JP5741835B2 - Syrup composition and laminate - Google Patents

Description

  The present invention relates to a syrup composition and a laminate.

Conventionally, epoxy resins, urethane resins, acrylic resins, and the like are known as resins used for coating materials for concrete and asphalt of buildings and structures.
When applying these synthetic resin-coated flooring materials to concrete, apply primer in advance for the purpose of improving adhesion to concrete, suppressing the influence of the foundation, etc., and then overlaying the synthetic resin-coated flooring material on it. The construction method is generally adopted.

  Examples of the primer used include solvent-based resins, emulsion-based resins, epoxy-based resins, unsaturated polyester resins, polyurethane resins, and acrylic resin-based resins.

  Among these resins, the radical polymerization type acrylic resin primer is used as a resin that can shorten the construction period due to its fast curing speed, moderate pot life, and excellent low-temperature curability and air curability. There are many cases.

  For this reason, radical polymerization type acrylic resin-based primer and radical polymerization type acrylic resin are applied to the concrete and asphalt coating materials for structures including buildings and road paving surfaces. By painting and curing a material containing aggregates in resin and forming a coating film to make a laminated structure, it is possible to enhance the functionality of buildings and road paving surfaces, and to apply flexible materials. Waterproof construction is done.

Examples of the waterproof construction method include a sheet-type waterproof method, a coating-type waterproof method, and a concrete lining.
The sheet-based waterproofing method is a method of attaching an asphalt-based waterproof sheet formed by impregnating a synthetic fiber nonwoven fabric with special asphalt to a floor slab, which provides adhesion between the floor slab and pavement and followability to cracks in the floor slab. Since it is excellent, there are many actual uses of the sheet waterproofing method.
Coating film waterproofing methods include, for example, synthetic rubber (solvent type) in which synthetic rubber such as chloroprene is dissolved in a volatile solvent, asphalt (heated type) in which synthetic rubber is added to asphalt, or modified epoxy resin, etc. This is a method of forming a waterproof layer by applying an epoxy resin waterproof material several times on a concrete floor slab, and has the advantage that it can be applied regardless of changes in the shape of the covering.

However, for example, when a synthetic rubber waterproof material is used, the solvent is volatilized to obtain a coating film, so that the construction time is long, and there are problems such as deterioration of the working environment and induction of air pollution.
Moreover, when using an asphalt type | system | group waterproofing material, there exists a concern of accidents, such as a fire and a burn by heating and melting.
Moreover, when using an epoxy resin waterproof material, the curing time is very long, and the workability is lowered due to the crack following ability and the high viscosity of the resin.

  In construction applications, examples of waterproof lining materials for concrete floors include various curable resin compositions mainly composed of resins such as epoxy resins, unsaturated polyester resins, vinyl ester resins, polyurethane resins, and methacrylic resins. It is done.

  As an example of waterproofing by forming a coating film to form a laminated structure or applying a flexible material, Patent Document 1 discloses an acrylic monomer (A) 60 having no alicyclic structure. Wax with respect to 100 parts by mass of syrup (X) containing -80% by mass and 20-40% by mass of a polymer (B) having a butyl methacrylate unit or isobornyl (meth) acrylate unit and having a double bond A syrup composition containing 0.1 to 5 parts by mass of (C) and a drainable top coat obtained by curing the syrup composition are disclosed.

  In addition, as an example in which a concrete floor slab is impregnated and cured and the surface layer of the concrete constituting the concrete slab is used as a waterproof layer, Patent Document 2 describes (a) two or more ethylenic unsaturations in one molecule. An ethylenically unsaturated double bond having a double bond and having two or more methacryloyl groups or acryloyl groups in the molecule, wherein the ethylenically unsaturated double bond is not adjacent to the carbonyl group. A composition for impregnation and resin concrete comprising a polyfunctional (meth) acrylate as a bond, (b) a monofunctional (meth) acrylate, (c) a polymerization initiator, and (d) a decomposition accelerator. A primer composition is disclosed.

JP 2009-161589 A Japanese Patent No. 3514601

However, all of the conventional techniques disclosed in Patent Documents 1 and 2 cure the radical polymerization type acrylic resin primer and form a coating film to form a laminated structure or apply a flexible material. If the surface of the structure is uneven when waterproofing is applied, the resin composition will flow when the radical polymerization type acrylic resin primer is applied, and the surface of the structure will be uniformly uniform It was not possible to paint so as to cover.
In addition, depending on the construction, pinholes may occur in the radical polymerization type acrylic resin primer due to the moisture contained in the concrete layer and asphalt layer of the structure, causing blisters in laminates and waterproof construction. was there.
For this reason, it was necessary to apply the radical polymerization type acrylic resin primer many times before forming a coating film to form a laminated structure, or to increase the coating thickness of the waterproof layer when performing waterproof construction .

  The present invention has been made in view of the above circumstances, so that even if the surface of the structure coated with the primer has irregularities, the resin composition does not flow when coated, and the surface is uniformly covered with the irregular shape. It can be painted, and when layered or waterproofed, it can prevent swelling caused by moisture contained in the concrete layer and asphalt layer of the frame, and reduce odor during construction It is an object to provide a syrup composition that can be used.

The present invention is a monomer having one (meth) acryloyl group and (A), a monomer having two or more (meth) acryloyl group (B), and methacrylate-based polymer having a double bond (C) and
The monomer (A) includes methyl methacrylate (a1) and (meth) acrylate (a2) having a heterocycle selected from the group consisting of a furan ring, a hydrofuran ring, a pyran ring and a hydropyran ring,
The monomer (B) includes a polyfunctional (meth) acrylate (b1) having a bisphenol skeleton ,
For the sum of the monomer (A), the monomer (B) and the methacrylate polymer (C),
The content of the methyl methacrylate (a1) is 5 to 40% by mass,
The content of the (meth) acrylate (a2) having a heterocycle is 30 to 70% by mass,
The content of the polyfunctional (meth) acrylate (b1) is 5 to 30% by mass,
The amount of the methacrylate polymer (C) is 15 to 40% by mass,
Provided is a syrup composition having a TI value (thixotropic index) determined by a measurement method defined in JIS-K6833 of 1.5 or more .

Syrup composition of the present invention, the measurement method the solution viscosity measured on a Brookfield viscometer BM type JIS-Z8803 defined in 23 ° C. is Ri 200~1,500mPa · s der, as defined in J IS-K7113 It is preferable that the tensile strength of the coating film obtained in step 1 is 20 N / mm ² or more.

  Moreover, this invention provides the laminated body by which the primer layer and the cured coating film of the said syrup composition based on this invention are laminated | stacked in order on the upper surface of a structure.

  Moreover, this invention provides the laminated body by which the cured coating film of the material which mix | blended the aggregate with the said syrup composition which concerns on this invention or the said syrup composition on the upper surface of the said laminated body is laminated | stacked.

  The present invention also provides a laminate in which a waterproof layer is further laminated on the upper surface of the laminate.

  The present invention also provides a laminate in which an adhesive layer (W) made of molten asphalt and a waterproof layer (X) made of a sheet waterproof layer are laminated on the upper surface of the laminate.

In order to shorten the construction time, the syrup composition of the present invention is applied to the upper layer of a structure coated with a primer on concrete to provide a resin layer, so that the surface of the structure coated with the primer has irregularities. Even if it is applied, the resin composition does not flow when applied, and can be applied so as to cover the surface evenly with the uneven shape.
Further, the syrup composition of the present invention can prevent the occurrence of blistering due to moisture contained in the concrete layer or asphalt layer of the structure when the laminate or waterproof construction is performed.
Moreover, the syrup composition of this invention can reduce the odor at the time of construction.

Since the laminate of the present invention is formed by sequentially laminating the primer layer and the cured coating film of the syrup composition according to the present invention on the upper surface of the structure, the surface of the structure coated with the primer has irregularities. Even if it is painted, the resin composition does not flow, it can be painted so as to cover the surface uniformly with uneven shapes, and before forming a coating film to form a laminated structure, a radical polymerization type acrylic resin primer It is not necessary to paint the waterproof layer many times or to increase the coating thickness of the waterproof layer when waterproofing.
In addition, the laminate of the present invention can prevent the occurrence of bulge caused by moisture contained in the concrete layer or asphalt layer of the structure when it is constructed. An excellent laminate can be provided.

<Syrup composition>
Syrup composition of the present invention has a monomer having one (meth) acryloyl group and (A), a monomer having two or more (meth) acryloyl group (B), and a double bond (Meth) acrylate polymer (C),
The monomer (A) contains methyl methacrylate (a1) and (meth) acrylate (a2) having a heterocycle selected from the group consisting of a furan ring, a hydrofuran ring, a pyran ring and a hydropyran ring,
The monomer (B) contains a polyfunctional (meth) acrylate (b1) having a bisphenol skeleton.
In the present invention, “(meth) acrylate” means “acrylate and / or methacrylate”.

