JPH05230423A - Adhesive composition and asphalt-composite coated structure - Google Patents

Abstract

PURPOSE:To provide an adhesive compsn. which forms a film curing quickly at a low temp. and perfectly including the film surface and is excellent in adhesion to various substrate such as asphalt even at a low temp. CONSTITUTION:The title compsn. contains a vinyl ester resin such as a so-called (un)satd. polyester (meth)acrylate comprising an adduct of an unsatd. glycidyl compd. to terminal carboxyl groups of an (un)satd. polyester or an epoxy acrylate obtd. by reacting terminal groups of an epoxy compd. with an alpha,beta- ethylenically unsatd. dibasic acid in an equivalent ratio of the terminal group to the acid of 1/2, an air-drying polymer, an ethylenically unsatd. monomer having a (meth)acryloyl group, and if necessary a fibrous reinforcement.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful adhesive composition, and an asphalt composite structure using the adhesive composition. More specifically, by including a specific thermosetting resin composition, the curing time at low temperature is short, and the adhesiveness with various materials is excellent,
In particular, an adhesive composition (adhesive material) excellent in adhesive compatibility with an asphalt composition, and an asphalt composite structure using the adhesive composition, and the adhesive material,
The present invention relates to an asphalt composition and an asphalt coating structure in the form of a combination of various materials.

[0002]

2. Description of the Related Art Conventionally, as an adhesive having a short curing time in a low temperature state and excellent adhesiveness, a radical curable thermosetting resin such as unsaturated polyester resin, epoxy acrylate resin or acrylic syrup is used. Resins and the like are known.

Particularly, the acrylic syrup resin has good curability and adhesiveness even in a temperature range of 0 ° C. or lower. However, a defect of these resins is that they are strongly anaerobic, and therefore, when air is present, they are apt to become an uncured phenomenon as soon as possible, which eventually leads to a problem that the adhesive performance is deteriorated.

Further, in all of these radical-curing thermosetting resins, a so-called cutback phenomenon occurs in which asphalt components have a small molecular weight, such as a martens component and a petrolene component, are dissolved. It means that the performance is degraded.

Therefore, it is difficult to use these resins as an adhesive when using an asphalt composition as an adherend. Epoxy resin is well known as a resin that does not cause the cutback phenomenon, but since it has a fatal defect in curability at low temperatures, it is not possible to use it outdoors in winter.

One of the major objects of the present invention is to find an asphalt-coated structure which uses an asphalt composition as an adherend and is combined with various materials. BACKGROUND ART Asphalt compositions have been used in large amounts as paving materials, various paints, flooring materials, and waterproofing materials as a basic material for civil engineering and construction. In particular, as a waterproof material, it has the oldest history of membrane waterproofing, and the amount used is the largest among various waterproof materials.

On the other hand, the use of asphalt for the structure of civil engineering structures, for example, the waterproofness on the roof of the building, the paint for roads, floors or walls, the marking material, and the adhesiveness to the asphalt are required. For such applications, or for adhesives, no suitable polymer material was found.

In a general-purpose adhesive, a phenomenon of cutting back asphalt occurs because various solvents are mixed, and as a result, as an adhesive,
It is almost impossible to use.

Therefore, in general, hot melt asphalt, asphalt emulsion and the like based on asphalt or modified asphalt are used.

Epoxy resins are also used in various fields by taking advantage of their properties such as good adhesiveness and high mechanical strength. However, in general, since various plasticizers and reactive diluents are used as a softening agent from the poor flexibility, these materials scatter during long-term exposure to lose flexibility, As a result, the adhesiveness decreases.

Further, since the curing time is long, the workability is poor, and particularly in winter, the workability is extremely poor at a temperature of 5 ° C. or lower. As will be described later, one of the objects of the present invention is to find out a novel asphalt composite coating structure using an asphalt waterproof material.

The asphalt waterproofing material and the waterproofing method are roughly classified into a method in which asphalt / roofing material is hot melt-bonded with molten asphalt and then laminated to form a waterproof coating structure. Using the burner as a heat source, one side of the asphalt / roofing material is melted while heating, and the asphalt / roofing layer is adhered to the substrate, a method called a torch method,

The modified asphalt is impregnated with synthetic fibers and the like, and the surface is finished with sand grains, while the back surface is protected by release paper and placed, at the time of use, at the site.
The so-called patch system is used, in which the release paper is peeled off and the asphalt / roofing layer is adhered to the substrate, and the method in which the asphalt is emulsified and used as a waterproof film is used.

Thus, the greatest advantage of using asphalt as a waterproof material is that the material is peculiar in that the price is significantly cheaper than other polymeric composition waterproof materials. It has the property of viscoelasticity.

That is, even if a breakage occurs in the asphalt waterproof material layer due to a large movement of the building structure, the viscous property is strengthened due to the temperature increase in summer, and the breakage is naturally self-adhesive. This is because it possesses the property that it will be transformed.

The asphalt composite coating structure of the present invention comprises:
The focus is on such asphalt self-adhesiveness.

On the other hand, as a waterproof coating film type structure having a concrete structure or a metal precursor as a base, Japanese Patent Application No. 2-16050 discloses a base having a tensile elongation of 30% or more. The various polymer composition layers represented by urethane resin and rubber sheet are formed on the
A fiber-reinforced thermosetting resin layer is formed through an adhesive layer having a CO group, and in particular, it has improved conformability, waterproofness, salt barrier property, scratch resistance, carbon dioxide gas barrier property, and the like. The composite coating structure has been proposed.

As the repairing method, a method of reconstructing asphalt, or a molded sheet made of butyl rubber or soft vinyl chloride, etc., is joined on-site by means such as an adhesive or heat fusion to form a waterproof layer. Or a method of applying a lining of a liquid material, drying and curing to form a uniform waterproof layer, a so-called coating waterproof method, or a radical curable resin composition, which itself has a fast curing speed. Japanese Patent Application Laid-Open No. Sho 6
A method of using an unsaturated polyester resin, which is described in JP-A-3-75248, is known.

