JPH08209058A - Curable composition and composition for road marking using the same - Google Patents

Abstract

PURPOSE: To obtain a composition for road marking, good in storage stability, curable in a short time and capable of providing coating films, having a high whiteness degree and good in strength, abrasion and weather resistances and adhesion to road surfaces when used as a road marking material. CONSTITUTION: This curable composition for road marking is obtained by adding a composition prepared by blending (A) 10-90 pts.wt. acrylic resin containing >=50wt.% amount of an acrylic or a methacrylic ester copolymerized therewith with (B) 10-90 pts.wt. (meth)acrylic ester monomer and (C) 1-20 pts.wt. cross- linking monomer containing >=2 (meth)acryloyl groups in one molecule so as to provide 100 pts.wt. sum total and a polymerization initiator thereto. Furthermore, the curable composition for road marking, as necessary, contains further 50-200 pts.wt. inorganic filler.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition capable of forming a thick film coating material by heat or light energy, and a road marking composition using the composition.

[0002]

2. Description of the Related Art Conventionally used as coating materials for floors, roads, and wall surfaces are solvent-based paints, water-based paints, epoxy resins, urethane resins, unsaturated polyester resins, vinyl ester resins, acrylic resins. Crosslinking-curable solventless paints using resins.

Among these paints, when a solvent-based paint or a water-based paint is used as a coating material, it is necessary to volatilize a large amount of the solvent or water from the coated surface in the process of forming a dry coating film, resulting in a thick film coated surface. It is difficult to form a coated surface, and it is difficult to form a coated surface having excellent durability, it takes a long time to form the coated surface, and there are problems such as odor due to volatilization of the solvent during formation of the coated surface.

A coating film formed from a coating material using an epoxy resin or a polyurethane resin takes a long time to dry due to its curing, and it is difficult to dry the coating film due to curing in a low temperature atmosphere. There is.

The coating materials such as polyester resin, vinyl ester resin, and acrylic resin which have been used so far can be compared with each other in curing and drying of the coating film even in a low temperature atmosphere by using a large amount of a curing agent together. Although it can be done in a relatively short time, this type of coating material has a very short pot life, which causes a problem that the workability is deteriorated.
In addition, the obtained coating film turns yellow, and when this coating film is used as a road marking, the visibility is poor and the cosmetic properties are not good.

Further, when a conventionally developed active energy ray curable solventless composition such as light or electron beam is used as a coating material, the photocurable one is a deep-curing coating of a thick film. Insufficient property occurs, electron beam curing type has a drawback that the coating film curing device becomes large and cannot be used for road marking, and a road marking composition without such a difficulty Development is strongly expected.

[0007]

Therefore, the present inventors have made a curable composition which does not have the above-mentioned drawbacks, and when used as a road marking material, can form road markings with good visibility and beauty. As a result of studying for the purpose of developing a composition capable of being cured, an acrylic resin coating material has good durability, good adhesion to a substrate, and curability for a short time, but has a relatively long pot life. It was found that a curable composition capable of achieving the object can be developed by utilizing the fact that it has a property of forming a coating film, and completed the present invention.

[0008]

Means for Solving the Problems The gist of the present invention is that the (meth) acrylic acid ester copolymerization amount is 50 to 50% by weight or more of acrylic resin (A) 10 to 90 parts by weight, and (meth)
Acrylic ester monomer (B) 10 to 90 parts by weight, 1 to 20 parts by weight of a crosslinkable monomer (C) having two or more (meth) acryloyl groups in one molecule were blended so that the total amount would be 100 parts by weight. The composition comprises a curable composition comprising a polymerization catalyst, and a road marking composition in which 50 to 200 parts by weight of an inorganic filler is added to 100 parts by weight of the curable composition.

The acrylic resin (A) used in the practice of the present invention has a copolymerization amount of (meth) acrylic acid ester of 50.
It is necessary that the content of the acrylic polymer is at least wt%. Copolymerization amount of (meth) acrylic acid ester is 50% by weight
A coating film formed from a curable composition containing less than 1% of acrylic resin is not preferable because it cannot have good weather resistance and good cosmetic properties.

Specific examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic. C ₁ -of (meth) acrylic acid such as acid-n-butyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid-2-ethylhexyl
Examples thereof include C ₁₈ alkyl esters, benzyl (meth) acrylate, and the like, and these (meth) acrylic acid esters can be used as a homopolymer or a copolymer.

