JP2002105395A - Surface prearrangement adjuster for coating film formation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a surface prearrangement adjuster having excellent coating workability, thickly coatable, having excellent adhesiveness to a surface prearrangement base, capable of securing durability. SOLUTION: This surface prearrangement adjuster comprises a hydroxy group-containing vinyl polymer, a polyisocyanate and sand. Preferably the surface prearrangement adjuster further contains a low-molecular weight polyhydric alcohol and a water absorbing agent. The content of sand is preferably 0.1-100 in terms of a weight ratio of sand to an organic component. The hydroxy group-containing vinyl polymer is preferably obtained by polymerizing an acrylic monomer at a high temperature of 150-300 deg.C. The surface prearrangement adjuster has preferably 110-200 flow value by a physical property test method of cement (JIS R 5201) in order to prevent sagging when the surface prearrangement adjuster is applied to a surface prearrangement base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a base adjustment material applied to the surface of a civil engineering or architectural structure for forming a coating film thereon.

[0002]

2. Description of the Related Art A base adjustment material repairs irregularities and burrows on a base surface of concrete or the like, and secures a good surface property as a coating base (hereinafter referred to as unevenness adjustment). As this kind of base adjustment material, for example, a composition in which a synthetic resin emulsion such as an acrylic emulsion and a vinyl acetate emulsion, a foam and a fibrous substance are mixed with cement is known (Japanese Patent Application Laid-Open No. 61-242969). .

A urethane two-part curable composition comprising an acrylic copolymer having a hydroxyl group and an organic polyisocyanate is also known (JP-A-10-17640).
No.).

[0004]

However, when the former preparation material is applied to the surface of a dried concrete base, the moisture in the preparation material is sucked into the concrete base, and the coating of the preparation material is applied. There were problems that the workability was deteriorated and that the base layer made of the base adjustment material was easily peeled off from the concrete base.

The latter two-part curable composition may be difficult to apply thickly depending on the application location and application conditions. The present invention has been made by paying attention to the problems existing in the prior art as described above. An object of the present invention is to provide a base adjustment material which has good coating workability, can be thickly coated, has excellent adhesive strength to a base substrate, and can ensure durability.

[0006]

In order to achieve the above-mentioned object, the undercoating material for forming a coating film according to the first aspect of the present invention contains a vinyl polymer having a hydroxyl group, a polyisocyanate and sand. It is characterized by the following.

According to a second aspect of the present invention, there is provided an undercoat conditioner for forming a coating film, which further comprises a low-molecular-weight polyhydric alcohol and a water-absorbing agent. .

According to a third aspect of the present invention, there is provided the base material for forming a coating film according to the first or second aspect, wherein the content of the sand is 0.1% by weight relative to the organic component.
１００100.

[0010] In a fourth aspect of the present invention, there is provided the undercoat conditioner for forming a coating film according to any one of the first to third aspects, wherein the vinyl polymer having a hydroxyl group comprises 150 or less.
It is obtained by polymerizing a vinyl monomer at a temperature of up to 350 ° C.

The undercoating material for forming a coating film according to the fifth aspect of the present invention is the invention according to any one of the first to fourth aspects, wherein the cement physical test method (JIS R)
5201) is 110 to 200.

[0011] In the invention according to the sixth aspect, the undercoating material for forming a coating film according to any one of the first to fifth aspects is provided on the undercoating base material disposed vertically. When the coating amount with respect to is 1 to 3 kg / m ² , the coating amount of 70
More than weight% is held without dripping.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. The base material for forming a coating film contains a vinyl polymer having a hydroxyl group, a polyisocyanate, and sand. This base adjustment material is mainly used for unevenness adjustment for ensuring good surface properties on the surface of a base material such as concrete.

First, a vinyl polymer having a hydroxyl group is one in which the hydroxyl group undergoes a urethanization reaction with an isocyanate group in the polyisocyanate to form a cured product. As the vinyl polymer, at least one kind of (meth) acrylate having a hydroxyl group (hereinafter, referred to as (meth) acrylate containing a hydroxyl group) and another monomer having an ethylenically unsaturated group (hereinafter, referred to as an ethylenically unsaturated group) A copolymer obtained from one or more kinds of vinyl monomers) is preferable. In this specification, acrylic and methacryl are collectively referred to as (meth) acryl.

As the hydroxyl group-containing (meth) acrylate, various ones can be used. For example, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate, and pentane Polyhydric alcohol mono- or poly (meth) acrylates such as erythritol tri (meth) acrylate and glycerin mono (meth) acrylate; and epoxides such as adducts of cyclohexene oxide with (meth) acrylic acid and (meth) acrylic acid. (Meth) acrylates having one or more hydroxyl groups in the molecule, such as adducts.

As the ethylenically unsaturated monomer, various ones can be used as long as they are other than the above-mentioned hydroxyl group-containing (meth) acrylate. Examples thereof include styrene, acrylonitrile, methacrylonitrile, vinyl acetate, and those having no hydroxyl group ( (Meth) acrylate and the like. Specific examples of the (meth) acrylate having no hydroxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth). Examples include acrylate, 2-ethoxyethyl (meth) acrylate, and isobornyl (meth) acrylate.