[0019]

As described above, as the adhesive for the asphalt composition, hot melt asphalt, asphalt emulsion, etc. using the same material are used, but There is a problem.

First, in the case of hot melt asphalt, it is necessary to use fire or heat due to its nature. Therefore, there is always a danger in handling. Further, equipment such as a melting pot for melting asphalt, a burner as such a melting means, a fuel tank and the like are required, and thus transportation and installation of the equipment are very troublesome.

Further, when asphalt waterproofing work is carried out in a dense area of a private house, pollution is caused due to the problem of odor of molten asphalt. Therefore, an extremely practical adhesive for asphalt, which can be easily handled and is excellent in workability, is earnestly desired.

On the other hand, since the asphalt emulsion itself is a one-pack type, it is easy to handle,
Moreover, since it is an emulsion type, it has advantages such as high safety and no risk of fire.

However, since it takes a long time for drying and curing, it takes a long time for construction. Due to the film forming temperature, it is difficult and difficult to carry out the construction at 5 ° C. or lower in winter, and in summer, there is a problem that the surface becomes sticky due to the high temperature.

Basically, it means that the physical properties are low. On the other hand, as mentioned above, a major object of the present invention is to find a novel asphalt waterproof composite coating structure using an asphalt waterproof material.

The FRP-coated structure is excellent in water resistance, heat resistance, salt barrier property, scratch resistance, weather resistance and gas barrier property depending on the performance of the resin used in FRP. Due to this, the elongation of the material is very small.

For this reason, in a structure such as concrete or mortar, when the low-speed and high-speed expansion / contraction motions repeatedly occur due to drying shrinkage, ground subsidence, earthquakes, etc., cracks occur on the surface.

Naturally, such a crack causes water leakage, so that these structures have
Inevitably, it becomes necessary to carry out waterproof construction. For those using polyurethane resin as a covering material, please refer to JIS A
Since it is a process for coating a high elongation type coating material as defined by -6021, the coating structure has a tensile elongation of F
Since it is superior to the RP-coated structure, it is very excellent in terms of crack followability.

On the other hand, however, it is inferior to other chemical properties and physical properties due to the characteristics of the resin. For example, in order to protect the structure from salt damage, for example, to prevent salt neutralization, or to prevent neutralization of concrete. In addition to the carbon dioxide gas barrier performance, there are problems in water resistance, weather resistance and scratch resistance.

As described above, the composite coating structure described in Japanese Patent Application No. Hei 2-16050 has, among other things, the following property of running body, waterproof property, salt barrier property, scratch resistance, carbon dioxide gas barrier property and the like. It can be said that the construction method using such a composite coating structure is an excellent one, which is a further improved one. However, this has the following problems.

1. Tensile elongation of 3 formed on the substrate
When 0% or more of the urethane resin or the rubber sheet has a rupture portion, it cannot be restored again because it has no self-adhesiveness.

2. In the case of coating type such as urethane waterproof material,
Uniformity of coating thickness is difficult. 3. In the case of a urethane resin or a rubber sheet, stress concentration is likely to occur because it does not contain a fiber reinforcing material like an asphalt / roofing material. That is, 0 span tension is easily received.

4. Since the adhesive layer is interposed between the polymer composition layer of the urethane resin or the rubber sheet and the fiber-reinforced thermosetting resin layer having a tensile elongation of 30% or more, the construction is complicated.

On the other hand, the above-mentioned waterproof repair of the asphalt waterproof structure also has a problem. That is, when reconstructing the above-mentioned asphalt, after pressing down and removing the asphalt layer of the old waterproof layer together,
A new asphalt waterproof layer is provided by applying molten asphalt or lining rubber asphalt latex in which asphalt is dispersed in synthetic rubber latex, but the asphalt layer of the old waterproof layer is removed. In addition to the large amount of cost involved in the work and the treatment of the removed material, in the case of molten asphalt, there are problems of environmental pollution due to the hot air from the kettle and the odor of the asphalt.

Further, the method of connecting the above-mentioned molded sheets to form a waterproof layer is further because a water tank, deaeration, etc., or other various facilities are provided on the roof. , From the structure of the building, where there are many irregular shapes such as entrances and exits, the number of joints between sheets is large, the work is troublesome, and the reliability of the joining work is not established, There is a problem with durability as a waterproof material.

Further, the waterproofing material composition for civil engineering and construction, the waterproof composite coating structure, and the asphalt waterproofing repairing method, which have good compatibility with the above-mentioned asphalt composition, have excellent adhesiveness to the asphalt composition and are also fully waterproofed. Since the waterproof composite coating structure in which the material composition and the asphalt composition are combined is excellent in the crack followability of the substrate, there is no water leakage and the waterproof property can be enhanced.

However, as a problem,
1. This resin composition has a drawback that it is unsuitable for field work in the field, because the resin composition cures slowly, especially when it is formed into a thin film of 2 mm or less, and the curing is significantly delayed.
In addition, 2. Due to the anaerobic resin composition, there is a drawback that the coating film surface remains tacky and the workability is poor.

[0037]

[Means for Solving the Problems] The present inventors can safely remove asphalt without cutting back.
We have found an adhesive that is fast-curing even at low temperatures and that has excellent adhesion to asphalt, and at the same time, by using such an extremely useful adhesive, it is possible to combine the asphalt layer with various substrates. It is possible to manufacture a novel asphalt waterproof composite coating structure in the form of a flat shape, or a composite of an asphalt layer, a fiber-reinforced thermosetting resin layer, and various types of substrates, etc. In order to solve the problem of easily repairing the existing asphalt waterproof layer, as a result of intensive studies, the present invention has been completed here.