Further, the acrylic resin (A) contains (meth)
Hydroxyl acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, etc., hydroxyl group-containing monomers, (meth) acrylic acid, itaconic acid, maleic acid, (meth) acryloyl phosphate-containing monomers, etc. , Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, nitrogen-containing monomers such as acrylamide, aromatic monomers such as styrene and α-methylstyrene, cyano group-containing monomers such as acrylonitrile and methacrylonitrile, acetic acid It is also possible to copolymerize one or more monomers selected from vinylic monomers such as vinyl and vinyl chloride.

As the acrylic resin (A), it is possible to use one kind of these resins or a composition in which two or more kinds of acrylic resins having different characteristics are mixed. The content of the acrylic resin (A) in the composition of the present invention is 100
It is necessary to make the ratio 10 to 90 parts by weight in the parts by weight. The curable composition of the present invention having an acrylic resin (A) content of 10 to 90 parts by weight has an appropriate viscosity, has good coatability, and has excellent curing characteristics. Further, the coating film formed from this composition has good strength and wear resistance, and also has high adhesive strength with the road surface serving as a base material, and has extremely excellent performance as a road marking material. it can.

Used in carrying out the present invention (meta)
Acrylic ester monomer (B) includes methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
Butyl acrylate, (meth) alkyl esters of C ₁ -C ₁₈ (meth) acrylic acid such as 2-ethylhexyl acrylate, hydroxyethyl (meth) acrylate, (meth) acrylic acid hydroxypropyl, (meth) Hydroxy group-containing monomers such as hydroxybutyl acrylate, nitrogen-containing monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate,
Functional group-containing monomers such as glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholyl (meth) acrylate, isobornyl (meth) acrylate, cycloaliphatic (meth) acrylate, etc. ) Acrylic acid esters and the like can be mentioned.

These (meth) acrylic acid ester monomers (B) are formed from this curable composition by using one or more kinds in an amount of 10 to 90 parts by weight per 100 parts by weight of the curable composition of the present invention. The strength, abrasion resistance, and adhesion to roads of the coated film can be improved, and this composition has extremely excellent properties as a road marking composition.

Specific examples of the crosslinkable monomer (C) having two or more (meth) acryloyl groups in one molecule used in the present invention include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate and hexane. Diol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Examples include isocyanuric acid tris [ethyloxy (meth) acrylate], urethane poly (meth) acrylate, polyester poly (meth) acrylate, polyether poly (meth) acrylate, and the like. These crosslinkable monomers may be used alone or in combination of two or more.

The amount of the crosslinkable monomer (C) used is preferably 1 to 20 parts by weight per 100 parts by weight of the composition of the present invention. The curable composition in which the content of the crosslinkable monomer (C) is in the above ratio has a viscosity suitable for making a coating material, and its coatability is good. The coated and cured coating film has good strength and abrasion resistance, and the adhesion strength of the coating film to the road surface is also good, and is sufficiently suitable as a road marking material.

As the polymerization catalyst used for curing the composition of the present invention, a thermosetting catalyst and a photocurable catalyst may be used alone or a mixture of both may be used. In order to prolong the pot life of the curable composition of the present invention, these polymerization catalysts should be added to the composition of the present invention immediately before its use.

As the thermosetting catalyst which can be used, any commercially available heat decomposable radical generating catalyst can be used, and in particular, peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide and cyclohexanone peroxide. Is preferably used. Further, in order to accelerate the curing of the curable composition, it is preferable to add various amines and metal salts such as cobalt naphthenate in addition to the radical generator. Particularly, benzoyl peroxide and aromatic tertiary Most preferably, a combination catalyst with a primary amine is used.

