy resin, polyurethane resin, petroleum resin, etc., a resin which is polymerized and cured by an addition reaction or a condensation reaction, or an unsaturated polyester Resins such as resins and (meth) acrylic acid ester-based resins that are cured by radical reaction, and epoxy acrylate resins, polyester acrylate resins, etc., as a composite type resin of these, alone or in a mixture with a polymerizable unsaturated monomer. Used in form.

[0003]

However, although the epoxy resin exhibits excellent properties in alkali resistance and mechanical strength, it lacks flexibility and is apt to crack, and has insufficient weather resistance. Has excellent acid resistance, but has the drawback that it lacks flexibility like epoxy resin and has a large curing shrinkage. On the other hand, polyurethane resin is excellent in elasticity, flexibility, and abrasion resistance, but has problems in chemical resistance and weather resistance. Further, these resins commonly have the problems that the curing time is long and the curing rate is highly dependent on the environmental temperature. (Meth) acrylic acid ester resins are excellent in weather resistance and load resistance, but have problems in acid resistance, elasticity and abrasion resistance.

In order to make up for the drawbacks of these resins, so-called vinyl ester resins such as vinyl acrylate and polyester acrylate having a (meth) acrylate group at the molecular end, and these vinyl ester resins and polymerizable unsaturated monomers. A mixture of is proposed. These resins have the performance as composite materials and are excellent in weather resistance, resistance to moisture and heat deterioration, and low temperature flexibility, but satisfactory in tensile strength and elongation balance, wear resistance, and fatigue resistance characteristics. The characteristics that do not have been obtained.

[0005]

The present invention is directed to a reactive (meth) acrylic polyurethane modified composite oligomer, at least one (meth) acrylic acid alkyl ester, a petroleum wax having a melting point of 40 ° C. or higher, and a polymerization inhibitor. And a polymer compound having a weight average molecular weight of 500,000 or less, which is soluble in the (meth) acrylic acid alkyl ester monomer.
It further relates to the curable composition added. The expression “(meth) acrylic” described herein means that it is a derivative of acrylic acid and / or a derivative of methacrylic acid, and a double bond derived from acrylic acid and / or methacrylic acid is used. Indicates having.

The acrylic double bond has a high reaction rate, and the influence of the ambient temperature on the curing time is small, and the use of the reactive (meth) acrylic polyurethane-modified composite oligomer makes the characteristics of polyurethane more than acrylic resin. It is possible to impart elasticity, especially low-temperature flexibility, and obtain an excellent waterproof film or coating film.

The reactive acrylic polyurethane modified composite oligomer used in the present invention comprises a diisocyanate compound, a polyoxyalkylene glycol having a molecular weight of 600 or more and 3000 or less, and an organic compound having at least two active hydrogen groups in an excess isocyanate group. An NCO-terminated prepolymer obtained by reacting
It is a reactive acrylic polyurethane modified composite oligomer obtained by reacting at least one kind of (meth) acrylic acid ester having at least one active hydrogen group. "Organic compound having at least two active hydrogen groups" means "polyol" or both "polyol" and "chain extender" in the polyurethane art.

Since such an oligomer has a double bond derived from acrylic acid and / or methacrylic acid, that is, an acrylic double bond at the terminal, it can be copolymerized with the (meth) acrylic ester which is a component of the composition. And above,
Particularly, a polymer excellent in low temperature flexibility is formed.

It is also preferable to use a chain extender together with the polyol as one of the components forming the oligomer. The chain extender is a polyfunctional compound having a relatively low molecular weight and is bonded to a diisocyanate compound to form a segment having high cohesive force.
Various characteristics such as hardness, strength, flexibility and low temperature characteristics of the urethane portion can be arbitrarily set by selecting a combination of diisocyanate compounds and a composition ratio. As the polyoxyalkylene glycol forming the polyurethane portion, it is preferable to use polyoxytetramethylene glycol. Polyurethanes using polyoxytetramethylene glycol exhibit particularly excellent physical strength, low-temperature flexibility, and resistance to wet heat deterioration.