That is, the present invention comprises a vinyl ester resin polymer (a), an air-drying imparting polymer (b) and an ethylenically unsaturated monomer (ha) having a (meth) acryloyl group. It is an object of the present invention to provide a novel and useful adhesive composition comprising a thermosetting resin composition.

Furthermore, the present invention is intended to provide an adhesive composition which also comprises a fiber reinforcing material (d). Furthermore, it is intended to provide a waterproof composite coating structure in the form of a composite of an asphalt composition layer and various substrates using each of the adhesive compositions described above, or Fiber reinforced thermosetting resin layer,
Another object of the present invention is to provide a waterproof composite coating structure in the form of a composite with various substrates.

[0040]

[Structure] The vinyl ester resin (a) of the present invention includes:
Preferably, a terminal carboxyl group of a saturated or unsaturated polyester and an unsaturated glycidyl compound are subjected to an addition reaction, which is referred to as a saturated or unsaturated polyester (meth) acrylate, and an epoxy skeleton (epoxy resin). Examples thereof include those referred to as epoxy acrylates obtained by reacting the terminal with α, β-ethylenically unsaturated dibasic acid at an equivalent ratio of 1: 2, but these are used alone. However, two or more kinds may be used in combination.

The polyester (meth) acrylate resin is a saturated or unsaturated polyester having at least one (meth) acrylic acid ester group in one molecule,
Alternatively, it means a mixed solution of the (meth) acrylic acid ester group-containing (un) saturated polyester and polymerizable unsaturated monomers.

Here, the (un) saturated polyester is a polybasic acid (polycarboxylic acid) having a glycol component as a main component, a triol component as a polyol, and a dibasic acid mainly as a tribasic acid component. Refers to those obtained by the ester reaction with. In that case,
If necessary, a monoepoxide compound, an epoxy compound and / or an isocyanate compound may be used in combination.

As the glycols for preparing the (un) saturated polyester, only representative glycols are listed. Ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexylene glycol, dimethylolcyclohexane, 2, 4,4
-Alkylene glycols represented by trimethyl-1,3-pentanediol and the like;

Polyalkylene glycols represented by diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol and polypropylene glycol;

Examples thereof include addition reaction products of a dihydric phenol typified by bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A, and an alkylene oxide typified by ethylene oxide and propylene oxide.

As typical triols, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol and the like can be given as typical examples.

As the tetraol unit, pentaerythritol, diglycerol, 1,2,3,4-butanetetriol and the like are particularly representative.

Further, only representative dibasic acids (anhydrides) are listed, o-phthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
Tetrachlorophthalic acid, tetrabromophthalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, 1,1,2
-Dodecanoic acid, maleic acid, fumaric acid, itaconic acid, hymitic acid or het acid, etc., and if only particularly representative tribasic acid units are listed, trimellitic acid, aconitic acid, butanetricarboxylic acid Acid or 6-carboxy-3-methyl-1,2,3,6-hexahydrophthalic acid and the like, and as the tetrabasic acid unit, pyromellitic acid, butanetetracarboxylic acid and the like are particularly typical. is there.

As the monoepoxide unit, only representative ones are listed. Ethylene oxide,
Examples include propylene oxide, epichlorohydrin, styrene oxide, and phenyl dalycidyl ether.

A so-called epoxy resin can be preferably used as the epoxy compound, and one example thereof is plastic material course 1 "epoxy resin" (May 10, 1991, Nikkan Kogyo Shimbun). Published by Kuniyuki Shiramoto), pp. 19-48.

As the isocyanate compound unit, a polyvalent isocyanate compound known in the polyurethane industry can be preferably used. One example thereof is the plastic material course 2 “Polyurethane resin” (Showa 44).
(Published by Nikkan Kogyo Shimbun, June 30, 2013, by Keiji Iwata)
Polyvalent isocyanate compounds as described on page 46, as well as pages 175-178.

The above-mentioned resin can be produced by an esterification reaction of a divalent, trivalent or tetravalent glycol with acrylic acid and / or methacrylic acid and a polybasic acid, or a (meth) acrylic group and a hydroxyl group. And a method of using an esterification reaction of a compound having

The unsaturated polyester is, for example, α,
produced by polycondensation reaction of β-ethylenically unsaturated dibasic acid or acid anhydride thereof, aromatic saturated dibasic acid or acid anhydride thereof, and glycols, and optionally, as an acid component, fat Examples thereof include those produced by using a group or alicyclic saturated dibasic acid together.

As the above α, β-unsaturated dibasic acids or their acid anhydrides, only typical ones are listed. Maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid or Examples include chloromaleic acid and esters thereof.

To list only particularly representative aromatic saturated dibasic acids or their acid anhydrides,
Phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride or halogenated phthalic anhydride, or esters thereof, etc., which are aliphatic or alicyclic. Specific examples of the saturated dibasic acid are oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid or hexahydrophthalic anhydride, or their esters. And each may be used alone or in combination of two or more.

As the glycols, only typical ones are listed. Ester glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane- 1,3-diol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,
6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate or 2,2-di- (4-hydroxypropoxydiphenyl)
Propane and the like may be used alone or in combination of two or more kinds, but in addition to them, an adduct with ethylene oxide, propylene oxide or the like may be similarly used.

Polyglycols and polycondensates such as polyethylene terephthalate can also be used as a part of the acid component.

As the unsaturated glycidyl compounds, only representative ones are listed. Glycidyl esters of various unsaturated monobasic acids such as acrylic acid or methacrylic acid, for example, glycidyl acrylate or glycidyl methacrylate. Is.

It should be noted that only specific representative examples of such unsaturated glycidyl compounds are glycidyl acrylate and the like, among which the use of glycidyl acrylate is desirable.

