JP2564077B2 - Synthetic resin coating film manufacturing method and synthetic resin coating film forming agent used therefor - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a synthetic resin coating film for forming a coating film used as a waterproof membrane material, floor coating material and the like, and a synthetic resin coating agent used therefor.

[0002]

Methyl methacrylate (hereinafter abbreviated as "MMA") syrup composition is used as a coating material for floors, roofs or outer walls made of concrete, asphalt, metal, etc., because of its excellent weather resistance, chemical resistance and fastness. It is used as a curable material. The MMA-based syrup composition is obtained by dissolving an MMA homopolymer in an MMA monomer or by partially polymerizing the MMA monomer alone or the above monomer and another vinyl polymerizable monomer. It contains an MMA-based monomer or a prepolymer as a reaction component and paraffin wax as an air barrier. When the above composition is applied alone or in combination with a filler such as silica powder, calcium carbonate, quartz powder, a coloring agent such as red iron oxide, phthalocyanine blue, and the like,
The paraffin wax floats on the surface of the coating film to form a thin film, and the radical polymerization reaction proceeds in a state where the air is blocked, so that a cured film having excellent weather resistance and chemical resistance can be obtained.

[0003]

However, the above-mentioned M
When a coating film is formed using a MA-based syrup composition in a wet base or in a high-humidity atmosphere, there is a problem that the polymerization reaction layer is insufficiently cured due to contact with moisture. Further, since the shrinkage factor during curing is large, there is a problem that the coating film may be warped or distorted depending on the type of the base.

The present invention has been made in view of the above circumstances, and a method for producing a synthetic resin coating film which is excellent in curability in a wet substrate and in a high humidity atmosphere, and which is not impaired in curing shrinkage and flexibility and a method therefor. It is an object of the present invention to provide a synthetic resin coating film-forming agent to be used.

[0005]

In order to achieve the above object, the present invention provides a method for applying a synthetic resin-based coating film forming material to a cement component in advance when the synthetic resin-based coating film forming material is applied to the surface of a substrate. Is used to form a synthetic resin-based coating film, which is a method for producing a synthetic resin-based coating film using the following components (A) and (B) as the synthetic resin-based coating film forming material. The summary is 1. (A) A liquid acrylic polymerizable film forming agent composed of the following components (a) to (e). (A) At least one of alkyl acrylate and alkyl methacrylate. (B) An acrylic polymer soluble in the component (a). (C) A plasticizer soluble in the component (a). (D) A compound having at least two polymerizable double bonds in one molecule. (E) A composition containing at least one paraffin wax having a melting point of 40 ° C. or higher. (B) The polymerization initiator of the component (A).

A second aspect of the present invention is a synthetic resin coating film-forming agent comprising the following components (A) and (C), and (A) is composed of the above components (a) to (e). Liquid acrylic polymerizable film forming agent. (C) A powdery material comprising the following components (x) and (y). (X) Cement powder. (Y) A polymerization initiator as the component (A). A synthetic resin-based coating film-forming agent comprising the following components (A), (D) and (E) is the third gist. (A) A liquid acrylic polymerizable film-forming agent composed of the above components (a) to (e). (D) Cement powder. (E) The liquid polymerization initiator of the above component (A).

[0007]

In other words, the present inventor has found that in the formation of a synthetic resin coating film in which a synthetic resin coating film is formed by a radical polymerization system, it has excellent curability under a wet base and a high humidity atmosphere, and does not undergo curing shrinkage. A series of studies were conducted in order to obtain a synthetic resin coating film-forming agent with less deterioration in flexibility. As a result, in addition to the acrylic-based polymerizable film forming agent and the polymerization initiator, when a cement component having a moisture absorption curing property and a shrinkage-reducing function is added, and a synthetic resin-based coating film is formed using this, high moisture content is obtained. Even in such cases, the inventors have found that the cement component absorbs moisture and is sufficiently cured to form a synthetic resin coating film, and that warpage and distortion due to curing shrinkage do not occur, and thus the present invention has been accomplished.

Next, the present invention will be described in detail.

The synthetic resin coating film forming agent of the present invention comprises a liquid acrylic polymerizable film forming agent (component A), and
It is obtained using a cement powder (x component) and a polymerization initiator (y component), or a cement powder (D component) and a liquid polymerization initiator (E component).

The liquid acrylic polymerizable film forming agent (component A) is composed of the following components (a) to (e).