As one component of the composition of the present invention, it is preferable to add a polymer compound which is soluble in (meth) acrylic acid alkyl ester and has a weight average molecular weight of 500,000 or less. The addition of such a polymer compound makes it possible to accelerate the apparent curing of the composition. When the molecular weight of this polymer compound exceeds 500,000, it becomes difficult to dissolve it in the (meth) acrylic acid alkyl ester, and the solution viscosity of the composition becomes too high, which makes the construction difficult.
The lower limit of the molecular weight of the polymer compound is not particularly limited, and it can be used as long as a gel effect is exhibited in the curing reaction, particularly in radical polymerization.

The curable composition of the present invention contains a polymerization inhibitor and suppresses alteration in the distribution process.
If it is applied on the substrate as it is, the curing time may not always be shortened. Therefore, in use, it is a preferred embodiment to add an appropriate amount of the curing catalyst.

Further, when the curable composition of the present invention is applied on concrete, it is preferable to use a primer for strengthening the adhesion between the concrete and the curable composition, if necessary.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The curable composition of the present invention comprises at least one reactive (meth) acrylic polyurethane modified composite oligomer, at least one acrylic acid alkyl ester or at least one methacrylic acid alkyl ester, and a melting point of 40.
A petroleum wax having a temperature of not less than 0 ° C., and a polymerization inhibitor are contained, and a high molecular weight polymer and other components and additives are added, dissolved, and mixed, if necessary. The reactive (meth) acrylic polyurethane-modified composite oligomer used in the present invention has a polyurethane portion and a (meth) acrylic 2
It is an oligomer having a heavy bond, and is synthesized by the following means, for example.

A diisocyanate compound is reacted with a polyoxyalkylene glycol having a molecular weight of 600 or more and 3000 or less and an organic compound having at least two active hydrogen groups so as to have an excess of isocyanate groups to obtain an isocyanate group (NCO) -terminated prepolymer. . Next, the obtained NCO-terminated prepolymer is reacted with (meth) acrylic acid ester having at least one active hydrogen group, that is, one or more kinds of acrylic acid ester or methacrylic acid ester. In this case, the NCO / OH ratio finally becomes 1.0.

During the synthesis of the NCO-terminated prepolymer,
The NCO / OH equivalent ratio is in the range of about 1.5 to 2.5, preferably about 2.0. If the equivalent ratio is too small, the concentration of the acrylic double bond in the oligomer becomes too low, and if it is too large, only the (meth) acrylic acid ester is bonded to the diisocyanate compound, and a compound having no so-called soft segment part is obtained. A large amount will be mixed, which is not preferable.

Examples of the (meth) acrylic acid ester having an active hydrogen group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, N-methylol (meth) acrylamide and the like. .

The chain extender is used in both the prepolymer synthesis step and the (meth) acrylic acid ester reaction step.
Also, both can be added and reacted,
In general, in consideration of the high reactivity of the low molecular weight component, it is preferable to react after the prepolymer synthesis, before the reaction with the active hydrogen-containing (meth) acrylic acid ester, or at the same time. In particular, a method in which a polyol and a diisocyanate compound are reacted to form an NCO-terminated prepolymer, which is then reacted with a chain extender, and an excess isocyanate group is reacted with an active hydrogen-containing (meth) acrylic acid ester is a reactive oligomer synthesis. Preferred as a method. The reactive (meth) acrylic polyurethane modified composite oligomer (hereinafter, simply referred to as "reactive oligomer").
3000 following polyoxyalkylene glycol molecular weight of 600 or more for use in the production of are those represented by the general formula _{HO- (R-O) n H} , R is a straight-chain having 2 to 5 carbon atoms Alternatively, it is a branched alkylene group.

The polyoxyalkylene glycol is synthesized, for example, by ring-opening polymerization of a cyclic ether having the above alkylene group based on a low molecular weight active hydrogen-containing compound. As the cyclic ether, one or more kinds are arbitrarily selected from ethylene oxide, propylene oxide, oxetane, tetrahydrofuran and the like, and they are used as a homopolymer, a random copolymer or a block copolymer. The most preferred material is polyoxytetramethylene glycol (PTMG).

When the molecular weight of the polyoxyalkylene glycol is 600 or less, the flexibility of the cured product finally obtained is not satisfactory, and when it is 3000 or more, the acrylic double in the reactive oligomer is The concentration of the bond may be reduced, causing problems in terms of cure speed.