The number average molecular weight of the unsaturated polyester acrylate is preferably 1,500 to
3,000, particularly preferably in the range of 1,800 to 2,800 is suitable.

If the molecular weight is less than 1,500, the obtained cured product will inevitably become tacky or the physical properties will deteriorate, whereas if it is greater than 3,000, the curing time will inevitably occur. It becomes longer and productivity becomes worse.

The epoxy acrylate resin used in the present invention is, for example, a bisphenol type epoxy resin alone or a combination of a bisphenol type epoxy resin and a novolac type epoxy resin. An epoxy vinyl ester obtained by reacting an epoxy resin having an average epoxy equivalent of 150 to 450 with an unsaturated monobasic acid in the presence of an esterification catalyst. Is.

Here, to mention only representative ones of the above-mentioned bisphenol type epoxy resins, epichlorohydrin and bisphenol A will be given.
Or obtained by reaction with bisphenol F,
A glycidyl ether type epoxy resin having substantially two or more epoxy groups in one molecule;

Or a dimethylglycidyl ether type epoxy resin obtained by the reaction of methyl epichlorohydrin with bisphenol A or bisphenol F; or an epoxy obtained by the reaction of an alkylene oxide adduct of bisphenol A with epichlorohydrin or methyl epichlorohydrin. Resin, etc.

Further, only the typical novolac type epoxy resins mentioned above are listed, for example, an epoxy resin obtained by the reaction of phenol novolac or cresol novolac with epichlorohydrin or methyl epichlorohydrin. .

Further, to mention only representative ones of the above-mentioned unsaturated monobasic acids, acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorbic acid,
Examples include monomethylmalate, monopropylmalate, monobutylmalate, or mono (2-ethylhexyl) malate.

These unsaturated monobasic acids may be used alone or in combination of two or more kinds. The reaction between the above-mentioned epoxy resin and unsaturated monobasic acid is preferably 60 to 14
It is carried out with an esterification catalyst at a temperature of 0 ° C., particularly preferably 80 to 120 ° C.

As the esterification catalyst, known and commonly used compounds can be used as they are, but if only representative ones among them are mentioned, triethylamine,
Various tertiary amines such as N, N-dimethylbenzylamine, N, N-dimethylaniline or diazabicyclooctane; or diethylamine hydrochloride.

The number average molecular weight of such an epoxy acrylate is preferably 900 to 2,500, particularly preferably 1,300 to 2,200. When the molecular weight is less than 900, the obtained cured product becomes sticky or the physical properties are deteriorated, while when it is more than 2,500, the curing time becomes long. , Productivity will come to decline.

The above-mentioned (meth) acryloyl group-containing ethylenically unsaturated monomer (c) used in the present invention is an unsaturated monomer capable of undergoing a crosslinking reaction with the above-mentioned vinyl ester resin (a). Unsaturated oligomers and the like can be mentioned as typical ones,
Above all, the use of (meth) acrylic acid ester monomers is desirable.

Any such (meth) acryloyl group is
If the monomers not used are used and the amount used is too large, the copolymerizability with the vinyl ester resin will inevitably deteriorate, and as a result, the disadvantage of longer curing time may occur. Become.

As the ethylenically unsaturated monomer containing a (meth) acryloyl group, only typical ones will be exemplified. Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, T-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, acrylate 2
-Hydroxyethyl, 2-hydroxypropyl acrylate, β-ethoxyethyl acrylate, acrylic acid 2
-Cyanoethyl, cyclohexyl acrylate or diethylaminoethyl acrylate,

Alternatively, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate or methacrylate. 2-hydroxypropyl,

Alternatively, it may be phenylcarbitol acrylate, noniphenylcarbitol acrylate, nonifenoxypropyl acrylate, N-vinylpyrrolidone, polycaprolactone acrylate, acryloyloxyethyl phthalate or acryloyloxysuccinate.

Further, as various derivatives of dicyclopentanediene, silicylcyclodecane or triazine which can improve the surface dryness of the cured resin,
For example, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tricyclodecanyl acrylate, tricyclodecanyl methacrylate, tris (2-hydroxyethyl) isocyanuric acrylate and the like are particularly representative examples.

Of course, the copolymerizability during the crosslinking reaction is a little
Although inferior, vinyl monomers other than these may be used in combination. Examples of such monomers include only styrene, vinyl acetate, vinyltoluene, α-methylstyrene, diallyl phthalate, diallyl isophthalate, triallyl isocyanurate, diallyl tetraprom phthalate, etc. Allyl monomers; acrylonitrile, glycidyl methacrylate, n
-Such as methylol acrylamide-butyl ether, n-methylol acrylamide or acrylamide,
Examples include so-called hard monomers.

In the present invention, an unsaturated alcohol or a polyfunctional unsaturated monomer may be used in combination. First, the unsaturated alcohol refers to a compound having an acryloyl group and a hydroxyl group, and specific examples of the compound include 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, and 2-hydroxyethyl acrylate. Or hydroxypropyl acrylate or the like.

These compounds are used when the composition of the present invention is used, as compared with those using asphalt.

Next, the above-mentioned polyfunctional unsaturated monomers are defined as compounds having at least two polymerizable double bonds in one molecule, and refer to the compounds. Above all, the wear resistance of the surface of the cured product,
It is preferably used for the purpose of improving scratch resistance, sliding resistance and chemical resistance.

Among them, particularly preferable compounds are polyfunctional (meth) acrylic acid ester monomers, for example, ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1 , 3-butylene glycol di (meth) acrylate or 1,6-hexanediol di (meth) acrylate
Various alkanediol di (meth) acrylates such as acrylates;

Various polyoxyalkylene glycol di (meth) acrylates such as dipropylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate or polyethylene glycol (meth) acrylate. Kind; or

Divinylbenzene, diallyl phthalate,
Triallyl phthalate, triallyl cyanurate, triallyl isocyanurate, allyl (meth) acrylate, diallyl fumarate and the like are mentioned as particularly representative ones, and these may be used alone or in combination of two or more kinds, Of course.