The vinyl polymer having a hydroxyl group preferably has a hydroxyl value of 10 to 400 mgKOH / g, more preferably 50 to 300 mgKOH / g. When the hydroxyl value is less than 10 mgKOH / g, the reaction with the polyisocyanate is insufficient, resulting in poor curing, or the chemical resistance, abrasion resistance, and tensile properties of the obtained coating film (underlayer by the underlayer adjusting material). Tends to be inferior. Conversely, 4
If it exceeds 00 mgKOH / g, the resulting underlayer tends to be brittle.

The vinyl polymer having a hydroxyl group preferably has a number average molecular weight of 500 to 20,000, more preferably 1,000 to 10,000. If the number average molecular weight is less than 500, the base adjustment material cannot be thickly applied on the base substrate, or the base layer becomes inferior in flexibility. On the other hand, when it exceeds 20,000, the viscosity of the base adjustment material becomes high, and the workability at the time of coating or the like becomes poor.

In the present specification, the number average molecular weight (hereinafter, referred to as the number average molecular weight)
The abbreviation of Mn if necessary) and the weight average molecular weight (hereinafter abbreviated as Mw if necessary) refer to the molecular weight measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. It is the value converted to.

The vinyl polymer having a hydroxyl group preferably has a glass transition temperature (hereinafter, referred to as Tg) of -70 to 30 ° C, more preferably -60 to 20 ° C. When Tg is lower than -70 ° C, the strength of the obtained underlayer tends to be inferior. When Tg exceeds 30 ° C., the underlayer tends to become brittle.

The copolymer of a hydroxyl group-containing (meth) acrylate and an ethylenically unsaturated monomer may be prepared by a conventionally known method, for example, a bulk polymerization method, a solution polymerization method, an emulsion polymerization method or the like. Accordingly, it is produced by heating and stirring a hydroxyl group-containing (meth) acrylate and an ethylenically unsaturated monomer in the presence of a polymerization solvent, a radical polymerization initiator and a chain transfer agent.

In this case, the reaction temperature may be appropriately selected depending on the monomer used, the presence or absence and type of radical polymerization initiator, the presence or absence of a polymerization solvent, the boiling point, and the like.
Is appropriate. If the temperature is lower than 50 ° C., the molecular weight of the obtained polymer may be too large or the reaction rate may be slow. On the other hand, if the temperature is higher than 350 ° C., a decomposition reaction is generated and the reaction solution is colored. May be seen. When polymerizing at 150 to 350 ° C., a polymer having a target molecular weight can be easily obtained without using a radical polymerization initiator or a chain transfer agent or by using a small amount thereof, and the impurity concentration derived therefrom can be reduced. This is a preferable method because the weather resistance becomes good.

The radical polymerization initiator is not particularly limited, and examples thereof include an azo polymerization initiator and a peroxide polymerization initiator generally used in thermal polymerization. Examples of the azo polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) and 2,2'-azobis (2,4-dimethylvalero). Nitrile) and the like. Examples of the peroxide-based polymerization initiator include hydrogen peroxide, di-t-butyl peroxide, benzoyl peroxide, and the like. The amount of the thermal polymerization initiator used is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the hydroxyl group-containing (meth) acrylate and the ethylenically unsaturated monomer.

The polymerization solvent is not particularly limited as long as it can dissolve the produced copolymer. For example, aromatic hydrocarbons such as toluene and xylene, ethyl acetate, butyl acetate, cellosolve acetate, methyl propylene glycol acetate, carbitol acetate and methyl propylene glycol acetate, acetate such as carbitol acetate and ethyl carbitol acetate, and And ketones such as acetone and methyl ethyl ketone. The amount of the polymerization solvent used is preferably such that the solid content concentration of the obtained copolymer is 10 to 90% by weight.

In particular, a method for continuous polymerization at 150 to 350 ° C. (hereinafter referred to as “high temperature continuous polymerization”) is to use a copolymer having a uniform molecular weight distribution, that is, a copolymer having Mw / Mn in the range of 1.2 to 3.0. It is preferable because it is easy to obtain and it is easy to obtain a good balance of the viscosity of the composition and the physical properties (strength, elongation, etc.) of the cured product.

As the high-temperature continuous polymerization method, JP-A-57-5
02171, 59-6207, 60-2150
A known method disclosed in each gazette such as No. 07 may be used. For example, a pressurizable reactor is filled with a solvent, and after a predetermined temperature is set under pressure, a monomer comprising a hydroxyl group-containing (meth) acrylate, an ethylenically unsaturated monomer, and, if necessary, a polymerization solvent is used. There is a method in which the body mixture is supplied to the reactor at a constant supply rate, and an amount of the reaction solution corresponding to the supply amount of the monomer mixture is withdrawn.

When a polymerization solvent is used, the solvent charged into the reactor before the start of the reaction and the polymerization solvent to be mixed with the monomer mixture may be the same or different. As the charged solvent or the polymerization solvent before the start of the reaction, the same solvents as those described above can be used, and glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and tripropylene glycol,
These monoalkyl ethers, dialkyl ethers and the like can be used. The mixing ratio of the polymerization solvent is preferably 200 parts by weight or less based on 100 parts by weight of the monomer mixture.

