JP2005239955A - Heat-resistant repairing agent, method for coating the agent, and article coated with the agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a plate repairing agent which can be applied to give a high hardness and heat resistance and used in a secondary processing to show excellent properties, and to provide a method for applying the same. <P>SOLUTION: The repairing agent comprises a main component and a crosslinking agent, wherein the main component comprises an aqueous resin emulsion and/or an aqueous latex composed of a polymer having a terminal functional group having an active hydrogen, a filler having a content of 30 wt% or more, and a surfactant; the crosslinking agent is one or more selected from the group consisting of (1) a polyfunctional aziridine compound having two or more aziridinyl groups in the molecule, (2) an aqueous epoxy compound, (3) an organic silicon compound, and (4) an isocyanate compound; and the cured product of the repairing agent has a D hardness Y between Y<SB>1</SB>and Y<SB>2</SB>(Y<SB>1</SB>≤Y≤Y<SB>2</SB>) provided Y<SB>1</SB>and Y<SB>2</SB>are defined by equations (1) and (2), when the cured product is immersed in boiling water for 4 hr and then dried at 60°C when measured at a constant time interval X by using a type D durometer (JIS K7215): (1) Y<SB>1</SB>=7X+20, and (2) Y<SB>2</SB>=7X+60, where Y<SB>1</SB>and Y<SB>2</SB>are each a D hardness, and X is a drying time (hr) after boiling. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  TECHNICAL FIELD The present invention relates to a heat-resistant repair agent for plate-like materials, particularly a repair agent capable of exhibiting excellent performance in secondary processing after repair, a coating method thereof, and a plate-like material to which the repair agent is applied. .

The surface of plate-like objects such as plywood and other inorganic boards such as rock wool boards has cracks in the conduit, worm-eaten holes, or cracks, cracks, and other defects. In the past, it has been practiced to apply repair agents or sealants, and for these, sealants such as abrasive powder and titanium paste, and repair agents such as various latex, epoxy resins, and urethane resin paints are used. ing.
However, separate sealants and repair agents according to the above-mentioned prior art are used separately, so that the sealant has a sealing effect, but it fills cavities such as wood and cracks in large conduits. I couldn't. In addition, the recesses to be repaired, such as wormholes, vary depending on the type of material, the size, depth, and shape of the holes, and do not occur at a specific location. It is based on the repair method (hand repair) which paints with etc. (patent document 1).

In addition to the above-mentioned manual repair method, a method of using a normal thermosetting resin or aqueous resin emulsion in the method of repairing the entire surface of a board or plywood using a conventional knife coater (full repair) is also proposed. (Patent Documents 2, 3, and 4).
However, although these repair agents have some effects in that they do not cause clogging of the sander used for polishing the repair surface, the hardness and heat resistance of the cured product after application and drying are somewhat low, so the veneer adhesion The actual situation is that the secondary processing such as the above does not completely eliminate the concern of poor adhesion due to shrinkage and depression of the painted surface (repair surface) and rough surface deterioration.
Therefore, there is a strong demand for the development of a repair agent that has high hardness after coating, good heat resistance, and does not cause problems such as poor adhesion in secondary processing.

Japanese Patent Publication No. 50-27058 JP-A-3-136806 JP-A-3-267174 JP-A-8-85769

  The present invention is for solving the above-mentioned problems related to conventional sealing and repair work, and has a high hardness after coating, good heat resistance, and a repair agent that exhibits excellent performance even in secondary processing, and its coating It is intended to provide a method.

As a result of intensive studies to achieve this object, the present inventors have found that when a repair agent having a specific property is used, a coated product having good paintability and excellent heat resistance can be obtained. Completed the invention.
That is, the present invention includes an aqueous resin emulsion and / or aqueous latex composed of a polymer having a functional group having active hydrogen at the terminal, an aqueous latex, a filler, and a surfactant, and the filler content is 30% by weight or more. And (1) one or more selected from the group consisting of a polyfunctional aziridine compound having two or more aziridinyl groups in the molecule, (2) an aqueous epoxy compound, (3) an organosilicon compound, and (4) an isocyanate compound A curing agent comprising a crosslinking agent comprising: a curing restoration rate within a range defined by the following formulas (1) and (2) (Y ₁ ≦ Y ≦ Y ₂ ) It is a repair agent. Curing restoration speed is the D hardness of the cured product measured with a type D durometer (JIS K7215) immediately after the cured product of the repair agent is immersed in boiling water for 4 hours and further dried in a dryer at 60 ° C. for a certain period of time. It is. A cured product of this repair agent is a 12 mm thick, 5-ply plywood surface with a 10 mm wide, 150 mm long, 5 mm deep groove, coated with the repair agent, and dried at 40 ° C. for 24 hours. And then smoothed with sandpaper (No. 120; the same applies hereinafter).
(1) Y ₁ = 7X + 20
(2) Y ₂ = 7X + 60
Y ₁ , Y ₂ = D hardness,
X = drying time after boiling water immersion (hours)