The air-drying imparting polymer (b) used in the present invention means an air-drying component (air-drying imparting component) as an essential component to unsaturated polyester or vinyl ester resin. It refers to something that can be obtained by forcing.

Examples of the method for introducing the air-drying component into the unsaturated polyester or vinyl ester resin as the above-mentioned polymer to be crosslinked are as follows.

One of them is --O--C as a glycol component.
In this method, a compound having an allyl ether group represented by H2-CH = CH2 is used together. Next, it is a method of using a compound derived from a cycloaliphatic unsaturated polybasic acid or a derivative thereof together with the acid component.

Further, there is a method in which a compound derived from dicyclopentadiene is used in combination, and a drying oil, an epoxy reactive diluent and the like are also used in combination.

Of these various methods, first of all, as the allyl ether group-containing compound, known compounds can be used. Among them, only representative ones are listed. Glycol monoallyl ether, diethylene glycol monoallyl ether,
Triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether or polypropylene glycol monoallyl ether,

Or 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, hexylene glycol monoallyl ether,
Various kinds of polyhydric alcohols such as octylene glycol monoallyl ether, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, glycerin monoallyl ether, glycerin diallyl ether, pentaerythritol monoallyl ether, pentaerythritol triallyl ether. Examples include allyl ether compounds and various allyl ether compounds having an oxirane ring such as allyl glycidyl ether.

Next, as a glycol component which is also used in combination, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butynediol, 2-methylpropane-1. , 3-diol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6
-Hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di (4-hydroxypropoxydiphenyl) propane and the like can be mentioned, and they may be used alone or in combination of two or more kinds.

Further, other oxides such as ethylene oxide and propylene oxide can be used in the same manner. Also, as a part of the glycol component and the acid component,
Polycondensates such as polyethylene terephthalate can also be used.

Further, as mentioned above, only typical compounds of the various kinds of cycloaliphatic unsaturated polybasic acids or their derivatives are exemplified by tetrahydrophthalic anhydride, endomethylene. Examples thereof include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, α-terhinene-maleic anhydride adduct, rosin and ester gum.

When used in combination with these cycloaliphatic unsaturated polybasic acids or their derivatives, first,
As only α, β-ethylenically unsaturated dibasic acids or their acid anhydrides, only typical ones are exemplified, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormalein. Acids or their esters and the like. Then, only specific examples of aromatic saturated dibasic acids or their acid anhydrides are listed, and phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid can be mentioned. , Nitrophthalic acid, halogenated phthalic anhydride or esters thereof, and further, only representative examples of aliphatic or alicyclic saturated dibasic acids are exemplified, and oxalic acid, malonic acid,
Examples thereof include succinic acid, adipic acid, sebacic acid, aceraic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. These may be used alone or in combination of two or more kinds.

Further, synthesized from glycol and acid,
A resin obtained by reacting a terminal carboxyl group of an unsaturated alkyd resin with a reactive monomer having a glycidyl group can also be used.

Examples of the glycidyl group-containing reactive monomers include glycidyl acrylate and glycidimemethacrylate, but only representative examples are given.

Further, β-PM which is cis-3-methyl-4-cyclohexene-cis-1,2-dicarboxylic acid and its anhydride (hereinafter abbreviated as β-PMAA).
AA unit compounds can also be used, but the compound refers to β-PMAA as described above, which is represented by [IA] or [IB] as shown below, and these compounds are , Trans-piperylene and maleic anhydride, or an acid anhydride group in the adduct obtained by ring-opening.

Further, particularly representative compounds having dicyclopentanediene include hydroxylated dicyclopentanediene and the like. Further, only to exemplify only a typical dry oil, linseed oil, soybean oil, cottonseed oil, various fatty oils such as coconut oil or peanut oil, further, these fatty oils, Examples include reaction products with polyhydric alcohols such as glycerin.

As the epoxy-reactive diluent, a monoepoxy compound and a polyepoxy compound are particularly representative. Examples of the former include allyl glycidyl ether, n-butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylic acid ester or "CARDURA E" (product of Shell Co., Netherlands), and the latter example. As for belonging, "Unox 206" (American Union
Carbide product), "Epicoat 812" [product of Dainippon Ink and Chemicals, Inc.], DGE (diglycidyl ether), and the like.

In the production of unsaturated polyester, vinyl ester resin and epoxy vinyl ester resin, a polymerization inhibitor is used for the purpose of preventing gelation and controlling storage stability or curability of the produced resin. Is recommended.

Typical examples of the above-mentioned polymerization inhibitor to be used here are hydroquinones such as hydroquinone, pt-butylcatechol or mono-t-butylhydroquinone; hydroquinone monomethyl ether or di-t-. Phenols such as butyl-p-cresol: quinones such as p-benzoquinone, naphthoquinone or p-toluquinone; and copper salts such as copper naphthenate.

In addition to the curing agent and the curing accelerator, a thickener, a low shrinkage agent and the like may be added to the resin composition of the present invention. In particular, the curing accelerator and the curing agent may be added. It is preferable to contain

Examples of the curing agent include organic peroxides. Specifically, known conventional ones such as diacyl peroxide type, peroxy ester type, hydroperoxide type, dialkyl peroxide type, ketone peroxide type, peroxyketal type, alkyl perester type or percarbonate type. Is used and is appropriately selected depending on the kneading conditions and the curing temperature. The amount added is usually the amount used, preferably 0.01 to 4 parts by weight per 100 parts by weight of the unsaturated polyester resin composition, various curing agents such as the above, They may be used in combination as appropriate.