(A) At least one of acrylic acid alkyl ester and methacrylic acid alkyl ester. (B) An acrylic polymer soluble in the component (a). (C) A plasticizer soluble in the component (a). (D) A compound having at least two polymerizable double bonds in one molecule. (E) A composition containing at least one paraffin wax having a melting point of 40 ° C. or higher.

The above-mentioned component (a) is polymerized to form the skeleton of a synthetic resin coating film, and examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, Examples thereof include i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate and the like. Examples of the methacrylic acid ester include lauryl methacrylate. These may be used alone or in combination. Among them, a homopolymer having a glass transition temperature of 80 ° C. or higher (for example, ethyl methacrylate, t-butyl methacrylate, etc.),
Similarly, a mixture obtained by combining a homopolymer having a glass transition temperature of 0 ° C. or higher (for example, butyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, etc.) with a mixture has suitable strength and flexibility in the resulting synthetic resin coating film. It is suitable because it can impart the property. Then, the mixing ratio of the monomer (M) having a glass transition temperature of 80 ° C. or higher and the monomer (N) having a glass transition temperature of 0 ° C. or higher is a weight ratio,
It is preferable to set the ratio of M / N = 30/70 to 85/15.

The content of the above-mentioned component (a) can be appropriately set, but is particularly preferably 51 to 85% by weight (hereinafter referred to as "%") in the liquid acrylic polymerizable film-forming agent (component A). It is preferable to set it to (abbreviation), more preferably 60
˜75%. That is, when the content of the component (a) is less than 51%, the viscosity of the obtained synthetic resin coating film-forming agent becomes high, and the coating workability and self-leveling property (ability to form a film having a uniform thickness) tend to decrease. On the contrary, if it exceeds 85%, the curability tends to deteriorate.

The acrylic polymer which is the above-mentioned component (b) is
It is added to adjust the viscosity of the composition, shorten the curing time due to the presence of the polymer content, and improve the durability by balancing the strength and flexibility of the synthetic resin coating film, and it is soluble in the component (a). Must. Examples of such an acrylic polymer include methyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, and acrylic. Polymers obtained by polymerizing monomers such as n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, and 2-ethylhexyl acrylate, or 2 thereof.
An example of the copolymer is a combination of two or more kinds. Among them, methyl methacrylate polymers, monomers having a low glass transition temperature of methyl methacrylate and homopolymers (for example, methyl acrylate, ethyl acrylate, acrylic acid n
-Butyl, i-butyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, etc.) is preferably used. The molecular weight of these polymers is preferably 200 to 8000.

The content of the above-mentioned component (b) can be appropriately set, but it is particularly preferably set to 10 to 24% in the liquid acrylic polymerizable film-forming agent (component A), and more It is preferably set to 60 to 75%. That is, if the content of the component (b) is less than 10%, the curability of the resulting synthetic resin coating film-forming agent tends to deteriorate, and conversely, if it exceeds 24%, the viscosity of the synthetic resin film-forming agent is increased. This is because there is a tendency that the coating workability and the self-leveling property are deteriorated due to the increase of the value.

The plasticizer which is the component (c) is added for the purpose of adjusting the viscosity of the synthetic resin coating film forming agent and improving the followability to the underlying surface by plasticizing the cured product. Like the above-mentioned component (b), it must be soluble in the component (a). Examples of such a plasticizer include phthalic acid such as dibutyl phthalate, dibutyl phthalate-di-n-octyl phthalate, di-2-ethylhexyl phthalate, octyl decyl phthalate, di-n-decyl phthalate, diisodecyl phthalate and butyl benzyl phthalate. Ester acid, di-2-ethylhexyl adipate, octyldecyl adipate, di-2-ethylhexyl sebacate, dibutyl sebacate, di-2-
Ethylhexyl azelate, polypropylene glycol, chlorinated paraffin, adipic acid, azelaic acid, sebacic acid, phthalic acid polyester polymer plasticizers and epoxy polymer plasticizers such as epoxidized oil and epoxidized fatty acid ester Etc. These may be used alone or in combination.

The content of the above-mentioned component (c) is appropriately set, but it is particularly preferably set to 5 to 25%, more preferably in the liquid acrylic polymerizable film-forming agent (A component). It is to set to 5 to 20%. That is,
If it is less than 5%, the followability of the cured product to the underlayer tends to be insufficient.