Organic compounds having at least two active hydrogen groups are well-known materials in the polyurethane technical field as "polyols" and "chain extenders". Polyols are classified into ether type, ester type, etc., depending on the application. It is selected appropriately. The ether-based polyol is the above-mentioned polyoxyalkylene glycol, which is a constituent feature of the present invention, and the same or different ones may be used. For example, polyoxytetramethylene polyol (P
TMG), polyoxypropylene polyol (PP
G), polyoxyethylene polyol, etc. can be used. Further, as the ester-based polyol, polyethylene adipate (PEA), polybutylene adipate (PB)
A), polycaprolactone polyol (PCL) and the like are exemplified. (Note that "G" in PTMG and PPG
Is originally derived from "glycol", but in the industry it is 3
It means a generic name including more than sensuality). Other than this, polycarbonate polyol, polybutadiene polyol and the like can be used, and further, copolymers thereof, for example, a block copolymer of PTMG and caprolactone can be used. These copolymers include, for example, a method of ring-opening copolymerization of ε-caprolactone with PTMG, tetrahydrofuran or ethylene oxide with polyester polyol,
It can be synthesized by a method such as ring-opening copolymerization of propylene oxide. In addition, polyols include those having an amino group instead of a hydroxyl group, and there are commercially available products (for example, products of Ihara Chemical Co., Ltd.).

As the chain extender, ethylene glycol,
1,4-butanediol, neopentyl glycol,
Glycols such as 1,6-hexanediol, spiroglycol, bishydroxyethoxybenzene and methylenebis-o-chloroaniline, and diamines can be used. In addition, a trifunctional or higher-functional polyfunctional chain extender such as trimethylolpropane may be used depending on the required properties.

The diisocyanate compound is a compound having two or more isocyanate groups in the molecule,
Well-known ones can be used. Such an isocyanate compound can be roughly divided into an aromatic isocyanate compound and an aliphatic isocyanate compound, and both can be used,
When the curable composition of the present invention is used as a binder for paints, the use of an aliphatic isocyanate is preferred from the viewpoint of little discoloration, particularly yellowing. As such an isocyanate compound, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI) and the like as the aromatic isocyanate compound, and hexamethylene diisocyanate (HDI) as the aliphatic diisocyanate compound, Cyclohexane diisocyanate (C
HDI), hydrogenated MDI (HMDI, trade name Hiren-W, manufactured by Huls), isophorone diisocyanate (IPDI), m-xylylene diisocyanate (XD).
I), tetramethylxylylene diisocyanate (TM)
XDI), hydrogenated m-xylylene diisocyanate (HXDI) and the like can be exemplified, and a prepolymer which is a reaction product of these with a low molecular weight glycol and other adducts can also be used. These isocyanate compounds may be used alone or in combination of two or more. Instead of using a trifunctional or higher functional polyol or a chain extender, or simultaneously using a trifunctional or higher functional isocyanate compound.

When synthesizing the reactive oligomer, a catalyst may be used if necessary. The reaction of active hydrogen atoms, particularly hydroxyl groups, with isocyanate groups is promoted by metal-based catalysts such as dibutyltin dilaurate and amine-based catalysts such as diazabicyclooctane (trade name Dabco). It is also well known to use a metal-based catalyst and an amine-based catalyst together.

Specific examples of the (meth) acrylic acid alkyl ester used in the present invention include methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate and tributyl acrylate. Examples thereof include methylolpropane triacrylate and the like, and monomers obtained by adding a functional group thereto. Also, as methacrylic acid ester,
Alkyl methacrylate, specifically methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, lauryl methacrylate, trimethylolpropane trimethacrylate, glycidyl methacrylate, methoxydiethylene methacrylate, methoxypolyethylene Examples include glycol methacrylate, allyl methacrylate, and the like, and monomers obtained by adding a functional group to these.

The range of the blending ratio of the oligomer and the (meth) acrylic acid ester monomer is not particularly limited as long as the physical properties of the cured product obtained by curing the curable composition of the present invention meet the purpose. However, the range of oligomer / monomer = 10 to 70/90 to 30 (weight ratio) is preferable. When the amount of the oligomer is 10 or less, the effect derived from the oligomer may not be sufficiently exerted depending on the material used, and when it is 70 or more, the viscosity of the composition may increase depending on the material used, and the oligomer itself may be insufficient. Inhibition of the curing reaction due to steric hindrance may be excited. That is, it is within the above range that stable characteristics are obtained.