Further, a radical polymerization initiator can be added to the monomer mixture, if necessary, and the same compounds as those described above can be used. When the thermal polymerization initiator is blended with the monomer mixture, the blending amount is as follows.
It is preferably 0.001 to 5 parts by weight based on 00 parts by weight.

The reaction pressure depends on the reaction temperature and the boiling point of the monomer mixture and the solvent used and does not affect the reaction, but may be any pressure that can maintain the reaction temperature. The residence time of the monomer mixture is preferably 2 to 60 minutes. If the residence time is less than 2 minutes, the reaction rate of the monomer may decrease, and if it exceeds 60 minutes, the productivity of the hydroxyl group-containing vinyl polymer may deteriorate.

The method of polymerizing at a temperature of 50 ° C. or higher and lower than 150 ° C. has an advantage that the equipment for producing the polymer can be relatively inexpensive. In this case, a monomer mixture consisting of a hydroxyl group-containing (meth) acrylate and an ethylenically unsaturated monomer can be polymerized at once, but a part of the monomer mixture is used as a polymerization solvent and radical polymerization. The polymerization method of adding the initiator to the reactor charged and initiating the reaction, and then dropping the remaining monomer mixture into the reaction solution, in order to reduce the molecular weight distribution of the resulting hydroxyl-containing vinyl polymer. preferable.

Next, the polyisocyanate reacts with a vinyl polymer having a hydroxyl group by urethanation to form a cured product. The polyisocyanate is preferably a liquid at ordinary temperature which does not require dilution with a solvent.

Specifically, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate and the like, and aliphatic poly- mers having no aromatic ring such as burettes, isocyanurates and carbodiimide modified products thereof. Isocyanates are preferred for improving the weatherability of the cured product.

In addition, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, liquid diphenylmethane diisocyanate,
Various polyisocyanates such as tolylene diisocyanate, tolidine diisocyanate, tetramethyl xylylene diisocyanate, naphthalene diisocyanate and the like, and burettes, isocyanurates and carbodiimide modified products thereof can be used. These polyisocyanates may be used in combination of two or more.

The mixing ratio of the polyisocyanate and the hydroxyl group-containing vinyl polymer is preferably 0.5 to 2.0 as an equivalent ratio of the isocyanate group in the polyisocyanate to the hydroxyl group in the vinyl polymer.
More preferably, it is 0.7 to 1.5. Further, when the base adjustment material is a material to which a low molecular weight polyhydric alcohol described below is added, the equivalent ratio of the isocyanate group to the total amount of the hydroxyl group in the vinyl polymer and the hydroxyl group in the low molecular weight polyhydric alcohol is 0. It is preferably from 0.5 to 2.0, more preferably from 0.7 to 1.5. When the equivalent ratio is smaller than 0.5, the strength of the obtained underlayer is low and the chemical resistance becomes poor.
It is preferably 0.5 or more. The equivalent ratio is 2.
If it exceeds 0, the resulting underlayer is not suitable because it tends to foam under high humidity.

The sand is a component necessary for adjusting the unevenness of the ground surface with the ground adjusting material, and is made of fine particles of rock or mineral. The sand mentioned here has a particle size of 0.
The one containing 10% by weight or more of the one having a thickness of 0.5 to 2 mm is preferable, and the one containing 30% by weight or more is preferable. This makes it possible to adjust the fluidity of the base adjustment material to the base surface, maintain good coating workability, and enable thick coating. If the sand particle size is less than 0.05 mm exceeds 90% by weight, the elongation in the coating operation may be poor. If the sand size exceeds 2 mm exceeds 90% by weight, a smooth underlayer may be formed. May not be obtained. As the sand, silica sand mainly composed of quartz (SiO ₂ ) or feldspar, specifically, No. 7 silica sand is used.

The content of sand is preferably from 0.1 to 100, and more preferably from 0.2 to 50 in terms of a weight ratio to organic components such as a vinyl polymer having a hydroxyl group, a polyisocyanate, and a low molecular weight polyhydric alcohol described below. Is more preferable, and more preferably 0.3 to 30. When the weight ratio is less than 0.1, the flowability of the base adjustment material is adjusted to maintain good coating workability, and it becomes difficult to perform thick coating, and when it exceeds 100, the coating workability becomes poor, In some cases, a smooth underlayer cannot be obtained.

In order to improve the mechanical properties of the resulting coating film, it is preferable to blend a low-molecular-weight polyhydric alcohol with the base material. The low molecular weight polyhydric alcohol means a polyhydric alcohol having a total number of carbon atoms in the molecule of 2 to 8. Specific examples of the low molecular weight polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol,
1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, bisphenol A, trimethylolethane, trimethylolpropane, glycerin, sorbitol, etc. Is mentioned. These low molecular weight polyhydric alcohols can be used in combination of two or more.

When the low molecular weight polyhydric alcohol is blended, the preferred ratio is 0.1 to 200 parts by weight based on 100 parts by weight of the hydroxyl group-containing polymer, more preferably 1 to 200 parts by weight.
It is 150 parts by weight. When the proportion is less than 0.1 part by weight, the effect of improving the mechanical properties of the obtained underlayer is not sufficient, and when the proportion is more than 200 parts by weight,
The resulting underlayer may be hard and brittle.