<Monomer (A)>
The monomer (A) is a monomer having one (meth) acryloyl group. The molecular weight of the monomer (A) is preferably 300 or less. When the molecular weight of the monomer (A) is 300 or less, the reactivity of the syrup composition is good.

  The syrup composition of the present invention comprises, as the monomer (A), methyl methacrylate (a1) (hereinafter referred to as “monomer (a1)”), furan ring, hydrofuran ring, pyran ring and hydropyran ring. 2 components of (meth) acrylate (a2) having a heterocycle selected from the group consisting of (hereinafter referred to as “monomer (a2)”) are contained as essential components.

<Monomer (a1)>
The monomer (a1) is methyl methacrylate and is a component that adjusts properties such as the viscosity of the syrup composition and the mechanical strength of the coating film.
5-40 mass% is preferable with respect to the sum total of a monomer (A), a monomer (B), and a polymer (C), and, as for content of a monomer (a1), 5-30 mass% Is more preferable. By setting the content of the monomer (a1) to 5% by mass or more, it is possible to improve the tensile strength and swelling resistance of the coating film of the syrup composition. Moreover, the odor at the time of a coating operation can be reduced by making content of a monomer (a1) into 40 mass% or less.

<Monomer (a2)>
The monomer (a2) is a monomer having a (meth) acryloyl group and a hetero ring selected from the group consisting of a furan ring, a hydrofuran ring, a pyran ring and a hydropyran ring, and has a molecular weight of 300 or less. Preferably there is. A monomer (a2) is a component which adjusts characteristics, such as the viscosity of a syrup composition, and the mechanical strength of a coating film.

The monomer (a2) is preferably a (meth) acrylate having a heterocycle selected from the group consisting of a furan ring, a hydrofuran ring, a pyran ring and a hydropyran ring.
Examples of the (meth) acrylate having a furan ring include furyl (meth) acrylate and furfuryl (meth) acrylate.
Examples of the (meth) acrylate having a hydrofuran ring include tetrahydrofuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, and the like.
Examples of the (meth) acrylate having a pyran ring include pyranyl (meth) acrylate.
Examples of the (meth) acrylate having a hydropyran ring include dihydropyranyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, dimethyldihydropyranyl (meth) acrylate, and dimethyltetrahydropyranyl (meth) acrylate.

  In the present invention, particularly preferred monomers (a2) include tetrahydrofurfuryl methacrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, dimethyldihydropyranyl methacrylate, and dimethyltetrahydropyranyl methacrylate. A monomer (a2) may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the monomer (a2) is preferably 30 to 70% by mass, and 30 to 60% by mass with respect to the total of the monomer (A), the monomer (B) and the polymer (C). Is more preferable. By setting the content of the monomer (a2) to 30% by mass or more, the surface curability of the syrup composition and the mechanical strength of the coating film are improved. By making content of a monomer (a2) 70 mass% or less, it can prevent that a coating film becomes hard even if it is hard.

<Monomer (a3)>
In the syrup composition of the present invention, the monomer (A) other than the monomers (a1) to (a2) (hereinafter referred to as “monomer (a3)”) has low odor, curability and the like. Further, it may be contained within a range that does not impair the mechanical strength.
As the monomer (a3), hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; glycidyl groups such as glycidyl methacrylate Containing methacrylate; 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, etc. Carboxylic acid-containing (meth) acrylate; methyl acrylate, ethyl (meth) acrylate, (meth) acrylic acid, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, allyl (meth) acrylate, n-butyl methacrylate Rate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) Alkyl (meth) acrylates such as acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate; polyethylene glycol mono (meth) acrylate (ethylene glycol repeat number of 4 or less), polypropylene glycol mono (meta ) Hydroxyl-terminated polyalkylene glycol mono (meth) acrylates such as acrylate (polypropylene glycol repeat number of 2 or less); ethylene glycol monomethyl ester Termethacrylate, ethylene glycol monoethyl ether methacrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, 2-ethoxylated 2-ethylhexyl (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, Oligoethylene glycol monoalkyl ether (meth) acrylate such as polyethylene glycol monoethyl ether (meth) acrylate; trifluoroethyl (meth) acrylate, tetrafluoroethyl (meth) acrylate, hexafluoroethyl (meth) acrylate, octafluoroethyl acrylate Fluorine atom-containing (meth) acrylates such as dimethylcyclohexyl Di- or trialkylcyclohexyl group-containing (meth) acrylates such as (meth) acrylate and trimethylcyclohexyl (meth) acrylate; Di- or trialkylphenyl group-containing (meth) such as dimethylphenyl (meth) acrylate and trimethylphenyl (meth) acrylate Acrylates: benzyl methacrylate, isobornyl methacrylate, dicyclopentenyloxyethyl (meth) acrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, and the like.
It is preferable that content of a monomer (a3) is 0-20 mass% with respect to the sum total of a monomer (A), a monomer (B), and a polymer (C).

  In the present invention, the blending amount of the monomer (A) is preferably 40 to 85% by mass, and preferably 50 to 85% with respect to the total of the monomer (A), the monomer (B) and the polymer (C). 75 mass% is more preferable. By making a monomer (A) 40 mass% or more, the viscosity of a syrup composition does not become high too much and workability | operativity becomes favorable. By setting the monomer (A) to 85% by mass or less, the viscosity of the syrup composition does not become too low, and an appropriate coating thickness can be applied during operation.

<Other monomers>
As long as the syrup composition of the present invention is within the range not hindering the effects of the present invention, other monomers such as monomers and allyl monomers having a molecular weight exceeding 300 and having one (meth) acryloyl group It may contain.

Monomers having a molecular weight exceeding 300 and having one (meth) acryloyl group include stearyl (meth) acrylate, cetyl methacrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, and octafluoropentyl. Hydroxyl terminals such as methacrylate, heptadecafluorodecyl (meth) acrylate, polyethylene glycol mono (meth) acrylate (ethylene glycol repeat number is 5 or more), polypropylene glycol mono (meth) acrylate (polypropylene glycol repeat number is 3 or more) Polyalkylene glycol mono (meth) acrylate; polyalkylene glycol such as polyethylene glycol monomethyl ether (meth) acrylate (ethylene glycol repeat number of 5 or more) Monoalkyl ether (meth) acrylate.
Examples of the allyl monomer include vinyl acetate, vinyl toluene, α-methylstyrene, diallyl phthalate, diallyl isophthalate, triallyl isocyanurate, diallyl tetrabromophthalate and the like.

<Monomer (B)>
The monomer (B) is a polyfunctional monomer having two or more (meth) acryloyl groups. The monomer (B) improves the mechanical strength, abrasion resistance, chemical resistance and the like of the coating film.
The syrup composition of the present invention contains, as the essential component, the polyfunctional (meth) acrylate (b1) having a bisphenol skeleton (hereinafter referred to as “monomer (b1)”) as the monomer (B). To do.

<Monomer (b1)>
The monomer (b1) is a polyfunctional (meth) acrylate having a bisphenol skeleton, and is a component that adjusts properties such as mechanical strength, abrasion resistance, and chemical resistance of the coating film.
As the monomer (b1), bisphenol A skeleton such as bisphenol A ethylene oxide adduct di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether (meth) acrylic acid adduct, etc. Bisphenol A ethylene oxide adduct di (meth) acrylate, hydrogenated bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol F ethylene oxide adduct di (meth) acrylate, etc. .
The monomer (b1) preferably has a molecular weight of 1,500 or less. When a component having a monomer (b1) molecular weight of 1,500 or more is used, the cured coating film of the syrup composition becomes soft, so that the mechanical strength is not improved.
A monomer (b1) may be used individually by 1 type, and may be used in combination of 2 or more type.

  As for content of a monomer (b1), 5-30 mass% is preferable with respect to the sum total of a monomer (A), a monomer (B), and a polymer (C). By setting the content of the monomer (b1) to 5% by mass or more, the mechanical strength of the coating film of the syrup composition is improved. By making the content of the monomer (b1) 30% by mass or less, the swelling resistance of the coating film of the syrup composition is improved.