If desired, an ethylenically unsaturated monomer having two or more polymerizable double bonds in the molecule may be used in combination. Examples of such an ethylenically unsaturated monomer include alkanediol diacrylates such as ethylene glycol diacrylate, 1,2-propylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,6-hexanediol diacrylate. Kind,
Di- or polyoxyalkylene glycol diacrylates such as diethylene glycol diacrylate, dipropylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, divinylbenzene, diallyl phthalate, triallyl phthalate, triallyl cyanurate, triallyl Examples thereof include isocyanurate, allyl acrylate, diallyl fumarate and the like. In the above compound, a metacrylic acid ester may be used instead of an acrylic acid ester, and these compounds may be used alone or in combination of two or more kinds.

The amount of the ethylenically unsaturated monomer added is
In the range of the blending ratio of the oligomer and the (meth) acrylic acid ester monomer, it is preferable to blend by substituting a part of the (meth) acrylic acid ester monomer, and the addition amount is obtained by reacting and curing. There is no particular limitation so long as the cured product satisfies the required characteristics.

The petroleum wax component having a melting point of 40 ° C. or higher is
It is added for the purpose of providing an air barrier effect during the formation of the curable coating layer, and imparting gloss, stain resistance, moisture resistance and waterproofness to the surface of the curable coating layer. Examples of such petroleum wax components include paraffin wax 11
5, paraffin wax 135, paraffin wax 1
55 (all manufactured by Nippon Seiro Co., Ltd.) and the like having 20 to 40 carbon atoms
Paraffin wax composed of hydrocarbons having a molecular weight of about 300 to 500 and Hi-Mic-204
5, Hi-Mic-1070, Hi-Mic-2095
(All manufactured by Nippon Seiro Co., Ltd.) and other microcrystalline waxes composed of hydrocarbons having a carbon number of about 30 to 60 and a molecular weight of about 500 to 800, and JP-150.
No. 0, JP-064R (both manufactured by Nippon Seiro Co., Ltd.) and the like. Further, these petroleum waxes may be modified by an oxidation reaction or a polyaddition reaction, and two or more kinds of the above petroleum waxes may be used in combination. In this case, if the lower limit of the melting point of the mixture is 40 ° C. or higher, the mixing ratio can be appropriately changed according to the purpose of use. The amount of addition is generally set in the range of 0.1 to 5 parts, preferably 0.1 to 100 parts based on 100 parts of the total amount of the reactive oligomer and (meth) acrylic acid alkyl ester components.
-3 parts, particularly preferably 0.2-2 parts. That is, if the amount is less than 0.2 parts, the curability of the curable composition tends to be deteriorated, and conversely, if it exceeds 2 parts, the appearance of the curable coating layer is poor and adhesion inhibition during repeated coating occurs. Can be seen. However, depending on factors such as compatibility between the petroleum wax and the resin-forming component, addition in an amount of 0.1 to 5 parts may cause no problem. Further, when a petroleum wax having a melting point of 40 ° C. or lower is used, it is difficult for the curable composition to bleed to the air interface side when the curable composition is cured, impairing the air barrier property, and as a result, the curability tends to be impaired.

The polymerization inhibitor is used for maintaining the storage stability of the curable composition and adjusting the curing rate. Examples of this polymerization inhibitor include hydroquinone, monomethoxyhydroquinone, 2,6-di-t-butyl-p-cresol, and 2-t-butyl-p-cresol. Among these, it is easy to control the addition amount,
It is preferable to use 2,6-di-t-butyl-p-cresol and 2-t-butyl-p-cresol. Generally, the compounding ratio of the polymerization inhibitor is 10 in total for the reactive oligomer and the alkyl (meth) acrylate component.
It is set in the range of 0.001 to 0.005 parts with respect to 0 parts, and preferably in the range of 0.002 to 0.003 parts. That is, if it is less than 0.001 part, the effect of inhibiting polymerization may not be obtained, and conversely 0.005
This is because if it exceeds the amount, the curing reaction of the curable composition may be hindered.

The weight average molecular weight is 500,000 or less,
As the polymer substance soluble in (meth) acrylic acid alkyl ester, for example, delapet 60N, delapet 6
70N, Delapet SR (all manufactured by Asahi Kasei Corporation)
Such as methacrylic resin and Dick Elaststyrene # 200
(Dainippon Ink and Chemicals, Incorporated), Denkastyrol HRM-2 (produced by Denki Kagaku, Ltd.), and other styrene resins.