As the photocurable catalyst, commercially available photodegradable radical-generating initiators and cationic polymerization initiators can be used.
For example, 1-cyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthiophene ) Phenyl] -2-morpholinopropane-1 and other acetophenone photoinitiators, benzoin methyl ether, benzoin isopropyl ether, benzyl dimethyl ketal and other benzoin photoinitiators, benzophenone, benzoylbenzoic acid, 4-nylbenzophenone , Hydroxybenzophenone, benzophenone-based photopolymerization initiators such as 4-benzoyl-4′-methylphenylsulfide, thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, Thioxanthone series such as isopropylthioxanzone Polymerization initiator, bis - metallocene-based photopolymerization initiators such as pentafluorophenyl titanocene, triphenyl phosphine oxide,
An acylphosphine oxide photopolymerization initiator such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide can be used. These photopolymerization initiators may be used in combination of one or more in consideration of the wavelength characteristics of light used, the difference in solubility in the curable composition, and the like. In particular, it is preferable to use a phosphine oxide-based photopolymerization initiator capable of decomposing with long-wavelength light and exhibiting photopolymerization in the deep portion of the coating film.

In order to produce a road marking material using the above-mentioned curable composition, it is preferable that the inorganic filler is contained in an amount of 50 to 200 parts by weight per 100 parts by weight of the curable composition.
The road marking material thus obtained has good coating characteristics,
It has curing characteristics, and the marking after curing has good strength and wear resistance, and also has good adhesion to the road surface. Specific examples of inorganic fillers that can be used include calcium carbonate, titanium oxide, aluminum hydroxide, calcium sulfate, barium sulfate, aluminum oxide, silicon oxide, glass flakes, iron oxide, and chromium oxide. It is preferable to use one kind or a mixture of two or more kinds. In particular, to make road markings with good weather resistance and good visibility, titanium oxide as an inorganic filler,
It is preferable to use an inorganic filler whose main component is calcium carbonate.

By adding an antioxidant and an ultraviolet absorber to the above composition, the durability of the coating film formed from this composition can be improved. In addition, it is possible to improve the flexibility of the coating film by adding a plasticizer, add dyes and pigments for coloring the coating film, enhance the light reflectivity of the road marking that is the coating film, and improve the visibility. Therefore, glass beads or the like can be added. Further, a solvent may be added to improve the workability of the composition of the present invention or to improve the adhesion of the coating film to the road surface.

Further, paraffin wax, polyethylene wax, etc. may be added in order to accelerate the curability of the road marking formed from the composition of the present invention and to exhibit the characteristics as a marking material.

Hereinafter, the present invention will be described in more detail with reference to examples. Hereinafter, in the examples, “part” means “part by weight”.

[0024]

Example 1 [Polymerization of Acrylic Resin (A)] 200 parts of ion-exchanged water is charged into a separable flask equipped with a reflux tube, a nitrogen displacement device and a stirrer to dissolve 2 parts of Poval. Next, a monomer mixture of 50 parts of methyl methacrylate, 30 parts of butyl acrylate and 20 parts of butyl methacrylate, to which 3 parts of azobisisobutyronitrile was added, was placed in a flask. The temperature is raised with stirring under a nitrogen stream, the temperature is maintained at 80 ° C. for 3 hours, then the temperature is increased to 100 ° C. and maintained for 1 hour, and then the residual monomer is distilled off. Polymer particles were collected from the reaction product produced, dehydrated and dried to obtain an acrylic resin (A-1). yield
It was 95%. [Compounding] A mixture of 40 parts of acrylic resin (A-1) and 30 parts of methyl methacrylate, 30 parts of butyl acrylate and 15 parts of 2-ethylhexyl acrylate as the (meth) acrylic monomer (B) (total 55 parts), And crosslinkable monomer (C)
As dipentaerythritol hexaacrylate 5
Paraffin wax 130 in a mixture with 100 parts (total 100 parts)
(Manufactured by Nippon Seiro Co., Ltd.) 1.0 part and photopolymerization initiator Lucillin TPO
(BASF) 1.0 part is dissolved. Further, 20 parts of titanium oxide, 50 parts of calcium carbonate, and 50 parts of silica sand were added as a filler, and the mixture was degassed by stirring to obtain a white road marking composition. [Coating] The composition was applied to an asphalt road surface (surface temperature 30
℃) to a thickness of 0.2 mm. The illuminance of light during application
2.3 mW / cm ² , and the coating film was cured after 3 minutes. No yellowing was observed in the cured product.