<Monomer (b2)>
The syrup composition of the present invention contains a monomer (B) other than the monomer (b1) (hereinafter referred to as “monomer (b2)”) as long as the mechanical strength is not impaired. Also good.
As the monomer (b2), ethylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-cyclohexane Dimethanol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2- (meth) Methacryloyloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, polyfunctional (meth) acrylates such as dipentaerythritol hexa (meth) acrylate.
It is preferable that content of a monomer (b2) is 0-10 mass% with respect to the sum total of a monomer (A), a monomer (B), and a polymer (C).
A monomer (b2) may be used individually by 1 type, and may be used in combination of 2 or more type.

  In this invention, the compounding quantity of a monomer (B) has preferable 5-30 mass% with respect to the sum total of a monomer (A), a monomer (B), and a polymer (C). By setting the content of the monomer (B) to 5% by mass or more, the mechanical strength of the coating film of the syrup composition is improved. By making content of a monomer (b1) into 30 mass% or less, it can prevent that a coating film becomes hard even if it is hard.

<Polymer (C)>
The polymer (C) is a unit having an alkyl group having 2 or more carbon atoms or a polymer having a methyl methacrylate or alkyl (meth) acrylate unit and having a double bond (hereinafter referred to as “polymer C”). "). The polymer (C) is a component that imparts curability and imparts strength to the cured product. The double bond in the polymer (C) is a double bond involved in the radical polymerization reaction, and examples of the functional group having such a double bond include a vinyl group, an allyl group, and a (meth) acryloyl group. .
The polymer (C) contributes to the mechanical strength of the cured coating film of the syrup composition, and this is considered to be involved in the effect of the present invention.

As a monomer constituting the polymer (C), methyl methacrylate (c1) is essential, and other monofunctional acrylic monomers, polyfunctional acrylic monomers, (meth) acrylic acid, and the like can be given. .
As the monomer constituting the polymer (C), it is preferable to use another acrylic monomer (c2) not included in any of the above (c1).
As the monomer (c2), ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl Alkyl (meth) acrylates such as (meth) acrylate; cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and cyclohexyl (meth) acrylate; alkyl (meth) acrylate units having an alkyl group having 2 or more carbon atoms, In addition, glycidyl (meth) acrylate or (meth) acrylic acid is preferable as an acrylic unit not included in any of the cycloalkyl (meth) acrylate units, and these may be used in combination of two or more.
As monomers constituting the polymer (C), methyl methacrylate, alkyl methacrylate having an alkyl group having 2 to 4 carbon atoms and / or isobornyl (meth) acrylate, glycidyl (meth) acrylate, and (meth) acrylic It is preferable to use an acid, and it is more preferable to use methyl methacrylate, glycidyl (meth) acrylate, and (meth) acrylic acid.
The alkyl methacrylate having an alkyl group having 2 to 4 carbon atoms is preferably n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, or sec-butyl methacrylate, and particularly preferably n-butyl methacrylate.

Although the manufacturing method of a polymer (C) is not specifically limited, First, as a 1st step reaction, it participates in esterification reaction with two or more types, methyl methacrylate (c1) and another acrylic monomer (c2). A monomer having a first functional group is copolymerized to obtain a first copolymer having the first functional group, and then the first functional group and ester are used as a second stage reaction. A polymer (C) having a double bond is obtained by esterifying the second monomer having a second functional group and a double bond that undergo a hydration reaction with the first copolymer. The method is preferred.
As a combination of the first functional group and the second functional group, a carboxyl group and a glycidyl group, a hydroxyl group and an isocyanate group, and the like are preferable.

The specific polymerization method in the production of the polymer (C) is not particularly limited. First, in the first stage reaction, at least one of methyl methacrylate (c1) and other acrylic monomer (c2), (Meth) acrylic acid is subjected to suspension polymerization to obtain a first copolymer having a carboxyl group, and in the second stage reaction, the obtained first copolymer is added to methyl methacrylate (c1), A method of obtaining a polymer (C) by adding glycidyl (meth) acrylate to the first copolymer by an esterification reaction in a solution is preferred.
The polymerization temperature for suspension polymerization in the first stage reaction is preferably in the range of 70 to 98 ° C., and the polymerization time is preferably about 2 to 5 hours. The reaction temperature in the second stage reaction is preferably 90 to 95 ° C., and the reaction time is preferably about 1 to 4 hours.

  The preferred composition ratio of the monomer used in the first stage reaction is 53 to 99.5% by mass of methyl methacrylate (c1), 15 to 40% by mass of other acrylic monomer (c2), and (meth). Acrylic acid is preferably 0.5 to 7% by mass, and more preferably (meth) acrylic acid 1 to 4% by mass.

  In the second stage reaction, 100 parts by mass of the first stage copolymer was added to 70 to 150 parts by mass of the methyl methacrylate monomer (a1), and (meth) acrylic acid used for the first stage reaction. The glycidyl (meth) acrylate is preferably reacted in an amount of 0.9 to 1.2 mol, more preferably 1.0 to 1.1 mol.

The suspension in which suspension polymerization is performed in the first stage reaction is preferably an aqueous suspension. It is preferable to add a dispersant to the aqueous suspension. The dispersant is not particularly limited, and examples thereof include poorly water-soluble inorganic compounds such as calcium phosphate, aluminum hydroxide, and starch silica; nonionic polymer compounds such as polyvinyl alcohol, polyethylene oxide, and cellulose derivatives; alkali poly (meth) acrylates Examples thereof include metal salts and anionic polymer compounds such as alkali metal salts of (meth) acrylic acid and methyl (meth) acrylate copolymer. The amount of the dispersant used is preferably in the range of 0.005 to 5 mass%, more preferably in the range of 0.01 to 1 mass% with respect to the suspension.
Moreover, it is preferable to contain electrolytes, such as sodium carbonate, sodium sulfate, manganese sulfate, in the suspension at the time of the suspension polymerization. By containing an electrolyte, dispersion stability can be improved. The amount of electrolyte used is not particularly limited as long as it is set appropriately.

In the suspension polymerization, a polymerization initiator is used. The polymerization initiator is not particularly limited. For example, benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, bis (4-tert Organic peroxides such as -butylcyclohexyl) peroxydicarbonate; azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis-2-methylbutyronitrile. These may be used alone or in combination of two or more. The addition amount and addition method of the polymerization initiator may be set as appropriate and are not particularly limited.
It is preferable to use a chain transfer agent in the suspension polymerization. When a chain transfer agent is used, the polymerization reaction of the monofunctional acrylic monomer can be easily controlled.
A thiol compound is preferably used as the chain transfer agent. The thiol compound is not particularly limited, and examples thereof include alkyl mercaptans such as t-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan; aromatic mercaptans such as thiophenol thionaphthol: thioglycolic acid, thioglycolic acid thiol And alkyl glycolate. The addition amount and addition method of the chain transfer agent may be appropriately set and are not particularly limited.

In the second stage reaction, an esterification catalyst can be used to advance the reaction between the first functional group and the second functional group. Examples of the esterification catalyst include amines such as triethylamine; quaternary ammonium salts such as tetraethylammonium chloride and tetrabutylammonium bromide; and phosphorus compounds such as triphenylphosphine. These may be used alone or in combination of two or more. The addition amount of the esterification catalyst may be set as appropriate and is not particularly limited.
A polymerization inhibitor may be added in the second stage reaction. When a polymerization inhibitor is added, the second stage reaction can be performed more stably. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl 4-methylphenol, and the like. These may be used alone or in combination of two or more. The addition amount of the polymerization inhibitor may be set as appropriate and is not particularly limited.

The weight average molecular weight of the first copolymer obtained by the first stage reaction is preferably in the range of 10,000 to 150,000, more preferably in the range of 15,000 to 80,000. preferable. When the weight average molecular weight is 10,000 or more, the strength of the cured product tends to be sufficiently high. When the weight average molecular weight is 150,000 or less, workability when handling the syrup composition is improved.
The weight average molecular weight in the present specification is obtained by dissolving the resin in a solvent (tetrahydrofuran) and converting the molecular weight measured by gel permeation chromatography (hereinafter referred to as “GPC”) into polystyrene.

The polymer (C) obtained by the second stage reaction has a double bond, that is, the carboxyl group contained in the first copolymer reacts with the glycidyl group of glycidyl (meth) acrylate by the second stage reaction. This can be confirmed by the fact that the acid value of the polymer (C) is less than the value estimated from the (meth) acrylic acid used in the first stage reaction. The acid value (unit: mgKOH / g) is preferably 1 or less, and more preferably 0.5 or less.
The acid value in this specification is a value obtained by dissolving a polymer in toluene and titrating with 0.1N KOH ethanol solution using phenolphthalein as an indicator.