Further, as the above-mentioned curing accelerator, that is, as a substance having a function of decomposing an organic peroxide as a curing agent by a redox reaction and facilitating generation of active radicals, cobalt-based or vanadium-based In addition, various metal soaps such as manganese-based ones, tertiary amines, quaternary ammonium salts, mercaptans and the like are particularly representative.

A low shrinkage agent can be added to the unsaturated polyester resin composition used in the present invention for the purpose of reducing cure shrinkage. Examples of such a low-shrinking agent include thermoplastic resins, and of these, only typical ones are exemplified, such as methyl methacrylate ethyl methacrylate, butyl methacrylate, methyl acrylate or ethyl acrylate, acrylic acid or Various lower alkyl esters of methacrylic acid; homopolymers or copolymers of various monomers such as styrene, vinyl chloride or vinyl acetate; or

As described above, at least one of various vinyl monomers, lauryl methacrylate, isovinyl methacrylate, acrylamide, methacrylamide,
Hydroxyl alkyl-acrylate or -methacrylate, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid or cetylstearyl methacrylate, such as a copolymer with at least one kind of various monomers,

Further, cellulose acetate butyrate or cellulose acetate propionate, polyethylene or polypropylene, or saturated polyester is used.

As the above-mentioned fiber reinforcing material (d) used in the present invention, only typical ones will be exemplified, and glass fiber, amide fiber, aramid fiber, vinylon fiber, polyester fiber or phenol fiber. Various organic fibers; such as carbon fibers, metal fibers or ceramic fibers, various inorganic fibers; or
These are used in various combinations.

In view of workability and economical efficiency, preferred are glass fiber and organic fiber, among which,
It is glass fiber. The fiber may be in the form of plain weave, satin weave, non-woven fabric, mat, or the like, but it is preferable to use the mat-like form in terms of construction methods, maintaining thickness, and the like.

Further, a glass roving is put in a range of 20 to 10
It is of course also possible to cut it to 0 mm and use it as chopped strands. The ratio of the component (c) to the total of the three components (a), (b) and (c) is preferably in the range of 1 to 40% by weight.

As the substrate used in the present invention, only typical ones will be exemplified. Cement concrete, asphalt concrete, JIS A-540.
3 (asbestos slate), ALC plate, PC plate, FRP, plastic, wood or metal, etc., which are configured alone or in combination, and the shape thereof may be any structure Any surface such as a spherical surface, a curved surface, an extended surface, a flat surface or an inclined surface may be used.

Usually, it is a plane or slope of cement concrete or asphalt concrete. For solid substrates such as concrete and metal, it is recommended to perform surface treatment or primer treatment if necessary.

As the asphalt composition layer in the present invention, the following various materials can be mentioned. An asphalt waterproofing material as specified on pages 72 to 79 of "Building Construction Standard Specification / Commentary JASS8 Waterproofing", published and edited by the Architectural Institute of Japan in 1986.

Asphalt pavement materials as specified in “Asphalt Pavement Guidelines” edited and issued by the Japan Road Association. In addition, all compositions containing asphalt as specified in JIS K-2207.

As the underlying asphalt layer used for the improvement of the asphalt waterproofing in the present invention, the construction method can be applied by either a thermal method using a heat melting type or a cooling method using a rubber / asphalt emulsion. There is no problem even if it is done.

Generally, the asphalt waterproof layer is
The asphalt film and roofing are integrally formed, and they are laminated so that they exhibit excellent integrity and waterproofness. Depending on the application of the waterproof roof,
When walking, etc., apply a so-called waterproof holding layer such as concrete pouring or blocks to protect against damage, increase durability, or prevent rising, and in the case of non-walking Needless to say, it is also possible to hold down gravel and the like, or finish with roofing with sand.

Such an asphalt waterproof layer is provided with a thermosetting resin composition comprising (a), (b) and (c), or (a), (b), (c) and (d). When repairing using a fiber reinforced thermosetting resin composition consisting of), in the case of non-walking, except for the partial peeling off of the peeling and blistering parts and repairing it, be especially careful. It is possible to carry out the construction without performing the groundwork treatment, and in the case of walking, only the waterproof pressing layer is removed, the asphalt waterproof layer is dried, and then the construction can be carried out.

As a supply device for applying the adhesive composition of the present invention to an adherend, various known and conventional supply devices can be used.

[0117]

EXAMPLES Next, the present invention will be described more specifically with reference to Reference Examples, Examples and Comparative Examples. In the text, all “parts” and “%” are based on weight unless otherwise specified. I shall.

Here, the experimental procedure and the results of various performance evaluation tests will be described. As the resin for the present invention, epoxy acrylate (VE-1) and saturated polyester acrylate (UPA-1) are used as a vinyl ester resin polymer (hereinafter abbreviated as VE resin), respectively; United (below,
This is abbreviated as air-drying resin. ), An air-drying imparting type unsaturated polyester (UPE-1) was prepared.

On the other hand, unsaturated polyester (UPE-2) was prepared as a resin for comparison and control. In addition, as evaluation items, in order to see the cured state of the adhesive composition and the adhesive layer film at low temperature, Curing property measurement method, and 2. A surface dryness test method was performed.

Further, as the adhesive strength test, in order to evaluate the adhesiveness with the asphalt composition, each of them is described in 4. Adhesion test (B), 8. Peel adhesion test (A), and 9. A peel adhesion test (B) was performed.

Furthermore, in order to evaluate the adhesiveness to various general substrates, the following items are used: 4. Adhesion test (A) integrity test, Adhesion test (C), and 6. An adhesive strength test (D) was performed.

Further, in order to evaluate the adhesiveness in the presence of air, an ALC plate in which air is likely to remain on the adhesive surface is used. Adhesion test (E) was carried out.

As a result of various performance tests, Example 1 to Example 5
In the above cases, as shown in Table 1, both the curing characteristics at low temperature and the surface drying property are excellent in workability by being dry-cured in a very short time.