Further, it is preferable to add a water absorbing agent to the base material, and the water absorbing agent suppresses the reaction of moisture in the base material or air with the polyisocyanate to generate carbon dioxide gas and foam. can do. Therefore, by blending the water absorbing agent, it is possible to maintain the cosmetic properties of the obtained underlayer surface, the strength of the underlayer, and the adhesiveness of the underlayer to the undersubstrate. As this water absorbing agent, zeolite that physically adsorbs water, powdered silica gel,
Calcium oxide, anhydrous gypsum, which chemically adsorbs water,
Cement or the like can be used. The mixing ratio of the water absorbing agent is preferably 0.01 to 100 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the vinyl polymer having a hydroxyl group. When the proportion is less than 0.01 parts by weight, the foaming suppressing effect is not sufficiently exhibited, and when the proportion is more than 100 parts by weight, the obtained underlayer may be hard and brittle.

When the polyisocyanate does not have an aromatic ring, it is preferable that the base adjustment material is one to which a catalyst has been added in order to accelerate the curability. Such catalysts include triethylamine, N, N-dimethylcyclohexylamine, N, N, N'N'-tetramethylethylenediamine, N, N, N'N'-tetramethylpropane 1,3-
Diamine, N, N, N'N'-tetramethylhexane-1,6-diamine, N, N, N ', N``N''-pentamethyldiethylenetriamine, N, N, N', N''N '' -Pentamethyldipropylene-triamine, tetramethylguanidine, triethylenediamine, N, N'-dimethylpiperazine, N, -methyl, N '-(2-dimethylamino) -ethylpiperazine, N-methylmorpholine, N (N'-dimethylaminoethyl) -morpholine, 1,2-
Dimethylimidazole, dimethylaminoethanol, dimethylaminoethoxyethanol, N, N, N'-trimethylaminoethyl-ethanol, N-methyl-N '-(2-hydroxyethyl) -ethanolamine, N-methyl-N'-(2 -Hydroxyethyl) -piperazine, N- (2-hydroxyethyl)
Amine catalysts such as morpholine, bis (2-dimethylaminoethyl) ether and ethylene glycol bis (3-dimethyl) -aminopropyl ether, lead octenoate, lead octylate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxy And organic metal compounds such as dibutyltin dimalate, dioctyltin mercaptide and dioctyltin thiocarboxylate, and calcium carbonate and sodium bicarbonate. Among these, the use of an organometallic compound is preferable because of excellent reactivity of the urethanization reaction.

The amount of the catalyst to be added is 0.001 to 1 with respect to 100 parts by weight of the vinyl polymer having a hydroxyl group.
0 parts by weight is preferable, and 0.001 to 3 parts by weight is more preferable. When a catalyst is compounded in the composition, it is preferable to first mix the catalyst in a mixture excluding the polyisocyanate, and then mix the polyisocyanate, since a side reaction can be reduced.

In addition, a filler is blended into the underlayer adjusting material to adjust the fluidity thereof to improve the sagging property and the coating workability and to increase the strength of the underlayer. Examples of the filler include barium sulfate, silicon oxide, talc, mica, kaolin clay, calcium carbonate, and the like. The compounding amount of the filler is preferably such that the total weight of the filler and the sand is 1 to 100 with respect to the organic component.

In addition to the above components, the base conditioner of the present invention may further comprise other additives, if necessary, such as natural mineral fibers such as sepiolite, attapulgite, and bolastonite, glass fibers, carbon fibers, aramid fibers, and phenols. Fibers, artificial fibers such as polyvinyl alcohol fibers, thickening and anti-sagging agents such as organic thickeners, coloring pigments such as phthalocyanine blue, phthalocyanine green, titanium oxide, carbon black and iron oxide, carbodiimides, azo Hydrolysis inhibitors such as dicarboxylic acid esters and fatty acid amides, sterically hindered phenols, antioxidants such as aromatic diamines, ultraviolet absorbers such as benzotriazoles, benzophenones and salicylic acids, Silicone, acrylic and mineral defoamers and leveling It can be blended, or the like.

When these other additives are mixed, the mixing ratio is 1 to 100 parts by weight of the organic component.
It is preferably not more than 00 parts by weight. When the base material obtained as described above is applied to a base material, a cement physical test method (JIS) is required to maintain the fluidity of the base material properly and to improve the sagging property and the coating workability. R 52
It is preferable that the flow value according to 01) is 110 to 200. If the flow value is less than 110, the fluidity of the base adjustment material is low and the coating workability is poor. If the flow value exceeds 200, the flowability of the base adjustment material is high and sagging occurs during the coating operation. It is not preferable because it becomes easy. Examples of the base material include an inorganic material represented by concrete and mortar.

In the case where the base material is applied to the base material arranged vertically, when the coating amount on the base material is 1 to 3 kg / m ² , It is desirable that 70% by weight or more of the work is held without dripping.
Thereby, the underlayer adjusting material can be prevented from dripping from the underlayer base material, the thickness of the underlayer can be made substantially uniform, and the appearance of the underlayer can be well maintained.