The compounding quantity of the polymer (C) in the syrup composition of this invention is 15-40 mass% with respect to the sum total of a monomer (A), a monomer (B), and a polymer (C). 15-35 mass% is preferable, and the range of 18-30 mass% is more preferable. When the content is 15% by mass or more, the tensile strength and anti-swelling property of the coating film are improved, and when it is 35% by mass or less, workability when handling the syrup composition is improved.
As a result, the solution viscosity measured with a Brookfield viscometer BM type stipulated in JIS-Z8803 at 23 ° C. can be in the range of 200 to 1500 mPa · s, and determined by the measuring method stipulated in JIS-K7113. The tensile strength of the coating film can be improved.

<Other ingredients>
It is preferable to add a wax to the syrup composition of the present invention in order to improve surface curability by blocking air on the coating film surface during the curing reaction. Examples of the wax include various known waxes such as paraffin wax and microcrystalline wax.
Further, as the wax, a wax dispersed in an organic solvent may be used from the viewpoint of improving the surface curability. Since the wax is dispersed in the organic solvent and is finely divided, the air blocking action is effectively expressed. This dispersed wax is commercially available, and the syrup composition of the present invention can be prepared by adding the wax as it is. In this case, the syrup composition of the present invention will also contain an organic solvent.
The wax in the dispersed state may be one in which the wax is dispersed in the monomer (A) without containing any organic solvent.
The melting point of the wax is preferably 40 ° C. or higher, and the upper limit of the melting point of the wax is preferably 120 ° C. Two or more kinds of waxes having different melting points can be used in combination.

  The addition amount of the wax is 100 parts by mass in total of the monomer (A), the monomer (B) and the polymer (C) from the viewpoint of balance between air curability and physical properties of the coating film. 0.1 to 5 parts by mass is preferable, and 0.1 to 2 parts by mass is more preferable. When the added amount of the wax is 0.1 parts by mass or more, when the syrup composition is coated and cured, a sufficient air blocking action is obtained, and the surface curability is improved. By making the addition amount of the wax 5 parts by mass or less, the viscosity of the syrup composition does not become too high, and the curing speed and the physical properties of the coating film tend to be good, and the syrup composition is stable during storage. Dispersion and good stain resistance when the syrup composition is paint-cured.

  In order to cure the syrup composition of the present invention, it is preferable to use a curing agent and a curing accelerator, and the working time and curing time can be controlled by the addition amount thereof.

<Curing accelerator>
Examples of the curing accelerator include tertiary amines and metal soaps. These hardening | curing agents and hardening accelerators can be used individually by 1 type or in mixture of 2 or more types.
Specific examples of the tertiary amine include aniline, N, N-dimethylaniline, N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl). -P-toluidine, 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, N, N-bis (2-hydroxypropyl) -p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N, N-bis (hydroxyethyl) ) N, N-substituted anilines such as aniline and diethanolaniline, N, N-substituted-p- Toluidine, 4- (N, N- disubstituted amino) benzaldehyde, and the like.

As the tertiary amine, an aromatic tertiary amine is preferable.
As the aromatic tertiary amine, those in which at least one aromatic residue is directly bonded to the nitrogen atom are preferable. Examples of the aromatic tertiary amine include N, N-dimethyl-p-toluidine, N, N-diethylaniline, N, N-diethyl-p-toluidine, N- (2-hydroxyethyl) N-methyl-p-. Toluidine, N, N-di (2-hydroxyethyl) -p-toluidine, N, N-di (2-hydroxypropyl) -p-toluidine; N, N-di (2-hydroxyethyl) -p-toluidine or Examples thereof include ethylene oxide or propylene oxide adducts of N, N-di (2-hydroxypropyl) -p-toluidine. Moreover, it is not limited to p (para) body, o (ortho) body and m (meta) body may be sufficient.

As the aromatic tertiary amine, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-di (2-hydroxy) are used from the viewpoint of the reactivity and curability of the syrup composition. Ethyl) -p-toluidine and N, N-di (2-hydroxypropyl) -p-toluidine are preferred.
A tertiary amine may be used individually by 1 type, and may be used in combination of 2 or more type.

The tertiary amine may be added immediately before the syrup composition is cured, or may be added in advance to the syrup composition.
The added amount of the tertiary amine is 100 mass in total of the monomer (A), the monomer (B) and the polymer (C) from the viewpoint of balance between curability and pot life (workability). 0.05-10 mass parts is preferable with respect to parts, 0.2-8 mass parts is more preferable, and 0.3-5 mass parts is especially preferable. When the addition amount of the tertiary amine is 0.05 parts by mass or more, the surface curability is improved. By setting the amount of tertiary amine added to 10 parts by mass or less, an appropriate pot life can be obtained.

  Examples of the metal soaps include polyvalent metal soaps such as cobalt naphthenate, manganese naphthenate, nickel octylate, cobalt octylate, and cobalt acetoacetylate.

The addition amount of the metal soaps is a total of 100 masses of the monomer (A), the monomer (B) and the polymer (C) from the viewpoint of balance between curability and pot life (workability). The metal content derived from the polyvalent metal soap is preferably 0.3 parts by mass or less, more preferably 0.2 parts by mass with respect to parts. The surface curability is improved by adding metal soaps.
The addition amount of these curing accelerators varies depending on the type of curing accelerator used and the temperature environment, but when the use temperature is different, it is preferable to adjust the addition amount as appropriate.

<Curing agent>
In order to cure the syrup composition of the present invention, it is preferable to use a redox catalyst in which a curing accelerator and a curing agent are combined.
Examples of the curing agent include known curing agents capable of initiating radical polymerization. Specific examples of the curing agent include ketone peroxides such as methyl ethyl ketone peroxide; 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexyl). Peroxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane and the like; 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroper Hydroperoxides such as oxides; Dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; Diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide; Di (4-t-butylcyclohexyl) peroxide Oxydicarbonate, di ( Peroxydicarbonates such as -ethylhexyl) peroxydicarbonate; peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxybenzoate It is done.

As the curing agent, diacyl peroxide, peroxyester and hydroperoxide are preferable, and benzoyl peroxide is particularly preferable. The benzoyl peroxide is preferably in the form of liquid, paste or powder diluted with an inert liquid or solid to a concentration of about 30 to 55% by mass from the viewpoint of handleability.
A hardening | curing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

The addition amount of the curing agent is preferably adjusted appropriately so that the pot life of the syrup composition is 20 to 60 minutes. If a hardening | curing agent is added in this range, a polymerization reaction will be started immediately after addition and hardening of a syrup composition will advance.
When use temperature differs, it is preferable to adjust and use the quantity of hardening | curing agents suitably.
The addition amount of benzoyl peroxide is preferably 0.25 to 5 parts by mass with respect to a total of 100 parts by mass of the monomer (A), the monomer (B) and the polymer (C). 25-4 mass parts is more preferable. When the amount of benzoyl peroxide added is 0.25 parts by mass or more, the curability tends to be good. When the amount of benzoyl peroxide added is 5 parts by mass or less, the coating workability of the syrup composition and various physical properties of the resulting coating film tend to be improved.

<Oligomer>
In order to improve surface curability, an oligomer having a (meth) acryloyl group may be added to the syrup composition of the present invention.
Examples of the oligomer include urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate.
Urethane (meth) acrylate reacts with hydroxyl group-containing (meth) acrylate, polyisocyanate having two or more isocyanate groups in one molecule, and polyol having two or more hydroxyl groups in one molecule by a known method. Can be obtained.
The epoxy (meth) acrylate is obtained by reacting a polybasic acid anhydride, a partially esterified product of a hydroxyl group-containing (meth) acrylate, a bifunctional bisphenol A type epoxy resin, and an unsaturated monobasic acid by a known method. It is what The bifunctional bisphenol A type epoxy resin is a general-purpose epoxy resin obtained by reacting bisphenol A and epichlorohydrin.
Polyester (meth) acrylates are polybasic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, succinic acid, maleic acid, fumaric acid and adipic acid or their anhydrides, and polyhydric alcohol compounds such as ethylene glycol and propylene glycol. And a (meth) acrylic acid adduct or glycidyl (meth) acrylate and a polybasic acid anhydride.

<Other polymer components>
In the syrup composition of the present invention, a styrene / butadiene copolymer, a vinyl chloride / vinyl acetate copolymer, a cellulose acetate butyrate resin, an epoxy resin, and the like can be contained as other polymer components.

  The syrup composition of the present invention includes a polymerization inhibitor, a silane coupling agent, an ultraviolet absorber, a light resistance stabilizer, a thixotropic agent, a reinforcing material, a plasticizer, bones such as calcium carbonate, titanium oxide and cinnabar as necessary. Materials, inorganic pigments such as chromium oxide and bengara, and organic pigments such as phthalocyanine blue can be used.