The curable composition of the present invention can be cured by a so-called redox catalyst which is a combination of a curing agent and a curing accelerator. Examples of the curing agent include benzoyl peroxide, methyl ethyl ketone peroxide, bis (4-t-butylcyclohexyl)
Organic peroxides such as peroxydicarbonate and dicumyl peroxide are used, but the addition amount is about 0.1 to 10 parts with respect to 100 parts of the curable composition.

Examples of the curing accelerator include cobalt salts such as cobalt naphthenate and cobalt octenoate, and aromatic tertiary amines. These cobalt salts and aromatic tertiary amines may be used alone or in combination. Examples of aromatic tertiary amines include N, N
-Dimethylaniline, N, N-dimethyltoluidine,
N, N-diethyltoluidine, N, N-diethylanisidine, N, N-dimethyl-p-chloroaniline, N, N
-Dimethylaminobenzaldehyde, N, N-di (2-
Hydroxyethyl) -p-toluidine, N, N-di (2
-Hydroxypropyl) -p-toluidine, N, N-di (2-hydroxyethyl) alinine, N, N-di (2-
Hydroxypropyl) alinine, and the like. Of these, N, N-di (2-hydroxyethyl) -p-toluidine, N, N-di (2-hydroxypropyl) -p
-Toluidine, N, N-di (2-hydroxyethyl) alinine, N, N-di (2-hydroxypropyl) alinine are preferred.

The organic peroxide type curing agent has a molecular weight of −0-0.
It has a -bond, and normally, the -0-0-bond is decomposed by physical energy such as heat to generate a free radical, whereby the curing reaction proceeds. Further, by using a curing accelerator in combination, the -0-0-bond is decomposed by the redox reaction mechanism and a free radical is generated. In this case, the curing rate can be easily adjusted by the type and the amount of the curing accelerator used together. In particular, a mechanism in which free radicals are generated through the formation of a charge transfer complex in the decomposition process by the redox reaction mechanism is desirable. Examples of the combination of the curing agent and the curing accelerator having the decomposition mechanism include a combination of benzoyl peroxide and N, N-di (2-hydroxyethyl) -p-toluidine.

If the amount of the curing accelerator is within the range of the addition amount of the above-mentioned curing agent, 0.2 to 0.
Used in the range of about 6 parts. When the amount of the curing accelerator exceeds 0.6 parts, depending on the environmental temperature condition of the curing reaction, the radical generation amount increases and the molecular weight of the cured product decreases, so the tensile strength of the cured product decreases and the residual monomer also increases. Tend. Further, when the amount of the curing accelerator is less than 0.2 part, the amount of radicals generated and the heat of reaction are reduced, and the termination reaction is likely to occur, which may result in poor curing.

These curing agents and curing accelerators are usually added to and mixed with the curable composition immediately before the curing reaction such as coating operation. When an aromatic tertiary amine is used as the curing accelerator, it is used alone. Since the curing reaction does not proceed, it can be added to the curable composition in advance and stored.

[0036]

Embodiments of the present invention will be described below. [Reactive Oligomer Production Example] (Oligomer Production Example 1) A 4-liter flask with a capacity of 1 liter equipped with a stirrer, a reflux condenser, a nitrogen introduction tube and a thermometer was placed in a nitrogen stream under a nitrogen stream to give polyoxytetrahydrofuran having a molecular weight of 1500 Methylene glycol 375g (0.25mo
1), and 250.4 g (0.25 mol) of butylene adipate glycol having a molecular weight of 1000 were charged at 80 ° C.
After heating to isophorone diisocyanate (IPDI)
222.4 g (1.0 mol) was added, and the mixture was stirred and reacted while adjusting the temperature in the reaction system to 70 to 75 ° C., and reacted until the residual isocyanate group concentration reached 50 mol%. Then add 1,4-butanediol to 1
3.52 g (0.15 mol) was added, and the mixture was stirred and reacted for 30 minutes while adjusting the temperature in the reaction system to 70 to 75 ° C in the same manner, and then 110.4 g (HEMA) of hydroxyethyl methacrylate (HEMA) was added. 0.85 mol) was added, and the reaction was continued until the residual isocyanate group became 0%. The reaction mixture was cooled to 20 ° C. to give a viscous reactive oligomer.