In the case of applying, pouring or filling the base material to the base material, similarly to the conventional two-component curable urethane composition, a vinyl polymer having a hydroxyl group, a water absorbing agent and a The polyisocyanate may be mixed immediately before use with the one in which the molecular weight polyhydric alcohol has been mixed in advance.

A mixture of a vinyl polymer having a hydroxyl group, a water absorbing agent and a low molecular weight polyhydric alcohol may be subjected to a dehydration operation after blending a catalyst and other blends if necessary and before blending a polyisocyanate. preferable.
By performing the dehydration operation, it is possible to further effectively prevent the foaming of the composition resulting from the reaction between the water and the polyisocyanate contained in the vinyl polymer having a hydroxyl group, the water absorbing agent and the low molecular weight polyhydric alcohol. it can. As a method of the dehydration operation, a vacuum dehydration method and the like can be mentioned.

As a method of applying the base adjustment material, a roller,
Examples include methods using rakes, trowels, sprays, and the like, and as an injection or filling method, a caulking gun,
Examples include a method using a spatula, a spatula, a trowel, and the like. The base adjustment material as described above can be suitably used for various uses such as a coating material such as a paint, a waterproof material, a wall material and a painted floor material, and a sealing material.

When the underlayer is formed by the above-described underlayer adjusting material, a coating film (overcoat layer) of an overcoat is formed thereon. As the overcoat paint, the above-mentioned hydroxyl group-containing vinyl polymer having a number average molecular weight of 1,000 to 2,000
No. 0 and a composition containing the above-mentioned polyisocyanate are preferably used. Furthermore, 1 to 50 parts by weight of the low-molecular-weight polyhydric alcohol is mixed with 100 parts by weight of the hydroxyl-containing vinyl polymer in the overcoat paint for the same reason as described above. Then, an undercoat layer made of an undercoat adjustment material is formed on the undercoat base material, and an overcoat layer of an overcoat paint is formed thereon.

As described above, according to the base conditioner described in detail in the embodiment, since the sand is contained in addition to the vinyl polymer having a hydroxyl group and the polyisocyanate, the fluidity of the base conditioner can be adjusted. The coating workability is good, thick coating is possible, and irregularity adjustment on the surface of the base substrate can be easily performed, and good surface properties can be secured.

Moreover, the adhesive strength to the underlying substrate is excellent, and the durability can be ensured. In addition, the following effects unique to the embodiment can be obtained. By using a vinyl polymer having a hydroxyl group, particularly one having a number average molecular weight of 500 to 20,000, the viscosity of the base adjustment material can be reduced, and workability in coating, pouring or filling of the base adjustment material. Can be improved.

The base material can be made to have a low viscosity as described above and can be used as a solvent-free composition that does not use an organic solvent, so that problems such as odor can be suppressed. -Since the base adjustment material can be a solvent-free composition, the coating film of the base adjustment material can be thickened.

When the vinyl polymer having a hydroxyl group constituting the base adjustment material is obtained by a high-temperature polymerization method at 150 to 350 ° C., a phosphoric ester is added to the base polymer until the base adjustment material is cured. Time (pot life)
Can be lengthened, and coating workability can be improved.

When hydroxyethyl methacrylate is used as the hydroxyl group-containing (meth) acrylate for forming the hydroxyl group-containing vinyl polymer, the hydroxyl group-containing vinyl polymer and the polyisocyanate are used as compared with the case where hydroxyethyl acrylate is used. The cured product (underlayer) has excellent hydrolysis resistance.

[0054]

EXAMPLES Hereinafter, the above embodiment will be described more specifically with reference to Production Examples, Examples and Comparative Examples. In the following examples, “part” means “part by weight” and “%” means “% by weight”. (Production Example 1, Production of Polymer Having a Hydroxyl Group by High-Temperature Continuous Polymerization Method) A 300-ml pressurized stirred tank reactor equipped with an electric heater was filled with diethylene glycol monoethyl ether, and the temperature was raised to 250 ° C. The pressure is adjusted to a gauge pressure of 2.45 to 2.65 MPa (2
5 to 27 kgf / cm ² ).

Then, while keeping the pressure of the reactor constant, 16 parts of 2-hydroxyethyl methacrylate and 20 parts of 2-hydroxyethyl acrylate as the hydroxyl group-containing (meth) acrylate, and 2-ethylhexyl acrylate as the ethylenically unsaturated monomer. A monomer mixture A-1 consisting of 54 parts of rate and 10 parts of styrene was continuously supplied from the raw material tank to the reactor at a constant supply rate (23 g / min, residence time: 12 minutes), and A reactant corresponding to the supply amount of the body mixture A-1 was continuously extracted from the outlet. Immediately after the start of the reaction, after the reaction temperature once decreased, a temperature increase due to the heat of polymerization was observed. However, the reaction temperature was maintained at 270 to 271 ° C. by controlling the heater.

The time when the temperature was stabilized after the start of the supply of the monomer mixture A-1 was defined as the starting point of the withdrawal of the reaction solution, and the reaction was continued for 50 minutes. As a result, 1150 parts of the monomer mixture A-1 was obtained. Then, 1130 parts of the reaction solution was recovered.