  As a polymerization inhibitor, for the purpose of improving storage stability, it is preferable to add hydroquinone, hydroquinone monomethyl ether, 2-6-di-t-butyl 4-methylphenol or the like.

The silane coupling agent is used for the purpose of improving adhesion to inorganic substances, and includes vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, γ- (methacryloxypropyl) trimethoxysilane, γ-mercaptopropyltrimethoxysilane, Examples include γ-aminopropyltriethoxysilane.
The addition amount of the silane coupling agent is preferably 10 parts by mass or less with respect to 100 parts by mass in total of the monomer (A), the monomer (B), and the polymer (C), and has a curability and cost. From the above point, 5 parts by mass or less is more preferable. By making the addition amount of the silane coupling agent 10 parts by mass or less, the surface curability is improved while improving the adhesion of the syrup composition to the substrate.

The ultraviolet absorber is used for the purpose of further improving the weather resistance of the coating film.
Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-octyloxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4. Derivatives of 2-hydroxybenzophenone such as 4,4'-dibutoxybenzophenone, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-ditert-butyl) Phenyl) benzotriazole or a halide thereof, phenyl salicylate, p-tertiarybutylphenyl salicylate, and the like. These may be used alone or in combination of two or more.

  Examples of the light-resistant stabilizer include bis (2,2,6,6, -tetramethyl-4piperidyl) sebacate, bis (1,2,2,6,6, -pentamethyl-4-piperidyl) sebacate, 1- [2 -[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] Examples include -2,2,6,6, -tetramethylpiperidine and 4-benzoyloxy-2,2,6,6, -tetramethylpiperidine. These may be used alone or in combination of two or more.

The thixotropic agent is used for the purpose of imparting thixotropy to the syrup composition of the present invention.
As the thixotropic agent, an organic thixotropic agent such as urethane urea, fatty acid amide, organic bentonite, and oxidized polyethylene wax is preferable. If necessary, fine silica is used in combination. Examples of combinations of thixotropic agents include a combination of fatty acid amide and fine silica, a combination of organic bentonite and fine silica, a combination of fatty acid amide, organic bentonite and fine silica, and a combination of oxidized polyethylene wax and fine silica. The average primary particle diameter of the fine silica is preferably 7 to 40 μm.
By containing the thixotropic agent, structural viscosity is imparted to the syrup composition, the thixotropy is increased, and the hollow particles can be uniformly distributed, and the storage stability of the syrup composition is improved. Moreover, workability | operativity, such as when constructing the compound of this invention, for example to an inclined surface, can be improved.
The content of the thixotropic agent is urethane urea, fatty acid amide and / or organic bentonite with respect to 100 parts by mass in total of the monomer (A), the monomer (B) and the polymer (C). The total amount is preferably 0.5 to 5 parts by mass and the fine silica is preferably 1 to 10 parts by mass.
Thereby, TI value (thixotropic index) calculated | required with the measuring method prescribed | regulated to JIS-K6833 can be 1.5 or more.
If the content of the thixotropic agent is too small, the effect of addition becomes insufficient. On the other hand, when the content of the thixotropic agent is too large, the fluidity of the syrup composition is deteriorated and is not practical. The thixotropic agent may be added to the syrup composition or may be used in the aggregate.

The reinforcing material is preferably used when the flexibility or tensile elongation of the syrup composition is excessive with respect to the usage scene. Reinforcing materials include chopped strands, roving net-like glass fibers, vinylon fibers, nylon fibers, etc.Furthermore, antifoaming agents, defoaming agents, leveling agents, etc. may be used for the purpose of improving workability and appearance. Is possible.

A plasticizer may be added to reduce shrinkage during curing.
Plasticizers include phthalates such as dibutyl phthalate, di-2-ethylhexyl phthalate and diisodecyl phthalate, adipates such as di-2-ethylhexyl adipate and octyl adipate, dibutyl sebacate and di-2-ethylhexyl seba. Examples include dibasic fatty acid esters such as sebacic acid esters such as cate, azelain esters such as di-2-ethylhexyl azelate and octyl azelate; and paraffins such as chlorinated paraffin.
A plasticizer may be used individually by 1 type and may be used in combination of 2 or more type.
The addition amount of the plasticizer is preferably 20 parts by mass or less with respect to 100 parts by mass in total of the monomer (A), the monomer (B), and the polymer (C). When the addition amount of the plasticizer is 20 parts by mass or more, the mechanical strength of the syrup composition may be reduced, or the plasticizer may exude on the surface of the coating film.

The aggregate preferably has an average particle size of 1 μm or more and an oil absorption of 25 cc linseed oil / 100 g or less. Examples of the aggregate include sand, quartz sand, quartz sand, those colored or fired, rock powder such as quartz powder and quartz sand powder; ceramic fired and pulverized; inorganic filler such as calcium carbonate, alumina, glass beads, etc. Materials and the like. The aggregate is preferably a combination of aggregates having different particle diameters from the viewpoint of coating workability and self-leveling property.
The blending amount of the aggregate is determined based on the monomer (A), the monomer (B), and the polymer (C) from the viewpoints of mixability with the syrup composition, coating properties, curability, and physical properties of the coating film. 50 to 1000 parts by mass with respect to 100 parts by mass in total. When blending an aggregate with the syrup composition of the present invention, various additives such as thixotropic agents may be added as necessary.

<TI value>
The syrup composition of the present invention preferably has a thixotropic index (hereinafter referred to as “TI value”) of 1.5 or more.
A syrup composition having a TI value of 1.5 or more has a thixotropic property and is less fluid in a stationary state. Therefore, the syrup composition is different from a coating composition having fluidity in a stationary state. is there.

The TI value can be obtained from the viscosity measured using a BM type viscometer (manufactured by Tokimec) when the temperature of the composition is 23 ± 1 ° C. by the following formula.
TI value = [viscosity at 6 rpm (mPa · s)] / [viscosity at 60 rpm (mPa · s)]

When the TI value is 1.5 or more, the workability is good, and when the surface of the structure is uneven, the surface of the structure does not flow when the syrup coating is applied. Since the coating can be performed so as to uniformly cover the surface as it is, the swelling can be suppressed when the laminate is obtained by laminating on the surface.
If the TI value is less than 1.5, the syrup composition will flow even if it is applied, and the uneven surface of the structure cannot be covered uniformly, and the blistering of the material applied on it will be suppressed. I can't.

<Laminate>
The laminate of the present invention has a structure in which a primer layer and a cured coating film of the syrup composition according to the present invention are sequentially laminated on the upper surface of a structure.

Moreover, it is good also as a structure by which the cured coating film of the material which mix | blended the aggregate with the said syrup composition which concerns on this invention or the said syrup composition is laminated | stacked on the upper surface of the said laminated body.
Moreover, it is good also as a structure by which a waterproof layer is laminated | stacked on the upper surface of the said laminated body further.
Moreover, it is good also as a structure by which the contact bonding layer (W) which consists of molten asphalt, and the waterproof layer (X) which consists of a sheet | seat waterproof layer are laminated | stacked on the upper surface of the said laminated body further.

  In the laminate of the present invention, examples of the structure before the primer is applied include cement concrete, asphalt concrete, mortar concrete, resin concrete, water permeable concrete, ALC plate, and PC plate. These are comprised individually by 1 type or in combination of 2 or more types. Moreover, in the case of concrete, it may or may not contain a reinforcing bar. The structure before the primer is applied is used for floor slabs such as roads, bridges and viaducts, and floors of buildings, for example. For floor slab waterproof structures, there is a particular problem even if the existing structure already formed with a pavement layer or the structure after peeling off the existing pavement layer or existing waterproof layer is used as the structure before the primer is applied. There is no.

  The shape of the structure before coating the primer is not particularly limited, and may be any shape such as a flat surface, a curved surface, and an inclined surface.

  The primer layer used in the laminate of the present invention improves the adhesion of the syrup composition of the present invention to a structure before coating with a primer such as concrete or asphalt. This primer layer is not particularly limited, and for example, a resin or the like can be used. Specific examples of the resin include a solvent-based resin, an emulsion-based resin, or a synthetic resin-based paint that is cured after application of an epoxy resin, a polyurethane resin, an unsaturated polyester resin, a methacrylic resin, or the like. The primer characteristics required vary depending on the type, shape, and construction location of the groundwork, but radical polymerizable acrylic resin-based primers should be used because they can be cured for a short time at room and low temperatures and have excellent workability. preferable.

In order to form a cured coating film of the syrup composition, a method of forming the cured coating film by applying the syrup composition on the primer layer and curing the coating film can be mentioned.
Examples of the coating method include a known coating method using a roller, a gold trowel, a brush, a flexible bow, a coating machine (spray coating machine, etc.), etc. When using a two-part airless coating machine, the main agent side, a curing agent A method of adding a curing accelerator to the main agent side and adding benzoyl peroxide, for example, to the curing agent side is desirable.