(Oligomer Production Example 2) A 4-liter flask with a capacity of 1 liter equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer was placed under a nitrogen stream and a molecular weight of 100.
250 g of 0 polyoxytetramethylene glycol
(0.25 mol) and 250.4 g (0.25 mol) of butylene adipate glycol having a molecular weight of 1000 were charged, and after heating to 80 ° C., 174.2 g (1.0 mol) of toluene-2,4-diisocyanate (TDI) was added. While stirring so that the temperature in the reaction system becomes 70 to 75 ° C., the mixture is stirred and reacted, and the residual isocyanate group concentration becomes 5
The reaction was allowed to reach 0 mol%. Next, 13.42 g (0.15 mol) of 1,4-butanediol was added, and the mixture was stirred and reacted for 30 minutes while adjusting the temperature in the reaction system to 70 to 75 ° C., and then hydroxypropyl methacrylate. (HPMA) is 100.92
g (0.7 mol) was added, and the temperature in the reaction system was 70-
The mixture was stirred and reacted for 30 minutes while adjusting the temperature to 75 ° C. Then, the temperature in the reaction system was adjusted to 50 to 55 ° C., and 19.39 g (0.15 g) of dibutylamine was added.
mol) was added, and the reaction was continued until the residual isocyanate group became 0%. The reaction mixture was cooled to 20 ° C. to give a viscous reactive oligomer.

(Comparative Example 1 of Oligomer Production) Oligomer Production An oligomer was produced in the same manner as in Example 1 except that the polyoxytetramethylene glycol having a molecular weight of 1500 was used as the polycarbonate diol having a molecular weight of 1500.

(Comparative Example 2 of Oligomer Production) Oligomer Production An oligomer was produced in the same manner as in Example 1 except that polycaprolactone diol having a molecular weight of 1500 was used instead of polyoxytetramethylene glycol having a molecular weight of 1500.

(Comparative Example 3 of Oligomer Production) Oligomer Production An oligomer was produced in the same manner except that a polycarbonate diol having a molecular weight of 1500 was used instead of the polyoxytetramethylene glycol having a molecular weight of 1500 described in Example 2.

(Comparative Example 4 of Oligomer Production) Oligomer Production An oligomer was produced in the same manner as in Example 2 except that polycaprolactone diol having a molecular weight of 1500 was used instead of polyoxytetramethylene glycol having a molecular weight of 1500.

[Composition Production Example] (Example 1) An oligomer 264 obtained in (Oligomer Production Example 1) was placed in a 1-liter four-necked flask equipped with a stirrer, a reflux condenser and a thermometer. 0.7 g was charged and after heating to 65 ° C., methyl methacrylate 37
0 g and 24-6.8 g of 2-ethylhexyl acrylate are added, and the mixture is stirred and mixed until the oligomer is completely dissolved. Next, 6 g of paraffin wax (paraffin wax-140, Nippon Seiro Co., Ltd.) having a melting point of 61 ° C. was added, and stirring was continued until the wax was completely dissolved. Then 2-t-
Butyl-p-cresol (1.5 g) was added, and the mixture was stirred until it became uniform and cooled to 20 ° C to obtain a curable composition.

Example 2 The same method was used except that the oligomer obtained in (Oligomer Production Example 2) was used in place of the oligomer obtained in (Oligomer Production Example 1) used in Example 1. A curable composition was produced.