Then, the reaction solution was introduced into a thin film evaporator to separate volatile components such as unreacted monomers, to obtain 990 parts of a concentrated solution (copolymer B-1). From the gas chromatograph,
It was confirmed that no unreacted monomer was present in the concentrate. GPC using tetrahydrofuran as solvent
The number average molecular weight (hereinafter, abbreviated as Mn) of the copolymer B-1 in terms of polystyrene in terms of the molecular weight determined by (gel permeation chromatography) is 2,000, and the weight average molecular weight (hereinafter, abbreviated as Mw) is 3,600, Mw / Mn
Was 1.80. The concentrated solution has a hydroxyl value of 173.
mg KOH / g. (Production Example 2, Production of a polymer having a hydroxyl group by a solution polymerization method) 10 parts of hydroxyethyl methacrylate and 20 parts of hydroxyethyl acrylate as a hydroxyl group-containing (meth) acrylate, 2- as an ethylenically unsaturated monomer
A mixture obtained by mixing 70 parts of ethylhexyl acrylate was used as a monomer mixture A-2.

In a four-necked flask equipped with a reflux condenser, a thermometer, a dropping funnel, a glass tube for purging nitrogen and a stirrer, 15 parts of the monomer mixture A-2 and methyl isobutyl ketone (hereinafter referred to as MIBK). And 100 parts of 2,2′-azoisobutyronitrile were charged, and the polymerization reaction was started at 90 ° C. while blowing nitrogen. Thereafter, 85 parts of the monomer mixture A-2, 25 parts of MIBK and 2,2′-
A polymerization reaction was carried out by continuously dropping 31 parts of a solution composed of 6 parts of azobisisobutyronitrile over 6 hours.

The solvent was distilled off from the obtained reaction solution under reduced pressure to obtain a copolymer B-2. The molecular weight of copolymer B-2 determined by the same method as in Production Example 1 was Mn of 8,800 and Mw of 1
It was 9,000 and Mw / Mn was 2.2. The hydroxyl value was 146 mgKOH / g.

Example 1 100 parts of B-1 obtained in Production Example 1, 0.01 part of di-n-butyltin dilaurate,
100 parts of propylene glycol, 100 parts of polypropylene glycol [P-1000, manufactured by Asahi Denka Co., Ltd.], 5 parts of molecular sieve 5A, polysiloxane-based defoamer BYK-
066 [manufactured by Tetsutani Corporation] 1 part, calcium carbonate 500
Parts and 500 parts of No. 7 silica sand were stirred using a spatula,
A mixture C-1 was obtained.

Next, 100 parts of C-1 (0.27 meq
/ G) and an isocyanurate of hexamethylene diisocyanate [Sumidur N
3500, NCO group content 5.14 meq / g, manufactured by Sumitomo Bayer Urethane Co., Ltd.] with an NCO / OH equivalent ratio of 1.2
And the resulting mixture was sufficiently stirred to produce a substrate adjusting material. The obtained base material was evaluated according to the following method. Table 1 shows the results. <Evaluation> (Flow value) Measured according to JIS R 5201 “Physical test method for cement”. (Sagging) A wooden frame (inside dimensions 30 × 30 cm, thickness: 0.5, 1, 3 kg / m ² ) was placed on a slate plate (40 × 40 cm). After pouring and adjusting the above-mentioned base adjustment material adjusted to 30 ° C., the wooden frame was removed, the slate plate was set upright, and the film thickness was measured at all five points. Next, after 30 minutes, the dripping condition was observed and the film thickness was measured, and the change in the film thickness was examined. In Table 1, ○ and × have the following meanings. ：: No abnormality. X: A dripping trace is observed or a part of the coating film has a portion which is 5% or more thicker or thinner than at the time of coating. (Adhesion strength) 1kg of the above base adjustment material on concrete plate
/ M ² , and cured for 7 days at 20 ° C. and 60% humidity, and the adhesive strength of a test specimen was measured using a Kenken-type tensile tester. Also, this specimen was placed in water at 20 ° C. for 30 minutes.
The bond strength of the test specimen immersed in water for 60 days and the test specimen immersed in water of 60 ° C. for 7 days was similarly measured. (Workability of ironing) The above-mentioned base adjustment material is brought to a temperature of 15 ° C., and is applied to a vertically laid concrete plate (15 ° C.) with a metal iron,
Judgment was made based on the extensibility of the material, the weight applied to the trowel at the time of spreading, and the like. In Table 1, ○ and × indicate the following meanings. ：: Good spreadability and easy coating, ×: Poor spreadability, requiring considerable force to spread with a trowel, or low in viscosity, and flows down from trowel plate. Example 2 100 parts of B-1 obtained in Production Example 2, 0.005 part of di-n-butyltin dilaurate, 90 parts of propylene glycol, and 150 parts of polypropylene glycol
Part, 5 parts of molecular sieve 5A, defoamer BYK-066
1 part, 40 parts of glass balloon, 50 parts of No. 7 silica sand, 20 parts of light calcium carbonate, and 5 parts of sepiolite (trade name: Miracle LFC, manufactured by Omi Mining Co., Ltd.) were sufficiently stirred using a spatula, and the mixture C-2 was mixed. Obtained.