When manufacturing the laminated body of this invention, it is preferable that the said syrup composition is 1.5 or more in TI value. When using a syrup composition having a TI value of 1.5 or more, the workability is good, and when the surface of the structure has irregularities, it does not flow when the syrup paint is applied, The surface of the structure can be painted so as to uniformly cover the surface with the uneven shape.
Further, the temperature during coating is preferably -30 to 60 ° C, particularly preferably -10 to 40 ° C, and from the viewpoint of workability, the pot life is preferably 5 to 60 minutes, and the curing time is preferably within 10 to 90 minutes. The pot life and the curing time can be adjusted by adjusting the amounts of the curing agent and the curing accelerator according to the temperature at the time of coating.

In the laminate of the present invention, when the waterproof layer (X) is provided on the cured coating film, the primer layer and the syrup composition of the present invention are coated on the structure and waterproof using the adhesive layer (W). It is preferable that the layer (X) is attached.
Moreover, after providing another contact bonding layer (Y) on this waterproof layer (X), it is good also as a structure which laminated | stacked the paving material (Z) sequentially.
Moreover, it is good also as a structure which laminated | stacked the topcoat layer or the protective layer on the cured coating film of the said syrup composition.
When sufficient adhesive strength is obtained when the pavement material (Z) is laminated directly on the waterproof layer (X), the adhesive layer (Y) may be omitted.

  The top coat layer or the protective layer is a layer provided for the purpose of damage resistance and weather resistance. As a specific example thereof, it is preferable that the layer is a layer obtained by applying and curing a radical polymerization type acrylic resin primer in the same manner as the syrup composition of the present invention, but normal temperature such as epoxy resin, polyurethane resin, unsaturated polyester resin, etc. The layer which apply | coated and hardened the curable resin composition may be sufficient. Moreover, it is also possible to form a topcoat layer or a protective layer using a film or a sheet from the viewpoints of design properties and appearance.

  The adhesive layer (W) is a layer provided for the purpose of strengthening the adhesion between the cured coating film of the syrup composition and the waterproof layer (X). The shape of the adhesive used for forming the adhesive layer (W) is not particularly limited, and may be, for example, liquid, powder, granular, or sheet / film. The material of the adhesive is not particularly limited as long as it improves the adhesion between the syrup composition of the present invention and the waterproof layer (X). Specific examples of the adhesive include solid materials such as resin, rubber, and asphalt, and liquid materials such as petroleum asphalt and asphalt emulsion, and various liquid synthetic resins.

  When the adhesive is liquid, the liquid material may be applied onto the cured coating film of the syrup composition by brush, roller, spray, or the like. Further, when the adhesive is powdery or granular, it may be uniformly dispersed on the cured coating film of the syrup composition of the present invention, or after coating the syrup composition and before curing It may be sprayed on the surface. Further, when the adhesive is in a solid state, it may be applied after it is melted by heating and liquefied.

  As a method for forming the adhesive layer (W), when the waterproof layer (X) is composed of a sheet-like waterproof material, the adhesive layer (W) is coated by heating and melting asphalt or a thermoplastic resin. Before the temperature drops, a waterproof material is applied, and after the waterproof material is applied, it is cooled together with the waterproof material. At this time, the adhesive layer (W) strengthens the adhesion between the cured coating film of the syrup composition and the waterproof layer (X). Moreover, for the purpose of improving the shear adhesive force of the cured coating film of the syrup composition and the waterproof layer (X), silica sand or the like may be mixed and dispersed in granular asphalt or thermoplastic resin. These may be sprayed uniformly on the cured coating film of the syrup composition, or may be sprayed on the surface in a state after coating of the syrup composition and before curing.

Examples of the waterproof layer (X) include sheet-based waterproof materials, paint-based waterproof materials, and synthetic rubber-based waterproof materials. In either case, the thickness is about 0.5 mm to 4 mm.
The sheet-based waterproofing material is formed by impregnating special asphalt heated and melted into a synthetic fiber non-woven fabric manufactured at a factory, and spraying mineral powder.
As the waterproof coating material, there are a synthetic rubber type (solvent type) obtained by dissolving a synthetic rubber such as chloroprene rubber in a volatile solvent, and an epoxy resin type such as a modified epoxy.
Synthetic rubber-based waterproofing materials use high-viscosity solutions in which inorganic fillers, fibers, vulcanizing agents, pigments, and the like are added to the main components such as chloroprene and volatile solvents are added.

  When the pavement layer (Z) is provided on the waterproof layer (X), the adhesive layer (Y) laminated on the waterproof layer (X) is an adhesive between the waterproof layer (X) and the pavement layer (Z). It is a layer provided for the purpose of strengthening. The adhesive layer (Y) is made of the same material as the adhesive layer (W) described above.

  The material of the pavement layer (Z) is not particularly limited, and various materials conventionally known to be usable for pavement such as roads can be used. For example, asphalt pavement in which aggregate is mixed with asphalt, drainage pavement including modified asphalt, concrete pavement, resin pavement and the like can be mentioned.

Since the laminate of the present invention is formed by sequentially laminating the primer layer and the cured coating film of the syrup composition according to the present invention on the upper surface of the structure, the surface of the structure coated with the primer has irregularities. Even if it is painted, the resin composition does not flow, it can be painted so as to cover the surface uniformly with uneven shapes, and before forming a coating film to form a laminated structure, a radical polymerization type acrylic resin primer It is not necessary to paint the waterproof layer many times or to increase the coating thickness of the waterproof layer when waterproofing.
Moreover, since the laminate of the present invention can prevent the occurrence of blistering due to moisture contained in the concrete layer or asphalt layer of the casing when the laminate or waterproof construction is performed, pinholes are less likely to occur, A laminate having excellent durability can be provided.

Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to these examples.
In the following examples, all “parts” indicate “parts by mass” and all “%” other than the degree of saponification and humidity indicate “% by mass”.

[Synthesis Example 1: Preparation of Composition S-1 Containing Polymer (C)]
First, the first stage reaction was performed. That is, 135 parts of deionized water and 0.4 part of polyvinyl alcohol (degree of saponification 80%, degree of polymerization 1,700) as a dispersing agent were added to a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer and stirred. After the polyvinyl alcohol is completely dissolved, the stirring is once stopped, 4 parts of methacrylic acid (hereinafter abbreviated as “MAA”), 96 parts of methyl methacrylate (hereinafter abbreviated as “MMA”), a polymerization initiator. 2,2'-azobis-2-methylbutyronitrile (hereinafter abbreviated as "AMBN") 0.2 part, n-dodecyl mercaptan (hereinafter abbreviated as "n-DM") as chain transfer agent 8 parts, 0.1 parts of sodium carbonate as an electrolyte was added and stirred again, the temperature was raised to 75 ° C. and reacted for 2.5 hours, the temperature was raised to 98 ° C. and held for 1.5 hours to complete the reaction. It was. After cooling to 40 ° C., the obtained aqueous suspension is filtered through a nylon filter cloth having a mesh opening of 45 μm, the filtrate is washed with deionized water, dehydrated, dried at 40 ° C. for 16 hours, and granular vinyl. A system polymer (first copolymer) was obtained. The granular vinyl polymer obtained had a Tg of 100 ° C. and a weight average molecular weight of 40,000. The Tg of the granular vinyl polymer was calculated from the homopolymer Tg described in the polymer handbook using the Fox equation.

The second stage reaction was then performed. That is, 6.6 parts of glycidyl methacrylate (hereinafter abbreviated as “GMA”), 1.5 parts of tetrabutylammonium bromide as an esterification catalyst, polymerization inhibitor in a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer. 2,6-di-t-butyl-4-methylphenol (hereinafter abbreviated as “BHT”) 0.1 part and tetrahydrofurfuryl methacrylate (hereinafter abbreviated as “THFMA”) 252.2 parts In addition, with stirring, 100 parts of the granular vinyl polymer (first copolymer) obtained above was gradually added, and after the entire amount was added, the temperature was raised to 90 ° C. and held for 2 hours, and the acid value was 0.3 mg KOH. / G polymer (C) and THFMA-containing composition S-1 (hereinafter abbreviated as “S-1”) were obtained. The molar ratio of GMA used in the second stage reaction to 1.0 mole of MAA used in the first stage reaction was 1.0 / 1.0.
The composition of S-1 obtained was as follows.
S-1: First copolymer / GMA + THFMA = 100 / 6.6 + 252.2 (parts).
First copolymer = MMA / MAA = 96/4 (parts), Tg: 100 ° C., Mw: 40,000.