As described above, in the synthetic resin type coating film forming agent of the present invention, the coating workability, self-leveling property and curability are changed by changing the mutual content ratios of the above components (a) to (c). It is possible to adjust the viscosity that gives an influence to the preferable range, and also to adjust the balance between strength and flexibility of the cured product to the preferable range.

The compound (d), which is a compound having at least two polymerizable double bonds in one molecule, is added for the purpose of crosslinking the above component (a) and improving the durability of the cured product. This cross-linking also improves the chemical resistance and stain resistance of the synthetic resin coating film surface. Such compounds include ethylene glycol dimethacrylate, 1,2-propylene glycol dimethacrylate,
1,3-butylene glycol methacrylate, 1,6-
Hexanediol dimethacrylate, dipropylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyoxyalkylene glycol dimethacrylate such as polyethylene glycol dimethacrylate, divinylbenzene diallyl phthalate, triallyl phthalate, triaryl sialate, Examples include triallyl isocyanurate, allyl methacrylate, diallyl fumarate and the like. These may be used alone or in combination.

The content of the above-mentioned component (d) can be appropriately set, but if the content is too large, the flexibility of the cured product is impaired. Therefore, the total amount of the above-mentioned components (a) to (c) is 1
0.1 to 10 with respect to 00 parts by weight (hereinafter abbreviated as "part")
It is preferably set to 1 part, more preferably 1 to 5 parts. That is, if it is less than 0.1 part, curability and durability are deteriorated, and if it exceeds 10 parts, flexibility tends to be deteriorated.

The cement powder has a function of reacting with the inside of the chemical solution for forming the synthetic resin coating film, the water content of the base, and the water content in the atmosphere, and has the effect of reducing the inhibition of the polymerization reaction by the water content.
Moreover, it also has the effect of reducing shrinkage during curing. Examples of such cement powder include bolant cement, jet cement, alumina cement, and quick setting cement. Preferably, quick-setting cement, jet cement, alumina cement, and special cement, which have high reactivity with water, are effective for improving the hardening property. It should be noted that such cement powder may contain some impurities.

If the blending amount of the cement powder is too large, the fluidity will be poor and the synthetic resin coating film formed will be hard. Therefore, the total amount of the above components (a) to (e) is The amount is preferably set to 10 to 200 parts, and particularly preferably 50 to 150 parts per 100 parts. That is, if the amount is less than 10 parts, it becomes difficult to absorb water, which is the effect of the cement powder blended, and reduce the inhibition of the polymerization reaction. This is because there is a tendency that the fluidity of the resin deteriorates and the synthetic resin coating film also becomes hard.

The polymerization initiator may be in the form of powder or liquid. The curing of the synthetic resin coating film-forming agent of the present invention is usually performed by using a redox catalyst composed of a combination of a curing agent and a curing accelerator.
It is carried out by curing within a temperature range of 30 to 50 ° C. within 2 hours. Various types of redox catalysts can be used, but it is preferable to use a combination of a tertiary amine as the curing accelerator and an organic peroxide as the curing agent. As the above-mentioned tertiary amine, it is preferable to use one having at least one aromatic residue directly bonded to the nitrogen atom, and particularly N, N'-dimethylaniline, N, N'-dimethyl-p-toluidine. , N, N'-dihydroxyethyl-p-toluidine,
N, N'-di-2-hydroxypropyl-p-toluidine and the like can be mentioned, and they can be used alone or in combination. Further, it is preferable to use benzoyl peroxide as the organic peroxide. Furthermore, when using the above-mentioned benzoyl peroxide, it is more preferable to use a paste or powder which is diluted with an inert liquid or solid to a concentration of 50% in order to avoid handling hazards. Then, it is particularly preferable to use benzoyl peroxide whose surface is treated with an inorganic powder containing water of crystallization. Examples of the inorganic powder include calcium phosphate, calcium sulfate,
Examples include magnesium carbonate and aluminum hydroxide.

The synthetic resin coating film-forming agent of the present invention preferably has a short curing time in consideration of work productivity. However, when coating the roof floor or outer wall surface, there is a margin time to smooth the surface of the synthetic resin coating film after coating and before curing the chemicals, so the pot life and curing time are too short. If too much, the coating workability becomes difficult and a good synthetic resin coating film cannot be obtained. Therefore, the compounding amount of the curing agent and the curing accelerator to be used is adjusted so that the working time can be obtained in accordance with the work and the hardening is performed in such a short time that the construction efficiency is not lowered. ~
It is preferable to set the curing time to 30 minutes and the curing time to 10 to 90 minutes.