Next, 100 parts of C-2 (0.68 meq
/ G) and the isocyanurate of hexamethylene diisocyanate used in Example 1 were converted to an NCO / OH equivalent ratio of 1.2.
And the resulting mixture was sufficiently stirred to produce a substrate adjusting material. This base material was evaluated according to the following method. Table 1 shows the results. Example 3 100 parts of B-1 obtained in Production Example 1, 0.02 part of di-n-butyltin dilaurate, 100 parts of propylene glycol, and 100 parts of polypropylene glycol
Part, 5 parts of molecular sieve 5A, defoamer BYK-066
One part, 200 parts of calcium carbonate and 200 parts of No. 7 silica sand were sufficiently stirred with a spatula to obtain a mixture C-3.

Next, 100 parts of C-3 (0.51 meq
/ G) and the isocyanurate of hexamethylene diisocyanate used in Example 1 were converted to an NCO / OH equivalent ratio of 1.2.
And the resulting mixture was sufficiently stirred to produce a substrate adjusting material. This base material was evaluated according to the following method. Table 1 shows the results. Example 4 100 parts of B-1 obtained in Production Example 1, 0.1 part of di-n-butyltin dilaurate, 10 parts of hexylene glycol, polypropylene glycol [P-100
0, manufactured by Asahi Denka Co., Ltd.), 20 parts, molecular sieve 4A, 10 parts, polysiloxane-based defoamer BYK-066 [manufactured by Tetani Corporation], 3 parts, calcium carbonate, 20 parts, cement 10
0 parts and 200 parts of No. 7 silica sand were stirred using a spatula to obtain a mixture C-4.

Next, 100 parts of C-4 (0.78 meq
/ G) and an isocyanurate of hexamethylene diisocyanate [Sumidur N
3500, NCO group content 5.14 meq / g, manufactured by Sumitomo Bayer Urethane Co., Ltd.] with an NCO / OH equivalent ratio of 0.9
And the resulting mixture was sufficiently stirred to produce a substrate adjusting material. The obtained base material was evaluated according to the following method. Table 1 shows the results. (Comparative Example 1) Aron QD color AU (acrylic urethane top coat, manufactured by Toagosei Co., Ltd.) was evaluated according to the following method. Table 1 shows the results. In addition,
Due to the low viscosity of this material, the adhesion test was performed with a coating thickness of 0.2k.
g / m ² . Since this material contains a solvent, it is difficult to perform construction in a closed system structure, an underground structure, and the like. (Comparative Example 2) An urethane roof waterproofing material of another company containing polyether polyol and polyisocyanate as main components was evaluated according to the following method. Table 1 shows the results.

[0065]

[Table 1] As shown in Table 1, in Examples 1, 2, and 4, the flow value was in the range of 110 to 200, there was no sagging, the adhesive strength was maintained, and the ironing workability was good. In Example 3, since the flow value was slightly higher, sagging occurred when the coating amount was increased, but the adhesive strength and the iron workability were good. On the other hand, in Comparative Examples 1 and 2, the flow value is high, sagging occurs, the adhesive strength is low, and the ironing workability may be poor. (Embodiment 5) The base adjustment material of Embodiment 4 was dried by 30 × 30.
cm on a slate plate with a thickness of 1 kg / m ² ,
After curing at 90 ° C. and a humidity of 90% for one day, the surface condition and the cross section of the film were observed. As a result, no abnormalities such as swelling and pinholes were observed.

Further, an area of 30 × 30 cm and a thickness of 3 cm
After immersing the concrete plate in water for 2 days,
Gently wipe off, and 1 kg of the base adjustment material of Example 4
/ M ^TwoAnd dipped in water to a thickness of 1.5 cm
Cured for 1 day at 40 ° C and 90% humidity in the same condition
I thought. As a result, abnormalities such as swelling and pinholes are not seen.
Was not. The concrete plate has a diameter of 1c.
In advance, a hole with a depth of 1 cm and a depth of 1 cm was prepared.
Filling the holes with a ground conditioning material during coating, the swelling height after curing
Was examined. As a result, it is almost 0.3 mm swelling
I wasn't sure. (Comparative Example 3) The composition of Comparative Example 2 was dried 30 x 30 cm
1kg / m on slate board^TwoCoating with thickness of 40 ℃,
After curing at 90% humidity for 1 day, observe the surface condition and cross section of the film
did. As a result, there are many blisters having a diameter of 0.5 to 3 cm over the entire surface.
A number occurred. Further, the area is 30 × 30 cm and the thickness is 3 cm
After immersing the concrete plate in water for 2 days,
Gently wipe, and then apply the composition of Comparative Example 2 at 1 kg / m
^TwoIn a thickness of 1.5 cm and immersed in water to a thickness of 1.5 cm
Cured at 40 ° C and 90% humidity for 1 day and observed the appearance
Was.