[0025]

Example 2 Acrylic resin (A-1) made in Example 1,
A composition was obtained in the same manner as in Example 1 except that the (meth) acrylic monomer (B) and the crosslinkable monomer (C) were changed as shown in Table 1. [Coating] The composition was applied to an asphalt road surface (surface temperature 30
℃) to a thickness of 0.2 mm. The illuminance of light during application
2.3 mW / cm ² , and the coating film was cured after 3 minutes. No yellowing was observed in the cured product.

[0026]

Example 3 [Polymerization of Acrylic Resin (A)] 200 parts of ion-exchanged water is charged into a separable flask equipped with a reflux tube, a nitrogen replacement device and a stirrer to dissolve 2 parts of Poval. Then, a mixture of 60 parts of methyl methacrylate and 40 parts of n-butyl methacrylate, to which 3 parts of azobisisobutyronitrile was added, was placed in a flask. The temperature is raised with stirring under a nitrogen stream, and the temperature is maintained at 80 ° C. for 3 hours. Then, the temperature is raised to 100 ° C. and maintained for 1 hour, and then the residual monomer is distilled off.
Polymer particles are collected from the reaction product produced, dehydrated,
It was dried to obtain an acrylic resin (A-2). The yield was 96%. [Blending] 35 parts of this acrylic resin (A-2) and (meth) acrylic monomer (B), 25 parts of methyl methacrylate, 35 parts of acrylic acid-n-butyl (60 parts in total), crosslinkable monomer As (C), a mixture of 5 parts of 1,3-butylene glycol dimethacrylate (100 parts in total), 1.0 part of paraffin wax (manufactured by Nippon Seiro Co., Ltd.), a photopolymerization initiator and CG
Dissolve 1.0 part of I-1700 (Ciba Geigy). Furthermore, 30 parts of titanium oxide and 50 parts of calcium carbonate as filler
A part was added and the mixture was degassed with stirring to obtain a white composition. [Coating] The composition was applied to an asphalt road surface (surface temperature 32
℃) to a thickness of 0.2 mm. The illuminance of light during application
2.5 mW / cm ² and the coating film cured after 7 minutes. No yellowing was observed in the cured product.

[0027]

[Comparative Example 1] A composition was obtained in the same manner as in Example 3 except that a photopolymerization initiator was added, and the composition was applied onto an asphalt road surface (surface temperature 32 ° C) to a thickness of 0.2 mm
Was applied to. The illuminance of light during coating was 2.5 mW / cm ² , but the coating film did not cure even after 2 hours.

[0028]

Example 4 [Polymerization of Acrylic Resin (A)] 200 parts of ion-exchanged water is charged into a separable flask equipped with a reflux tube, a nitrogen replacement device and a stirrer to dissolve 2 parts of Poval. Next, a mixture of 80 parts of methyl methacrylate and 20 parts of ethyl acrylate, to which 3 parts of azobisisobutyronitrile was added, was placed in a flask. The temperature is raised with stirring under a nitrogen stream, and the temperature is maintained at 80 ° C. for 3 hours. Then, the temperature is raised to 100 ° C. and maintained for 1 hour, and then the residual monomer is distilled off. Polymer particles were collected from the reaction product thus formed, dehydrated and dried to obtain an acrylic resin (A-3). The yield was 96%. [Compounding] A mixture of 40 parts of this acrylic resin (A-3) and 30 parts of methyl methacrylate, 30 parts of methyl acrylate-n-butyl acrylate, and 16 parts of 2-ethylhexyl acrylate as the (meth) acrylic monomer (B). (Total 56 parts) and crosslinkable monomer
(C) As a mixture with 4 parts of trimethylolpropane trimethacrylate (total 100 parts), paraffin wax 13
0 (manufactured by Nippon Seiro Co., Ltd.) 1.0 part, dimethyl paratoluidine
1.0 part and a photopolymerization initiator, CGI-1700 (manufactured by Ciba Geigy) 1.0 part are dissolved. 2 parts of Nyper NS (40% benzoyl peroxide manufactured by NOF CORPORATION) and 35 parts of titanium oxide and 45 parts of calcium carbonate as a filler were added to the mixture, and the mixture was degassed by stirring to obtain a white composition. [Coating] This composition was immediately applied on an asphalt road surface (surface temperature 29 ° C) to a thickness of 5 mm. The illuminance of light during coating was 2.0 mW / cm ² , and the coating film was cured after 6 minutes. A slight yellowing was observed in the cured product, but this was not a problem.