In order to achieve such a pot life and a curing time, it is necessary to appropriately adjust at least one of the amount of the curing agent and the curing accelerator to be used according to the temperature of the chemical or the temperature at the time of coating. is there. Therefore, in the present invention, when an organic peroxide (50% concentration) is used as a curing agent, it is set to 0.5 to 10% in the synthetic resin coating film forming agent of the present invention. Is preferable, and more preferably 1 to 5%. When a tertiary amine is used as the curing accelerator, it is preferably set to 0.1 to 6%, more preferably 0.3 to 4%, similarly to the above.

The chemical solution for forming a synthetic resin coating film of the present invention comprises:
In addition to the components (a) to (e), the cement powder and the polymerization initiator, an ultraviolet absorber may be added, if necessary, for improving weather resistance.

Examples of the ultraviolet absorber include 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4,4'-dibutoxybenzophenone and other 2-hydroxybenzophenones. And their derivatives, 2-
(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2 [2'
-Hydroxy-3 ', 5'-bis (2,2'-dimethylpropyl) phenyl] benzotriazole or a benzotriazole derivative such as a halogen derivative thereof, or salicylate such as phenyl salicylate or pt-butylphenyl salicylate Examples thereof include esters. These ultraviolet absorbers are (a) to
It is preferable to add it in the range of 0.01 to 5 parts with respect to 100 parts of the total amount of the component (c).

For the purpose of stabilizing the curability of the chemical solution for forming a synthetic resin coating film of the present invention, tributyl phosphite, tri (2-ethylhexyl) phosphite, tridecyl phosphite, tristearyl phosphite, tris (nonyl). Phosphites such as phenyl) phosphite and triphenylphosphite can be added.

Further, various antifoaming agents and leveling agents can be added for the purpose of adjusting the synthetic resin coating film to be formed, and the storage stability of the chemical liquid for forming the synthetic resin coating film can be improved. Then, a polymerization inhibitor such as hydroquinone, hydroquinone methyl ether, or 2,4-dimethyl-6-t-butylphenol can be added.

For the purpose of enhancing the moisture absorption and hardening of the cement component, a dehydrating agent such as synthetic zeolite and calcium oxide may be mixed and used.

The synthetic resin coating film forming agent of the present invention may appropriately contain a filler and a pigment in addition to the cement component. Further, as the above-mentioned extender,
Examples include calcium carbonate, silica powder, aluminum hydroxide, and the like. Examples of the pigment include titanium oxide, barium sulfate, carbon black, chrome vermillion, and red iron oxide. However, it is preferable that the total amount of these extenders and pigments is 0 to 100 parts with respect to 100 parts of the synthetic resin coating film forming agent of the present invention.

The synthetic resin coating film forming agent of the present invention is produced, for example, as follows. That is, the components (a) to (e) are blended and mixed to prepare a liquid acrylic polymerizable film forming agent (component A). Then, the liquid acrylic polymerizable film-forming agent (component A), the cement component, the polymerization initiator, and other components that are appropriately blended as necessary are mixed and mixed to form a synthetic resin coating. A film forming agent is manufactured.

Further, when both components of a redox catalyst curing agent and a curing accelerator are mixed as the synthetic resin coating film forming agent of the present invention, the polymerization reaction of the components (a) and (d) is promptly carried out. Is started, and the hydration reaction between the cement component and the water in the air and the contact surface with the base and the drug in the medicine proceeds at the same time. Further, even if the liquid acrylic polymerizable film-forming agent (component A) of the present invention is mixed with the curing agent in the polymerization initiator, curing proceeds at room temperature, albeit slowly. Therefore, when it is expected that storage of the present drug for a relatively long period of time before coating is expected, the above (a) to
Liquid acrylic polymerizable film forming agent (A
(Component) and the curing accelerator in the polymerization initiator are mixed in advance as the first component. Meanwhile, the cement component and the curing agent in the polymerization initiator are mixed in advance. Then, both of them can be stored separately and the two components can be mixed and used before use.
This method is preferable because it simplifies the work for coating.