It is also shown that the adhesiveness has good adhesiveness to any substrate, not being affected by temperature. Comparative Example 1 is a composition in which there is no air-drying imparting polymer in the composition, that is, the use of the air-drying imparting polymer as a constituent of the composition is completely absent. In Comparative Example 2, styrene, which is a monomer not containing a (meth) acryloyl group, is used in combination, but in both cases, the surface is uncured and the adhesive strength is inferior to any substrate. Results have been obtained.

Although the acrylic syrup used in Comparative Examples 3 and 4 is excellent in the curing property at low temperature and the surface drying property, the so-called cut back phenomenon occurs in the adhesiveness with the asphalt composition. Then, the result that it is remarkably lowered is obtained.

Further, since the anaerobic property is strong, the adhesion strength with the ALC plate is poor. The epoxy resins used in Comparative Examples 5 and 6 are inferior in that they have poor curing characteristics at low temperatures and surface dryness, and have no adhesive strength at low temperatures.

Further, the acrylic emulsion resin adhesive used in Comparative Example 7 also has a result that the adhesive strength at low temperature is poor, like the epoxy resin.

Reference Example 1 [Epoxy acrylate (VE
-1) Preparation Example] "Epiclone 1050" having an epoxy equivalent of 470 obtained by the reaction of bisphenol A and epichlorohydrin in a three-necked flask equipped with a thermometer, a stirrer and a condenser [Dainippon Ink and Chemicals, Inc. ) Epoxy resin] of 4,600 g (corresponding to 10 epoxy groups), 860 g of methacrylic acid (corresponding to 10 carboxyl groups), 1.36 g of hydroquinone and 10.8 g of triethylamine until 120 ° C. When the temperature was raised and the reaction was continued for 10 hours at the same temperature, a liquid epoxy acrylate having an acid value of 3.5, a double bond strength of 536 and a color number of 2 was obtained. . Hereinafter, this is abbreviated as "VE-1".

Reference Example 2 [Preparation Example of Saturated Polyester Acrylate (UPA-1)] 3 mol of diethylene glycol, 7 mol of triethylene glycol, 10 mol of orthophthalic acid and 50 ppm of toluhydroquinone were added to 200 to 20 mol. It was heat-condensed at ℃ and cooled to 140 ℃ when the acid value reached 28.

Then, 2 mol of glycidyl methacrylate was charged and reacted at 140 ° C. for 10 hours to obtain a target saturated polyester acrylate (UPA-1) having a double bond titer of 1,476.

Reference Example 3 [Preparation example of air-drying imparting type unsaturated polyester (UPE-1)] 2 mol of β-PMAA, 2.5 mol of fumaric acid and 5.25 mol of diethylenedalicol were used. Under a known condition, it is heated and dehydrated and condensed, and the double bond titer is 450.
Moreover, the target unsaturated polyester (UPE-1) having an acid value of 18 was obtained.

<Test Method> 1. Curing property measurement method BPO paste (50%) for 100 PHR of resin
2 PHR, dimethyl paratoluidine 0.5 PHR
Was collected in a beaker and stored in a cryogenic constant temperature chamber of -10 ° C.
The time until gelation was measured.

2. Surface Dryness Test Method Three types of coating films were prepared on a glass plate using an applicator in an extremely low temperature constant temperature room of −10 ° C., and surface dryness was performed by a finger touch test.

The evaluation method was carried out by measuring the time until the absorbent cotton of about 2 to ³ cm ³ was pressed against the surface of the coating film until the absorbent cotton did not remain on the surface of the coating film due to adhesion. The compounding composition is as follows.

3. Adhesion test (A) Integrity test “Test method for surface protection of concrete structures (draft) and commentary” (Hanshin Expressway Public Corporation, Japan Society of Materials, March 1989) No. 13 integrity test (the size of the sample base concrete is 300 × 300 × 60 mm).

However, each material was applied and applied in an extremely low temperature constant temperature chamber of -10 ° C., and thereafter, it was further cured at -10 ° C. for 7 days under the low temperature method, and applied in a constant temperature chamber of 20 ° C. The construction was carried out, and after that, the condition of curing at 20 ° C. for 7 days was set to the room temperature method.

Then, the test piece obtained by applying the above-mentioned two temperature conditions and curing was treated with an epoxy-based quick-curing adhesive at 20 ° C. in a thermostatic chamber at 65% RH. Then, the attachment was adhered, and after curing for 3 hours, the Kenken uniaxial tensile adhesive strength was measured.

The measurement points were set at three points, and each measurement point was separated by 50 mm or more to measure the adhesive force. In addition, the measured value was an average value at three points. 4. Adhesion test (B) The test piece substrate was made to use dense grain size asphalt concrete having a size of 300 × 300 × 60 mm, and the other conditions were the same as those of the adhesion test (A).

5. Adhesion test (C) JIS A-6910-1988 "Multi-layer finish coating material,
It evaluated based on the adhesive strength test of "5.8".

JIS of 70 × 70 × 9 mm
Cold rolled steel sheet listed in G-3141, 40 × 40 ×
It was applied with a size of 1 mm. However, application construction,
And each condition of curing is adhesive strength test (A)
The adhesion test is performed in the same manner as the integrity test.
It was performed according to A-6910-1988.

The number of test specimens was three, and the average value of the three measured values was adopted. 6. Adhesion test (D) The natural granite “Capao Bonito” (Brazilian) of 70 × 70 × 20 mm was used, and all other conditions were the same as the adhesion test (C).

7. Adhesive force test (E) JIS A-54 having a size of 70 × 70 × 20 mm
Using the lightweight cellular concrete panel (for partitioning ALC panels) described in No. 16, the adhesive performance was evaluated when air was present due to the cell cross section on the adhesive surface.

All other conditions were the same as in the adhesive strength test (C). 8. Peel adhesion test (A) The peel adhesion test described in 180 of JIS K-6854 was followed.