[0029]

Example 5 [Formulation] In Example 4, dimethyl paratoluidine was added.
Other than adding 2.0 parts and adding a photopolymerization initiator,
A composition was obtained in the same manner as in Example 4. [Coating] This composition was immediately applied on an asphalt road surface (surface temperature 29 ° C) to a thickness of 5 mm. The coating film was cured 9 minutes after application. A slight yellowing was observed in the cured product, but there was no problem.

[0030]

Example 6 [Compounding] 38 parts of the acrylic resin (A-2) obtained in Example 3 and 26 parts of methyl methacrylate and 32 parts of n-butyl acrylate as the (meth) acrylic monomer (B). Mixture (58 parts in total) with 4 parts of trimethylolpropane trimethacrylate as crosslinkable monomer (C) (total 100 parts)
Part) paraffin wax 130 (manufactured by Nippon Seiro Co., Ltd.) 1.0
Parts, 1.5 parts of dimethyl paratoluidine, and CG photoinitiator
Dissolve 0.5 part of I-1700 (Ciba Geigy). To this, Niper NS (NOF Corporation benzoyl peroxide 40%
5 parts), as a filler, 35 parts of titanium oxide and 45 parts of calcium carbonate were added, and the mixture was degassed by stirring to obtain a white composition. [Coating] This composition was immediately applied on an asphalt road surface (surface temperature: 5 ° C) to a thickness of 0.3 mm. The illuminance of light during coating was 0.5 mW / cm ² , and the coating film was cured after 15 minutes. A little yellowing was observed in the cured product, but this was not a problem.

[0031]

Example 7 [Compounding] In Example 6, 0.3 part of Irgacure 907 (manufactured by Ciba-Geigy) as a photopolymerization initiator, Kayacure
A composition was obtained in the same manner as in Example 6 except that 0.2 part of DETX (manufactured by Nippon Kayaku Co., Ltd.) was added. [Coating] This composition was immediately applied on an asphalt road surface (surface temperature: 5 ° C) to a thickness of 0.3 mm. The illuminance of light during coating was 0.5 mW / cm ² , and the coating film was cured after 18 minutes. A little yellowing was observed in the cured product, but this was not a problem.

[0032]

[Comparative Example 2] [Composition] A composition was obtained in the same manner as in Example 6 except that the photopolymerization initiator was added in Example 6. [Coating] This composition was immediately applied on an asphalt road surface (surface temperature: 5 ° C) to a thickness of 0.3 mm. It took 25 minutes to coat and cure. A little yellowing was observed in the cured product.

The characteristics of the obtained compositions and the coating films formed from these compositions are shown in Table 1.

[Table 1]

[0034]

EFFECTS OF THE INVENTION The curable composition of the present invention comprises an acrylic resin coating material, has good durability and adhesion to a substrate, and has a relatively long pot life while being curable for a short time. A composition having a coating film-forming ability with beauty. Therefore, when used as a road marking material, it is possible to form a road marking having good visibility and aesthetic appeal.

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Claims (6)

[Claims] 1. A 50% by weight of (meth) acrylic acid ester.
10 to 90 parts by weight of the above-copolymerized acrylic resin (A), 10 to 90 parts by weight of (meth) acrylic acid ester monomer (B), 1
A composition prepared by blending 1 to 20 parts by weight of a crosslinkable monomer (C) having two or more (meth) acryloyl groups in the molecule so that the total amount is 100 parts by weight, and a curable composition comprising a polymerization catalyst. . 2. The curable composition according to claim 1, wherein the (meth) acrylic acid ester monomer (B) having a methyl methacrylate content of 10% by weight or more is used. 3. The curable composition according to claim 1, wherein a mixture of benzoyl peroxide and an amino compound and a polymerization initiator selected from acylphosphine oxide are used as a polymerization catalyst. . 4. The composition according to claim 1 or 2.
A road marking composition comprising a composition of 00 parts by weight and 50 to 200 parts by weight of an inorganic filler. 5. The road marking composition according to claim 4, wherein at least one of calcium carbonate and titanium oxide is used as the inorganic filler. 6. The composition for road marking according to claim 4 or 5, wherein a mixture of benzoyl peroxide and an amine compound and a polymerization catalyst selected from acylphosphine oxide are used as the polymerization catalyst. Stuff.