The synthetic resin coating film is produced using the synthetic resin coating film forming agent of the present invention, for example, as follows. First, the following is prepared as a synthetic resin coating film forming agent. That is, a liquid acrylic polymerizable film forming agent (component A) is prepared by blending the components (a) to (e).
Is prepared. Then, the liquid acrylic polymerizable film-forming agent (component A), the cement component, the polymerization initiator, and other components appropriately blended as necessary are mixed immediately before coating to prepare a synthetic resin system. Prepare a film-forming agent. Then, using this, the surface of the substrate is coated. Examples of the coating method include spraying, ironing iron, and brush coating. In addition, upon coating, it is preferable to apply a primer treatment to the base material as needed and then apply the synthetic resin coating film forming chemical solution thereon.

Examples of base materials to be coated with such a synthetic resin coating film forming chemical include floors such as concrete, asphalt, steel plates, rooftops, wall surfaces, etc. Used as etc.

[0036]

As described above, the present invention uses an acrylic polymerizable film forming agent and a polymerization initiator as a synthetic resin coating film forming material for forming a synthetic resin coating film on the surface of a substrate. What is added with a cement component when mixing is used. Therefore, since the cement component has a moisture-absorption hardening property and a shrinkage reducing function, when a synthetic resin coating film is formed using this, the cement component absorbs moisture even in a high-humidity atmosphere and sufficient curing is not achieved. Done. The synthetic resin coating film formed by such sufficient curing suppresses warpage and distortion due to curing shrinkage.

Next, examples will be described together with comparative examples.

[0038]

Example 1 The following components were charged in the following proportions into a dissolution tank equipped with a stirrer and a heating jacket, and a copolymer of methyl methacrylate (MMA) and butyl acrylate (BA) while stirring [ MMA / BA = 90/10 (weight ratio)] 20 parts were added little by little.

Component (a): Methyl methacrylate 40 parts (a) Component: 2-ethylhexyl acrylate 20 parts (c) Component: Chlorinated paraffin (chlorine content 50%) 10 parts: Octyldecyl phthalate 10 parts (d) ) Component: ethylene glycol dimethacrylate 2 parts: N, N'-di (2-hydroxypropyl) -p-toluidine 0.5 part: hydroquinone 0.0025 part

Then, the mixture was heated to 50 ° C. and 0.5 part of n-paraffin (melting point 54 to 56 ° C.) was added.
Similarly, 0.5 part of n-paraffin (melting point 64-66 ° C.) was added and completely dissolved to obtain a composition having a viscosity of 400 cps at 20 ° C. To 100 parts of this composition, 100 parts of 60-second hardening type quick-setting cement and 50% pure benzoyl peroxide (hereinafter referred to as "B. 3 parts (abbreviated as "PO powder") and mixed well. In this way, a synthetic resin-based coating film forming chemical was prepared.

Then, the above chemical solution for forming a synthetic resin coating film was applied onto a slate plate which had been immersed in water for 5 minutes and then air dried for 5 minutes. Then, this was cured at 25 ° C. in an atmosphere of 80% humidity, and it was in a good cured state. Furthermore, the shrinkage percentage after 24 hours of curing at 20 ° C. in a standard state of 60% humidity was 3%. No abnormality was found in the bending test.

The curability was evaluated by a sensory test on the basis of a cured product in a standard state to determine whether or not there is a significant difference. In addition, the shrinkage factor is 1 on the release-treated glass plate.
A frame having a thickness of 5 mm and a size of 5 cm × 30 cm was assembled, and a chemical solution having a thickness of 5 mm was poured into the frame to produce a sheet. The sheet was turned over in 12 hours, and the shrinkage rate for 30 cm was obtained after 24 hours.

[0043]

Comparative Example 1 Instead of the above cement powder, an average particle size of 1
3 μm ground calcium carbonate was used. Then, 100 parts of the composition of Example 1 was mixed with 100 parts of this heavy calcium carbonate.
Parts of B., and 50% pure B.I. treated with a powder having water of crystallization as a curing agent. P. O powder was added. A synthetic resin-based coating film forming chemical was prepared in the same manner as in Example 1 except for the above.

The same test as in Example 1 was conducted using this synthetic resin coating film forming chemical solution. As a result, the adhesive interface was in an uncured state, and when cured under high humidity atmosphere conditions, the surface was tacky and sufficient hardness could not be obtained. The shrinkage percentage after 24 hours of curing in the standard state was 5%. Further, some whitening was observed in the bending test.

[0045]

Example 2 The following components were charged in the following proportions into a dissolution tank equipped with a stirrer and a heating jacket, and a copolymer of methyl methacrylate (MMA) and butyl acrylate (BA) was added with stirring [ MMA / BA = 90/10 (weight ratio)] 20 parts were added little by little.