As a result, a large number of blisters having a diameter of 0.5 to 3 cm and many pinholes having a diameter of 1 to 3 mm occurred on the entire surface. Also, as in Example 4, the hole of 1 cm in diameter and 1 cm in depth was filled with the composition of Comparative Example 2, and as a result, the swollen height after curing was 3
mm, the blister became very noticeable. (Example 6) <Production of overcoating material A> 100 parts (2.34 meq / g) of C-1 in Example 1 and an isocyanurate of hexamethylene diisocyanate as a polyisocyanate [Sumidur N3500, NCO group Content 5.14 meq / g, manufactured by Sumitomo Bayer Urethane Co., Ltd.]
Was added at an NCO / OH equivalent ratio of 1.05, and the mixture was sufficiently stirred to produce a composition. <Testing> Drain the concrete water tank in use,
After drying for 5 days, the fragile portion on the surface was peeled off, and the base preparation material of Example 4 was applied to an area of 50 m ² at 1 kg / m ^2, and the next day, the top coating material A was applied at a thickness of 0.5 kg / m ² . Coated twice.
As a result, no swelling or holes are generated, and the adhesive strength is 2 MPa.
was gotten. The fracture mode was cohesive failure in the underlayer by the underlayer adjusting material. (Comparative Example 4) 100 parts of cement and sand 3 were added to the water tank of Example 6.
5 parts of mortar consisting of 00 parts, 55 parts of water and 1 part of water reducing agent
² kg / m ^{2 is} applied to the area of 0 m ² and the next day, 25 m ² , 7
Day after the thickness of each top coating material A to 25 m ² in of 0.5k
g / m ² was applied twice. As a result, both the coated part on the next day and the coated part after 7 days swelled and formed holes in the top coating material A, and the adhesive strength was 0.4 MPa and 0.6 MPa, respectively. The fracture mode was an interfacial fracture between the mortar base layer and the top coat A.

The technical idea grasped from the above embodiment will be described below. The base material for forming a coating film according to any one of claims 1 to 6, wherein the polyisocyanate is an aliphatic polyisocyanate that is liquid at room temperature and has no aromatic ring. In this case, it is not necessary to dilute the polyisocyanate with a solvent, and the coating film can have excellent weather resistance.

[0069]

As described above, according to the present invention, the following effects can be obtained. ADVANTAGE OF THE INVENTION According to the base | substrate adjustment material of invention of Claim 1, coating workability | operativity is good, a thick coating is possible, the adhesive strength with respect to a base | substrate base material is excellent, and durability can be ensured.

According to the second aspect of the present invention, in addition to the effects of the first aspect, the mechanical properties of the coating film can be improved, and foaming is generated by the generation of carbon dioxide gas. Can be suppressed.

According to the third aspect of the present invention, in addition to the effects of the first or second aspect,
It is possible to adjust the fluidity of the base adjustment material, maintain good coating workability, and enable thick coating.

According to the fourth aspect of the present invention, in addition to the effects of the first aspect of the present invention, a radical polymerization initiator or a chain transfer in the coating film. The concentration of impurities such as agents can be reduced, and the weather resistance of the coating film can be improved.

According to the fifth aspect of the present invention, in addition to the effects of the first aspect of the present invention, in addition to the effect of the first aspect, the fluidity is appropriately maintained and the sagging property is improved. Coating workability can be improved.

According to the sixth aspect of the present invention, in addition to the effect of the first aspect of the present invention, in addition to the effect of the first aspect of the present invention, the underlayer adjusting material is disposed in a vertical direction. When coated on the base substrate at a coating amount of 1 to 3 kg / m ² , the base adjustment material can be prevented from dripping from the base substrate.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masafumi Achinami 1 in Funamicho, Minato-ku, Nagoya-shi, Aichi Prefecture 1 within Toagosei Co., Ltd. (72) Inventor Kazuto Irita Funamicho, Minato-ku, Nagoya-shi, Aichi No. 1 in Toagosei Co., Ltd. Nagoya Research Institute Co., Ltd. (72) Inventor Yasuhiko Mori No. 1 in Funamicho, Minato-ku, Nagoya City, Aichi Prefecture No. 1 in Toagosei Co., Ltd. Nagoya Research Institute F-term (reference) 4J038 DG191 DG271 DG281 DG291 HA186 HA376 HA446 HA496 HA556 JA20 JA21 JA64 KA02 LA02 NA12 NA23 PB05 PC04

Claims (6)

[Claims] 1. An undercoat conditioner for forming a coating film, comprising a vinyl polymer having a hydroxyl group, polyisocyanate and sand. 2. The base adjustment material for forming a coating film according to claim 1, further comprising a low molecular weight polyhydric alcohol and a water absorbing agent. 3. The base material for forming a coating film according to claim 1, wherein the content of the sand is 0.1 to 100 in terms of a weight ratio to an organic component. 4. A vinyl polymer having a hydroxyl group of 150 to
The undercoat conditioner for forming a coating film according to any one of claims 1 to 3, which is obtained by polymerizing a vinyl monomer at a temperature of 350 ° C. 5. A physical test method for cement (JIS R)
The base material for coating film formation according to any one of claims 1 to 4, wherein the flow value according to 5201) is 110 to 200. 6. When the amount of coating on the base material arranged vertically is 1 to 3 kg / m ² , 70% by weight or more of the amount of coating is held without dripping. The base material for forming a coating film according to any one of claims 1 to 5.