As a rigid material test piece, JIS H-4
2,000 A105P, an aluminum plate having a thickness of 2 mm was used. On the other hand, as a flexible material test piece,
"Highness roof ohm G" which is a modified asphalt roofing material for normal temperature method manufactured by Shoishi Kako Co., Ltd. was used.

Adhesion was carried out by applying the composition (brushing was applied with a coating amount of 200 g / m ² ) in an extremely low temperature constant temperature room of −10 ° C., and then at −10 ° C. The low temperature method was applied under the condition that it was cured by pressure bonding for 7 days (the pressure was 0.1 Kg / cm ² ) and cured, while coating was carried out in a thermostatic chamber at 20 ° C. The room temperature method was carried out under the condition that the composition was pressure-bonded at 0 ° C. for 2 days for curing.

After that, the specimens obtained by construction and curing under these two temperature conditions were heated to 20 ° C.
And the peel adhesion was tested in a thermostatic chamber at 65% RH.

9. Peel Adhesion Test (B) It was based on the T-type peel adhesion test of JIS K-6854. As the flexible material test piece, "Soprelan Fram 180GR" which is an asphalt roofing material for the torch method of Shoishi Kako Co., Ltd. was used. The bonding processing conditions are
The peel adhesion test (A) was performed in the same manner.

Examples 1 to 4 The various resins obtained in Reference Examples 1, 2 and 3 were mixed with about 10
At a temperature of 0 ° C., with the ratios shown in Table 1,
In addition, unsaturated monomers as shown in the same table were dissolved at the compounding ratios listed in the same table to obtain various adhesive composition.

The amount of the adhesive composition used in each of the adhesive strength test and the peel adhesive strength test was 200.
It was set to g / m ² . In addition, in the low temperature method, the amount of the curing agent added is 100 PHR of the resin, and BPO paste (5
0%) 3 PHR and dimethyl paratoluidine 0.
It is blended so as to be 3 PHR.
2 PH of BPO paste (50%) against 0 PHR
R and dimethyl paratoluidine were blended so as to be 0.1 PHR.

Example 5 Calcium carbonate was used as the filler and the curing system was tested as in Examples 1-4.

Comparative Examples 1 and 2 As shown in Table 1, when the air-drying imparting resin is not used,
When using a styrene monomer which is an ethylenically unsaturated monomer having no (meth) acryloyl group. The curing system is
It tested like Example 1-4.

Comparative Examples 3 and 4 A commercially available acrylic resin was used, and the curing system was as in Examples 1 to 4.
Tested as above.

Comparative Examples 5 and 6 Using commercially available epoxy resins, tests were carried out with a main material / curing material blending composition as shown in Table 1.

[0154]

[Table 1]

[0155]

[Table 2]

<< Explanation of Test Results >> The units for both the low temperature curing time and the surface desiccation test are “time (h
rs. ) ”, And the unit of the adhesive strength test is“ Kg / cm
² ", and the unit of peel adhesion test is" g
/ Cm ", and the" prefixed value / postfixed numerical value "indicating the test result in the table, the front part represents the result of the adhesion test by the low temperature method, and the rear part Shows the result of the adhesive strength test by the room temperature method.

[0157]

[Table 3]

<< Footnote >> The indication "MMA / SM = 15/15" indicates that the combination system (mixed system) has MMA of 15% and SM of 15%.

[0159]

[Table 4]

[0160]

[Table 5]

[0161]

[Table 6]

[0162]

[Table 7]

[0163]

According to the present invention, as described above,
By using a specific adhesive composition, there are advantages that the curing time is short even at a low temperature, and the film surface is completely cured, so that the adhesive property with various materials is excellent even at a low temperature range.

Further, this adhesive composition is used in various asphalt compositions because it does not dissolve the low-molecular-weight components such as martens and petrolenes in the asphalt components, that is, the cut-back phenomenon does not occur. Since it has excellent adhesiveness to an object, an asphalt composition can be used as an adherend to produce a so-called asphalt composite coating structure in combination with various base materials.

These asphalt composite coating structures are
A structure of a civil engineering building that uses asphalt, for example, as a roof waterproofing for construction, as a paint or marking material for roads, floors or walls, or for various interior and exterior constructions. As a material, it is used for applications that require adhesiveness with asphalt.

Further, since this is an air-drying imparting type adhesive composition, it does not become an uncured phenomenon even in the presence of air, so that it can be used as an adhesive for various foams. It can be used.

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Claims (6)

[Claims] 1. A vinyl ester resin polymer,
(B) A thermosetting resin composition comprising an air-drying imparting polymer and (c) an ethylenically unsaturated monomer having an acryloyl group or a methacryloyl group, which is an adhesive composition. 2. A vinyl ester resin polymer,
(B) a thermosetting resin composition comprising an air-drying imparting polymer and (c) an ethylenically unsaturated monomer having an acryloyl group or a methacryloyl group, and (d) a fiber reinforcement. An adhesive composition. 3. An asphalt composite coating structure, comprising an asphalt composition layer, a layer of the adhesive composition according to claim 1, and a substrate in order from the top. 4. The fiber-reinforced thermosetting resin layer according to claim 1, the asphalt composition layer, and the asphalt composition layer in that order from the top.
An asphalt composite coating structure, which comprises a layer of the adhesive composition according to 1. and a substrate. 5. The fiber-reinforced thermosetting resin layer according to claim 2, the asphalt composition layer, and the asphalt composition layer in that order from the top.
An asphalt composite coating structure, which comprises a layer of the adhesive composition according to 1. and a substrate. 6. A fiber-reinforced thermosetting resin layer, an adhesive composition layer according to claim 1, an asphalt composition layer, and an adhesive composition layer according to claim 1 in that order from the top. To
And an asphalt composite coating structure comprising a substrate.