Component (a): Methyl methacrylate 40 parts (a) Component: 2-ethylhexyl acrylate 20 parts (c) Component: Chlorinated paraffin (chlorine content 50%) 10 parts: Octyldecyl phthalate 10 parts (d) ) Component: ethylene glycol dimethacrylate 2 parts: N, N'-di (2-hydroxypropyl) -p-toluidine 0.5 part: hydroquinone 0.0025 part

Then, the mixture was heated to 50 ° C. and 0.5 part of n-paraffin (melting point 54 to 56 ° C.) was added.
Similarly, 0.5 part of n-paraffin (melting point 64-66 ° C.) was added and completely dissolved to obtain a composition having a viscosity of 400 cps at 20 ° C. 100 parts of this composition was mixed with 100 parts of ordinary cement. In this way, the viscosity at 20 ° C is 3
A 500 cps formulation was obtained. To 100 parts of this formulation, 50% pure B.I. treated with an inorganic powder (magnesium carbonate) having water of crystallization as a curing agent. P. 3 parts of O powder was added and mixed well. In this way, a synthetic resin-based coating film forming chemical was prepared.

Then, a curing test was conducted under the same conditions as in Example 1. As a result, the adhesion on the wet surface was slightly delayed in reaction, but good adhesion was obtained, and the curability in an atmosphere of 80% humidity slightly disappeared as compared with Example 1, but the tack disappeared slightly. It was good. Furthermore, 24 in the standard condition
The shrinkage of the sheet after 2.5 hours was 2.5%. No abnormality was found in the bending test.

[0049]

Example 3 The following components were charged in the following proportions into a dissolution tank equipped with a stirrer and a heating jacket, and a copolymer of methyl methacrylate (MMA) and butyl acrylate (BA) while stirring [ MMA / BA = 90/10 (weight ratio)] 20 parts were added little by little.

Component (a): Methyl methacrylate 40 parts (a) Component: 2-ethylhexyl acrylate 20 parts (c) Component: Chlorinated paraffin (chlorine content 50%) 10 parts: Octyl decyl phthalate 10 parts (d) ) Component: ethylene glycol dimethacrylate 2 parts: N, N'-di (2-hydroxypropyl) -p-toluidine 0.5 part: hydroquinone 0.0025 part

Then, the mixture was heated to 50 ° C. and 0.5 part of n-paraffin (melting point 54 to 56 ° C.) was added.
Similarly, 0.5 part of n-paraffin (melting point 64-66 ° C.) was added and completely dissolved to obtain a composition having a viscosity of 400 cps at 20 ° C. To 100 parts of this composition, 100 parts of special cement (Fukui Chemical Co., Ltd., Eagle Q-6)
Part, and 50% pure B.I. treated with an inorganic powder (magnesium carbonate) having water of crystallization as a curing agent. P. 3 parts of O powder was added and mixed well. In this way, a synthetic resin-based coating film forming chemical was prepared.

Then, a curing test was conducted under the same conditions as in Example 1. As a result, the curability (wet curability) on the slate plate after being immersed in water for 5 minutes and after air-drying for 5 minutes and in an atmosphere of 25 ° C. and 80% humidity was good, and
The shrinkage percentage of the sheet after 24 hours in the standard state of 60 ° C. was 2%. No abnormality was found in the bending test.

[0053]

[Examples 4 and 5] The compounding amounts of the component (a), methyl methacrylate and 2-ethylhexyl acrylate, were changed to the ratios shown in Table 1 below. A composition was obtained in the same manner as in Example 3 except for the above. Inorganic powder (magnesium carbonate) having water of crystallization as a curing agent in 100 parts of the above composition
50% pure B. P. 3 parts of O powder was added and mixed well. In this way, a synthetic resin-based coating film forming chemical was prepared.

The above-mentioned chemical solution for forming a synthetic resin coating film was applied onto a glass plate and a mortar plate with a roller brush so as to have a rate of 0.5 kg / m ² . The curing time of this synthetic resin coating film was measured, and its coating workability, self-leveling property and curability were evaluated. Further, the flexibility and stain resistance of the obtained synthetic resin coating film were evaluated. The results are also shown in Table 1 below. The above evaluations were carried out as follows.

[Coating Workability] A sensory evaluation by an operator was performed.