(Example 3) 264.7 g of the oligomer obtained in (Oligomer Production Example 2) was placed in a 1-liter four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer. After charging and heating to 72 ° C, 10 g of polymethylmethacrylate having a weight average molecular weight of 100,000 in advance
380 g of dissolved methyl methacrylate and 246.8 g of 2-ethylhexyl acrylate are added, and the mixture is stirred and mixed until the oligomer is completely dissolved. Next, microcrystalline wax (Hi-Mi
c1045, 6 g of Nippon Seiro Co., Ltd.) was added, and stirring was continued until completely dissolved. Then, it cooled at 20 degreeC and obtained the curable composition. (Comparative Example 1) Curability was the same as in Example 1 except that the oligomer obtained in (Oligomer Production Comparative Example 1) was used in place of the oligomer obtained in (Oligomer Production Example 1) used in Example 1. A composition was produced. (Comparative Example 2) Curability was the same as that in Example 1 except that the oligomer obtained in (Oligomer Production Comparative Example 2) was used in place of the oligomer obtained in (Oligomer Production Example 1). A composition was produced. (Comparative Example 3) Curability was the same as in Example 1 except that the oligomer obtained in (Comparative Example 3 of Oligomer Production) was used in place of the oligomer obtained in (Comparative Example 1 of Oligomer Production). A composition was produced. (Comparative Example 4) Curability was the same as in Example 1 except that the oligomer obtained in (Oligomer Production Comparative Example 4) was used in place of the oligomer obtained in (Oligomer Production Example 1) used in Example 1. A composition was produced. (Comparative Example 5) Curability was the same as in Example 2 except that the oligomer obtained in (Oligomer Production Comparative Example 2) was used instead of the oligomer obtained in (Oligomer Production Example 2). A composition was produced. (Comparative Example 6) Curability was the same as in Example 3, except that the oligomer obtained in (Oligomer Production Comparative Example 2) was used instead of the oligomer obtained in (Oligomer Production Example 2). A composition was produced.

[Results of Characteristic Measurement] To 100 parts of the curable composition obtained in the above [Production Example of Composition], 3 parts of benzoyl peroxide (purity: 50%) was added and mixed, and then N, N-di Add 0.3 parts of (2-hydroxyethyl) -p-toluidine and mix quickly. This composition was cast on a release-treated aluminum plate (thickness: 1.5 mm),
It was cured under conditions of 65 ° C. and RH. Curing was completed in 25 minutes, and a cured film was obtained. The physical properties of the cured film were measured by ordinary methods. The results are summarized in Table 1.

[0046]

[Table 1]

[0047]

As described above, the curable composition obtained by the present invention cures rapidly even at low temperatures, and its physical properties are excellent in tensile strength, elongation and tear strength. Especially, the low temperature flexibility was good. In the present invention, it is possible to obtain the required characteristics by changing the composition of the (meth) acrylic acid alkyl ester, the composition of the reactive oligomer, the molecular weight, etc., and the compounding ratio thereof, and particularly, it is possible to obtain low-temperature properties. It is possible to adjust the balance of flexibility, resistance to moisture and heat deterioration, and physical properties of the film to obtain optimum properties according to the application.

Claims (6)

[Claims] 1. A curable composition comprising a reactive acrylic polyurethane modified composite oligomer, at least one (meth) acrylic acid alkyl ester, a petroleum wax having a melting point of 40 ° C. or higher, and a polymerization inhibitor. 2. A reactive acrylic polyurethane modified composite oligomer, at least one kind of (meth) acrylic acid alkyl ester, petroleum wax having a melting point of 40 ° C. or higher, and a weight which is soluble in the (meth) acrylic acid alkyl ester. A curable composition containing a polymer compound having an average molecular weight of 500,000 or less, and a polymerization inhibitor. 3. A reactive acrylic polyurethane modified composite oligomer comprising a diisocyanate compound, a polyoxyalkylene glycol having a molecular weight of 600 or more and 3000 or less, at least one organic compound having at least two active hydrogen groups, and at least one A reactive acrylic polyurethane modified composite oligomer having at least one kind of (meth) acrylic acid ester having an active hydrogen group as a constituent component and having a double bond derived from the (meth) acrylic acid ester, which is a reactive oligomer. The curable composition described. 4. The curable composition according to claim 1, wherein the polyoxyalkylene glycol is polyoxytetramethylene glycol. 5. A reactive acrylic polyurethane modified composite oligomer is reacted with a diisocyanate compound, a polyoxyalkylene glycol having a molecular weight of 600 or more and 3000 or less, and an organic compound having at least two active hydrogen groups so as to have an excess of isocyanate groups. The reactivity obtained by synthesizing the isocyanate group-terminated prepolymer obtained by reacting the obtained isocyanate group-terminated prepolymer with at least one (meth) acrylic acid ester having at least one active hydrogen group The curable composition according to claim 1 or 2, which is an acrylic polyurethane modified composite oligomer. 6. A method of using a curable composition, which comprises adding a polymerization catalyst to the curable composition according to any one of claims 1 to 5 and coating and curing the composition on a substrate.