[Synthesis Example 2: Preparation of Composition S-2 Containing Polymer (C)]
In the first stage reaction of Synthesis Example 1, the amount of MMA used was changed from 96 parts to 68 parts, 30 parts of isobornyl methacrylate (hereinafter abbreviated as “IBXMA”) was added, and the amount of MAA used was 4 parts. Tg119 except that 0.4 part of lauroyl peroxide (hereinafter abbreviated as “LPO”) was used instead of 0.2 part of AMBN. A granular vinyl polymer having a weight average molecular weight of 40,000 (first copolymer) was obtained.
Using the obtained granular vinyl polymer, a second-stage reaction was performed.
A composition comprising a polymer (C) having an acid value of 0.3 mgKOH / g and THFMA in the same manner as in Synthesis Example 1 except that the amount of THFMA used in Synthesis Example 1 was changed from 252.2 parts to 162.3 parts. S-2 (hereinafter abbreviated as “S-2”) was obtained.
The composition of S-2 obtained was as follows.
S-2: First copolymer / GMA + MMA = 100 / 6.6 + 162.3 (parts).
First copolymer = MMA / IBXMA / MAA = 68/30/2 (parts), Tg: 119 ° C., Mw: 40,000.

[Synthesis Example 3: Synthesis of Comparative Polymer P-1]
In the first stage reaction of Synthesis Example 1, the amount of MMA used was changed from 96 parts to 80 parts, and 20 parts of n-BMA was used instead of 4 parts of MAA. Otherwise, in the same manner as the first copolymer of Synthesis Example 1, a granular vinyl polymer P-1 having a Tg of 82 ° C. and a weight average molecular weight of 80,000 (hereinafter abbreviated as “P-1”) is obtained. It was.
The composition of P-1 obtained was as follows.
P-1: Comparative copolymer = MMA / n-BMA = 80 parts / 20 parts, Tg: 82 ° C., Mw: 80,000.

[Example 1]
Using S-1 obtained in Synthesis Example 1, a syrup composition was prepared with the formulation shown in Table 1. In addition, the compounding quantity (unit: mass part) of S-1 to S-2 described in Table 1 is the total quantity of the polymer (C) and THFMA contained in the composition, and is written together. The value in () is the amount (unit: part by mass) of the polymer (C) contained in the blended S-1 to S-2. Therefore, for example, in Example 1, the content of the THFMA monomer (a2) in a total of 100 parts of the monomer (A), the monomer (B) and the polymer (C) is 46 parts. .

  In a 1 L flask equipped with a stirrer, thermometer, and condenser, 60 parts of S-1 (including 46 parts of THFMA), 15 parts of MMA as a monomer (A), SLMA (product name Acryester SL, manufactured by Mitsubishi Rayon Co., Ltd.) ( Hereinafter, abbreviated as “SLMA.” 1 part, EO-modified bisphenol A diacrylate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: trade name New Frontier BPE-4) as the monomer (B) (hereinafter referred to as “BPE-4”) 20 parts, BHT 0.05 part as a polymerization inhibitor, paraffin wax (product name 115, manufactured by Nippon Seiki Co., Ltd., melting point 47 ° C.) (hereinafter abbreviated as “P-115”) 0.4 part, paraffin Wax (product name 130, manufactured by Nippon Seiki Co., Ltd., melting point 55 ° C.) (hereinafter abbreviated as “P-130”) 0.2 part, paraffin wax (product name 150, manufactured by Nippon Seisaku Co., Ltd., melting point 66 ° C.) (Less than "P-150".) 0.2 parts, N, N-di (2-hydroxyethyl) -p-toluidine (hereinafter abbreviated as "PTEO") as an accelerator, 2 parts, Disparone as an antifoaming agent 230 (manufactured by Enomoto Kasei Co., Ltd.) (hereinafter abbreviated as “Disparon 230”) 0.5 part, JF-77 (manufactured by Johoku Chemical Co., Ltd.) as an ultraviolet absorber (hereinafter abbreviated as “JF-77”) 3 parts, 1 part of BYK-410 (produced by Big Chemie Japan Co., Ltd.) (hereinafter abbreviated as “BYK-410”) as a thixotropic agent was added, and then heated, dissolved, cooled and cooled at 70 ° C. for 2 hours. 1 syrup composition (N-1) was obtained.

[Example 2]
A syrup composition (N-2) of Example 2 was obtained in the same manner as in Example 1 except that the thixotropic agent BYK-410 was not blended.

[Example 3]
Using S-2 containing the polymer (C) obtained in Synthesis Example 2, a syrup composition was prepared with the formulation shown in Table 1.
In a 1 L flask equipped with a stirrer, thermometer and condenser, 75 parts of S-2 (including 45 parts of THFMA), 5 parts of MMA as monomer (A), 10 parts of BPE-4 as monomer (B), 10 parts triethylene glycol dimethacrylate (manufactured by NOF Corporation: trade name Blemmer PDE-150) (hereinafter abbreviated as “PDE-150”), 0.05 part BHT as a polymerization inhibitor, and 0 P-115 as paraffin wax .4 parts, 0.2 part of P-130, 0.2 part of P-150, wax dispersion (manufactured by Big Chemie Japan) (hereinafter abbreviated as “BYK-S780”), 1 part, as an accelerator After adding 2 parts of PTEO, 0.5 part of Disparon 230 as an antifoaming agent, 0.3 part of JF-77 as an ultraviolet absorber, and 1 part of BYK-410 as a thixotropic agent, 70 ° C 2:00 The mixture was heated, dissolved, and cooled to obtain a syrup composition (N-3) of Example 3.

[Example 4]
A syrup composition (N-4) of Example 4 was obtained in the same manner as in Example 1 except that 60 parts of S-2 was used instead of 60 parts of S-1.

[Comparative Example 1]
A syrup composition (N-5) of Comparative Example 1 was obtained in the same manner as in Example 1 except that 18 parts of P-1 was used instead of 60 parts of S-1.

[Comparative Example 2]
As a monomer (B), instead of 20 parts of BPE-4, 20 parts of PDE-150 was used, and otherwise the same procedure as in Example 1 was carried out to obtain a syrup composition (N-6) of Comparative Example 2. It was.

[Comparative Example 3]
As a monomer (A), instead of 15 parts of MMA, THFMA was added, and 61 parts of THFMA was added. Otherwise, a syrup composition (N-7) of Comparative Example 3 was obtained in the same manner as in Example 1.

  For the syrup compositions (N-1 to N-4) of Examples 1 to 4 and the syrup compositions (N-5 to N-7) of Comparative Examples 1 to 3 prepared as described above, the viscosity was measured by the following measurement method. And TI values were measured. The results are summarized in Table 1.

<Viscosity>
The viscosity was measured at 23 ° C. (viscosity at 6 rpm and viscosity at 60 rpm) using a B-type viscometer (BM type, manufactured by Tokimec).

<TI value>
The TI value was determined by the following formula from the measured viscosity when the viscosity at 23 ° C. was measured using a B-type viscometer (BM type, manufactured by Tokimec).
TI value = [viscosity at 6 rpm (mPa · s)] / [viscosity at 60 rpm (mPa · s)]

[Performance evaluation]
For 100 parts of each of the syrup compositions (N-1 to N-4) of Examples 1 to 4 and Comparative Examples 1 to 3 (N-5 to N-7) prepared as described above. , 1 part of a cobalt naphthenate 6% solution (product name: naphthex cobalt 6% (T), cobalt content 6%, manufactured by Nippon Chemical Industry Co., Ltd.) (hereinafter abbreviated as "Co-6%") as an accelerator. Nyper NS (product name Nyper NS, manufactured by NOF Corporation, 40% benzoyl peroxide product) (hereinafter abbreviated as “Nyper NS”) as a curing agent was added, mixed well, and a syrup composition containing a curing agent. Got.
Hereinafter, the syrup composition containing a curing agent obtained using the syrup composition (N-1) of Example 1 is referred to as Example 1, and obtained using the syrup composition (N-2) of Example 2. The obtained syrup composition containing a curing agent was taken as Example 2, the syrup composition containing a curing agent obtained using the syrup composition (N-3) of Example 3 was taken as Example 3, and the syrup of Example 4 was used. The syrup composition containing a curing agent obtained using the composition (N-4) was taken as Example 4, and the syrup composition containing a curing agent obtained using the syrup composition (N-5) of Comparative Example 1 The product was set as Comparative Example 1, the syrup composition containing a curing agent obtained by using the syrup composition (N-6) of Comparative Example 2 was set as Comparative Example 2, and the syrup composition (N-7) of Comparative Example 3 was used. The syrup composition containing a curing agent obtained by using the above was designated as Comparative Example 3, and Examples 1 to And the curing agent mixed syrup compositions of Comparative Examples 1 to 3, as follows, setting time, tensile strength, coating workability were conducted fluidity, measurement and assessment of the resistance to blister resistance. The results are summarized in Table 2.