[Self-leveling property] 100 g of the above liquid synthetic resin-based coating film-forming agent was poured onto a polyethylene plate and spread into a disc shape having a diameter of 20 cm or more was marked with ◯, and less than 20 cm was marked with x. .

[Curing Property] The above liquid synthetic resin coating film forming agent was applied onto a polyethylene plate in a thickness of 2 mm, and after curing for 24 hours, the difference in hardness (JIS) between the front and back was 2 or less and the hardness was 40 or more. Things ○○
Those with 9 to 35 were marked with Δ, and those with 34 or less were marked with x.

[Flexibility of Synthetic Resin-Based Coating Film] A sheet having a thickness of 2 mm was prepared on a polyethylene plate using the liquid chemical solution for forming a synthetic resin-based coating film, and after 24 hours, an arc having a diameter of 100 mm was drawn. It was bent by 90 °, and it was visually observed whether cracking occurred at this time. And
No abnormality was evaluated as ◯, whitening was evaluated as Δ, and cracking was evaluated as x.

[Stain Resistance of Synthetic Resin-Based Coating Film] A synthetic resin-based coating film is formed using the liquid chemical solution for forming a synthetic resin-based coating film, and after curing and curing for 24 hours, drawing with a white chalk is performed. The degree of adhesion after wiping was evaluated. Then, the line completely disappeared was marked with O, the one remaining slightly was marked with Δ, and the line clearly left was marked with X.

[0060]

[Table 1]

[0061]

Examples 6 and 7 The blending amounts of the copolymer of methyl methacrylate and butyl acrylate as the component (b) are shown in Table 2 below.
The ratio was changed to. A composition was obtained in the same manner as in Example 3 except for the above. Then, 100 parts of the above composition was mixed with 50% pure B.I. treated with an inorganic powder (magnesium carbonate) having water of crystallization as a curing agent. P. 3 parts of O powder was added and mixed well. In this way, a synthetic resin-based coating film forming chemical was prepared.

Coating workability, self-leveling property, and curability were evaluated using the above synthetic resin coating film forming chemicals. Further, the flexibility and stain resistance of the obtained synthetic resin coating film were evaluated. The results are also shown in Table 2 below.

[0063]

[Table 2]

[0064]

[Examples 8 and 9] The blending amounts of chlorinated paraffin (chlorine content 50%) and octyldecyl phthalate as the component (c) were changed to the proportions shown in Table 3 below. A composition was obtained in the same manner as in Example 3 except for the above. Then, 100 parts of the above composition was mixed with 50% pure B.I. treated with an inorganic powder (magnesium carbonate) having water of crystallization as a curing agent. P. O
3 parts of powder were added and mixed well. In this way, a synthetic resin-based coating film forming chemical was prepared.

The coating workability, self-leveling property, and curability were evaluated using the above-mentioned chemical solution for forming a synthetic resin coating film. Further, the flexibility and stain resistance of the obtained synthetic resin coating film were evaluated. The results are also shown in Table 3 below.

[0066]

[Table 3]

[0067]

Examples 10 and 11 The amount of ethylene glycol as the component (d) was changed to the ratio shown in Table 4 below. A composition was obtained in the same manner as in Example 3 except for the above. Then, 100 parts of the above composition was mixed with 50% pure B.I. treated with an inorganic powder (magnesium carbonate) having water of crystallization as a curing agent. P. 3 parts of O powder was added and mixed well. In this way, a synthetic resin-based coating film forming chemical was prepared.

The coating workability, self-leveling property, and curability were evaluated using the above synthetic resin coating film forming chemicals. Further, the flexibility and stain resistance of the obtained synthetic resin coating film were evaluated. The results are also shown in Table 4 below.

[0069]

[Table 4]

[0070]

Examples 12 and 13 Paraffin wax as the component (e) was mixed in the proportions shown in Table 5 below. A composition was obtained in the same manner as in Example 3 except for the above. Then, 100 parts of the above composition was mixed with 50% pure B.I. treated with an inorganic powder (magnesium carbonate) having water of crystallization as a curing agent. P. 3 parts of O powder was added and mixed well. In this way, a synthetic resin-based coating film forming chemical was prepared. The paraffin wax has a melting point of 54 to 56 ° C.
A mixture of paraffin and n-paraffin having a melting point of 64 to 66 ° C. in a weight ratio of 1: 1.