<Curing time>
From the bottom of a test tube having a diameter of 10 mm and a length of 120 mm, the syrup compositions containing the curing agents of Examples 1 to 4 and Comparative Examples 1 to 3 are introduced, and a thermocouple is inserted in the depth direction of the syrup composition. I put it in the center. While the test tube was left in 23 ° C. water to cure the syrup composition, the exothermic temperature was measured over time with the thermocouple. The time from the addition of the curing agent to the time when the maximum exothermic temperature was reached was determined, and this time was taken as the curing time. The results are shown in Table 2.

<Tensile strength>
The defoaming operation was performed on the syrup compositions containing each of the curing agents of Examples 1 to 4 and Comparative Examples 1 to 3 in an indoor room at an ambient temperature of 23 ° C., and then poured into a mold for curing and curing. After demolding the next day after curing, a cast plate (test sample) having a thickness of 3 mm was obtained. The test sample was subjected to a tensile test according to JIS-K7113, and the tensile strength at break (N / mm ² ) when the tensile test was performed in an environment of 23 ° C. was measured. This tensile strength is one of the indicators of the mechanical strength of the cured coating film. The results are shown in Table 2.

<Coating workability>
As a radical polymerization type acrylic resin-based primer, a concrete plate (30 cm × 30 cm × 6 cm) obtained by applying and curing a product name “Acrysilap DR-90” manufactured by Ryojo Co., Ltd. at a rate of 0.3 kg / m ² is used. The workability when the syrup compositions containing the curing agents of Examples 1 to 4 and Comparative Examples 1 to 3 were applied at a rate of 0.4 kg / m ² was evaluated. Evaluation was judged based on the following criteria. The results are shown in Table 2.
Good (O): The blend could be sufficiently leveled with a brush and applied uniformly.
Poor (x): When leveling the formulation with a brush, the viscosity was high and difficult to level and / or it took a very long time to obtain a uniform surface.

<Flow resistance>
On the glass plate (15 cm × 15 cm × 2 mm) degreased with acetone, the syrup compositions containing the curing agents of Examples 1 to 4 and Comparative Examples 1 to 3 have a ratio of 0.4 kg / m ^2. After coating with a brush as described above, when the glass plate was cured while standing, the amount of the resin dropped from the glass was evaluated for the fluidity of the resin. Evaluation was judged based on the following criteria. The results are shown in Table 2.
Very good (◎): The amount of resin staying on the glass is 80% or more of the coating amount is good (O): The amount of resin staying on the glass is 40% or more and less than 80% of the coating amount (X): It stays on the glass Resin amount is less than 40% of coating amount

<Flip resistance>
As a radical polymerization type acrylic resin-based primer, a concrete plate (30 cm × 30 cm × 6 cm) obtained by applying and curing a product name “Acrysilap DR-90” manufactured by Ryojo Co., Ltd. at a rate of 0.3 kg / m ² is used. A sample was prepared by applying each of the curing agent-containing syrup compositions of Examples 1 to 4 and Comparative Examples 1 to 4 at a rate of 0.4 kg / m ² . The sample was subjected to the load test method described in JHS-433-2 “Bulging load method” to evaluate the swelling resistance.
As for the load test method, after curing the sample, it was cured at room temperature for 24 hours, and then immersed in water at 23 ± 2 ° C. for 24 hours or more. The sample was taken out of the water, and was kept at a temperature of 60 ± 2 ° C. and a humidity of 80 ± 5%. Let stand for 24 hours in a humidity chamber. If the cured coating is hard and brittle, blisters are likely to occur. The results are shown in Table 2.
Good (O): No swelling occurs in the sample.
Defect (x): A bulge occurred in the sample.

From the results in Table 2, the syrup compositions of Examples 1 to 4 according to the present invention provide a cured coating film having a curing time in a range suitable for a painting operation and a high tensile strength. In addition, the syrup compositions of Examples 1 to 4 were all good or very good with respect to the evaluation of coating workability, flow resistance, and swelling resistance.
On the other hand, it replaced with the polymer (C), the comparative example 1 which mix | blended the comparative polymer P-1 which does not have a double bond, the comparative example 2 which lacked the monomer (b1), and the monomer (a1) Each of the cured coating films of Comparative Example 3 lacking the tensile strength is lower than that of Example 1 containing the monomer (a1), the monomer (b1), and the polymer (C). The swelling property was poor.

[Example 5]
As a radical polymerization type acrylic resin-based primer, a concrete plate (30 cm × 30 cm × 6 cm) obtained by applying and curing a product name “Acrysilap DR-90” manufactured by Ryojo Co., Ltd. at a rate of 0.3 kg / m ² is used. The second layer of the syrup composition containing the curing agent of Example 1 was applied and cured so as to have a ratio of 0.4 kg / m ² . Furthermore, with respect to 100 parts of syrup composition N-1, 350 parts by trade name “KM-17A” (hereinafter abbreviated as “KM-17A”) manufactured by Ryohinsha Co., Ltd. as an aggregate, 1 part of Co-6% And 2 parts of Nyper NS were added and mixed, and the prepared syrup composition containing a curing agent was coated on the second layer so that the ratio was 10 kg / m ² on the second cured film. A sample was prepared by coating and curing.
With respect to this sample, the load test method described in JHS-433-2 “Swelling load method” was carried out to evaluate the swelling resistance.
As for the load test method, after curing the sample, it was cured at room temperature for 24 hours, then immersed in water at 23 ± 2 ° C. for 24 hours or more, and the sample was taken out of the water, and the temperature was constant 60 ± 2 ° C. and humidity 80 ± 5% Let stand for 24 hours in a humidity chamber. The results are shown in Table 3.
Good (○) ○: No swelling occurred in the sample.
Defect (x): A bulge occurred in the sample.

  From the results of Table 3, the laminate of Example 5 having a configuration in which a plurality of cured coating films obtained by applying and curing the syrup composition according to the present invention on the primer layer does not generate swelling. In addition, the resistance to swelling was good.

The syrup composition of the present invention is applied so that the resin composition does not flow even when the surface of the structure coated with the primer has unevenness, and the surface is uniformly covered with the uneven shape when applied. Can be prevented.
The syrup composition of the present invention is suitably used for applications such as coating of concrete and asphalt of buildings and structures on a primer coated with a primer and curing to form a cured coating film. Is done.

Claims (6)

Monomers having one (meth) acryloyl group and (A), a monomer having two or more (meth) acryloyl group (B), and methacrylate-based polymer having a double bond and (C) Containing
The monomer (A) includes methyl methacrylate (a1) and (meth) acrylate (a2) having a heterocycle selected from the group consisting of a furan ring, a hydrofuran ring, a pyran ring and a hydropyran ring,
The monomer (B) includes a polyfunctional (meth) acrylate (b1) having a bisphenol skeleton ,
For the sum of the monomer (A), the monomer (B) and the methacrylate polymer (C),
The content of the methyl methacrylate (a1) is 5 to 40% by mass,
The content of the (meth) acrylate (a2) having a heterocycle is 30 to 70% by mass,
The content of the polyfunctional (meth) acrylate (b1) is 5 to 30% by mass,
The amount of the methacrylate polymer (C) is 15 to 40% by mass,
The syrup composition whose TI value (thixotropic index) calculated | required with the measuring method prescribed | regulated to JIS-K6833 is 1.5 or more . 23 solution viscosity measured on a Brookfield viscometer BM type JIS-Z8803 defined in ℃ is Ri 200~1,500mPa · s der, tensile strength of the coating film obtained by the measurement method defined in J IS-K7113 The syrup composition according to claim 1, wherein is 20 N / mm ² or more.   The laminated body by which a primer layer and the cured coating film of the syrup composition of Claim 1 or 2 are laminated | stacked in order on the upper surface of a structure.   The laminated body by which the cured coating film of the material which mix | blended the syrup composition of Claim 1 or 2 or the said syrup composition with the aggregate is laminated | stacked on the upper surface of the laminated body of Claim 3.   The laminated body by which a waterproof layer is laminated | stacked further on the upper surface of the laminated body of Claim 3 or 4.   A laminate in which an adhesive layer (W) made of molten asphalt and a waterproof layer (X) made of a sheet waterproof layer are laminated on the upper surface of the laminate according to any one of claims 3 to 5.