Coating workability, self-leveling property, and curability were evaluated using the above-mentioned chemical solution for forming a synthetic resin coating film. Further, the flexibility and stain resistance of the obtained synthetic resin coating film were evaluated. The results are also shown in Table 5 below.

[0072]

[Table 5]

[0073]

Examples 14 and 15 Cement powder (Eaglement Q-6, manufactured by Fukui Chemical Co., Ltd.) was mixed in the proportions shown in Table 6 below. A composition was obtained in the same manner as in Example 3 except for the above. Then, 100 parts of the above composition was mixed with 50% pure B.I. treated with an inorganic powder (magnesium carbonate) having water of crystallization as a curing agent. P. 3 parts of O powder was added and mixed well. In this way, a synthetic resin-based coating film forming chemical was prepared.

Using the above synthetic resin-based coating film forming chemicals, coating workability, self-leveling property and curability were evaluated. Further, the flexibility and stain resistance of the obtained synthetic resin coating film were evaluated. Further, the shrinkage ratio, the wet curability and the wet atmosphere curability were measured and evaluated in the same manner as in Example 1. The results are also shown in Table 6 below.

[0075]

[Table 6]

From the results shown in Tables 1 to 6 above, all of the example products were excellent in coating workability, self-leveling property, curability, flexibility of the synthetic resin coating film, and stain resistance of the synthetic resin coating film. There is. Moreover, in addition to the above-mentioned evaluation, the shrinkage rate was low, and the evaluation was excellent in wet curability and curability in a humid atmosphere.

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Claims (7)

(57) [Claims] 1. A coating a synthetic resin coating film-forming material on the substrate surface
Before processing, apply the synthetic resin coating film forming material
Ment component is added to form a synthetic resin coating film, wherein the following resin components (A) and (B) are used as the synthetic resin coating film forming material. Method of producing a base coating film. (A) A liquid acrylic-based polymerizable film forming agent composed of the following components (a) to (e) . (A) Acrylic acid alkyl ester, methacrylic acid al
At least one of the kill ester. (B) An acrylic polymer soluble in the component (a). (C) A plasticizer soluble in the component (a). (D) Having at least two polymerizable double bonds in one molecule
Compound to do. (E) of paraffin wax having a melting point of 40 ° C. or higher
A composition containing at least one. (B) The polymerization initiator of the component (A) . 2. The synthetic resin system according to claim 1, wherein the addition amount of the cement component is set to 10 to 200 parts by weight with respect to 100 parts by weight of the liquid acrylic polymerizable film forming agent which is the component (A). How to make a coating film. 3. The method for producing a synthetic resin coating film according to claim 1, wherein the polymerization initiator as the component (B) is in powder form. 4. A synthetic resin coating film forming agent comprising the following components (A) and (C). (A) A liquid acrylic polymerizable film forming agent composed of the following components (a) to (e) . (A) Acrylic acid alkyl ester, methacrylic acid al
At least one of the kill ester. (B) An acrylic polymer soluble in the component (a). (C) A plasticizer soluble in the component (a). (D) Having at least two polymerizable double bonds in one molecule
Compound to do. (E) of paraffin wax having a melting point of 40 ° C. or higher
A composition containing at least one. (C) A powdery material comprising the following components (x) and (y). (X) Cement powder. (Y) A polymerization initiator as the component (A) . 5. A liquid acrylic polymerizable film forming agent 1 in which the amount of the cement component, which is the component (x), is the amount of the component (A).
The synthetic resin coating film forming agent according to claim 4, which is set to 10 to 200 parts by weight with respect to 00 parts by weight. 6. A synthetic resin coating film forming agent comprising the following components (A), (D) and (E). (A) A liquid acrylic polymerizable film forming agent composed of the following components (a) to (e) . (A) Acrylic acid alkyl ester, methacrylic acid al
At least one of the kill ester. (B) An acrylic polymer soluble in the component (a). (C) A plasticizer soluble in the component (a). (D) Having at least two polymerizable double bonds in one molecule
Compound to do. (E) of paraffin wax having a melting point of 40 ° C. or higher
A composition containing at least one. (D) Cement powder. (E) The liquid polymerization initiator of the above component (A) . 7. A liquid acrylic polymerizable film-forming agent 1 in which the amount of the cement component, which is the component (D), is the amount of the component (A).
The synthetic resin coating film forming agent according to claim 6, which is set to 10 to 200 parts by weight with respect to 00 parts by weight.