Furthermore, the repair agent of the present invention is characterized in that the volume residual ratio Y ₃ after hot pressing is above the straight line represented by the following formula, in other words, larger than the value obtained by the following formula.
Y ₃ = -3X ₃ +100
Y ₃ = volume residual rate (%), X ₃ = moisture content of repaired plywood (%)
This volume residual rate is expressed by the following measuring method.
Measuring method: A groove having a width of 10 mm, a length of 50 mm, and a depth of 5 mm is formed on the surface of a 12 mm thick, 5-ply plywood, a repair agent is applied to the groove, dried for 24 hours, and then smoothed with sandpaper. . After adjusting the moisture content of the plywood, a decorative sheet (0.5 mm thick PET sheet) is placed on the surface and hot pressed at 150 ° C. for 5 minutes. The volume of the repair agent filled in the repaired defect portion is changed by the hot pressure, and the volume ratio after the change (after the hot press) with respect to the volume before the hot press is defined as the volume residual ratio.
These hardness and volume residual ratio are realized when the functional group at the polymer terminal having active hydrogen in the aqueous resin emulsion is crosslinked with the above-mentioned crosslinking agent and contains a certain amount of filler.
If the hardness and volume residual ratio are outside the above ranges, the repaired part will become defective again when a wooden decorative board or resin sheet is bonded to a plate that has been repaired using a repair agent. turn into. In addition, clogging of sandpaper occurs during sanding after repair, and it becomes difficult to obtain good smoothness.

The viscosity of the repair agent of the present invention is such that when used by manual repair, the viscosity V measured by a B-type viscometer is within the range defined by the following formulas (1) and (2) (V ₁ ≦ V ≦ V ₂ ) It is preferable that it exists in.
(1) V ₁ = -4T + 180
(2) V ₂ = -4T + 1080
V ₁ , V ₂ = viscosity (Pa · s), T = temperature (° C.)

Furthermore, when painting a plate-like object manually using a repair agent (manual repair), 1) made of metal or synthetic resin having a width of 5 to 150 mm, a length of 50 to 300 mm, and a thickness of 10 mm or less. The spatula is pressed diagonally against the painted surface of the plate-like object, 2) the length at which the angle of the spatula with respect to the painted surface of the spatula is 15 degrees or less is set as a uniform pressure width, and 3) the spatula is The relationship between the moving speed N on the coated surface of the plate-like object and the time M during which the uniform pressure width is applied is within the range defined by the following equations (1) and (2) (M ₁ ≦ M ≦ It is preferable to take a coating method in which the spatula is moved manually so as to enter M ₂ ).
(1) M ₁ = −0.002N + 0.062
(2) M ₂ = −0.1N + 3.1
M ₁ , M ₂ = the time during which the uniform pressure width is uniformly pressurized (seconds)
N = speed of moving the spatula against the plate (m / min)
Outside of the above range, it is impossible to provide a sufficient repair agent when applying with a spatula or the like, resulting in deterioration of the repair state such as final smoothness. In addition, the coatability becomes difficult, leading to a decrease in productivity and economy.

The viscosity of the repair agent of the present invention is such that the viscosity v by the visco tester is within the range defined by the following formulas (1) and (2) (v ₁ ≦ v ≦ v _2). ).
(1) v ₁ = −0.045t + 1.9
(2) v ₂ = −0.045t + 80.9
v ₁ , v ₂ = viscosity (Pa · s), t = temperature (° C.)

Furthermore, when using this repair agent to paint a plate-like object with a knife coater, 1) Add a knife with a knife coater equipped with a knife having a width of 300 to 1800 mm, a length of 50 to 300 mm, and a thickness of 5 mm or less. 2) The pressure at which the angle of the knife tip with respect to the coated surface of the plate-like object is 15 degrees or less is defined as the uniform pressure width, and 3) the uniform pressure width is applied. A coating method in which the relationship between the pressing time m and the feed speed n of the plate is within the range defined by the following equations (1) and (2) (m ₁ ≦ m ≦ m ₂ ) Is preferred.
(1) m ₁ = −0.0005n + 0.035
(2) m ₂ = −0.005n + 0.35
m ₁ , m ₂ = the time (in seconds) during which the uniform pressure range is uniformly pressurized,
n = Plate-shaped object feed speed with knife coater (m / min)
Outside of the above range, it is impossible to sufficiently fill the repair agent when painting with a knife coater, which causes deterioration of the repair state such as final smoothness. In addition, the coatability becomes difficult, leading to a decrease in productivity and economy.

  When the repair agent of the present invention is used, clogging of the sander after coating hardly occurs, and a product with good adhesiveness and surface property can be obtained even if secondary processing such as veneer bonding is performed.

Examples of the aqueous resin emulsion and / or aqueous latex polymer comprising a polymer having a functional group having active hydrogen at the terminal in the present invention include polyurethane resin emulsions and dispersions, carboxylated styrene-butadiene latex, acrylic acid-acrylic acid ester co-polymers. There are aqueous emulsions / aqueous latexes such as polymerized emulsions, and these can be used alone or in combination of two or more.
In addition, examples of the functional group having active hydrogen include a carboxyl group, an amino group, an amide group, a hydroxyl group, a mercapto group, a sulfonyl group, and an acetoacetyl group. These may be used alone or in combination of two or more in the polymer. Can be used.

The crosslinking agent was selected from the group consisting of (1) a polyfunctional aziridine compound having two or more aziridinyl groups in the molecule, (2) an aqueous epoxy compound, (3) an organosilicon compound, and (4) an isocyanate compound. One or more compounds can be used.
Examples of the polyfunctional aziridine compound having two or more aziridinyl groups in the molecule include trimethylolpropane tris [3- (1-aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) butyrate], trimethylol. Propanetris [3- (1- (2-methyl) aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) -2-propionate], pentaerythritol tris [3- (1-aziridinyl) propionate], Pentaerythritol tetra [3- (1-aziridinyl) propionate], diphenylmethane-4,4'-bis-N, N'-ethyleneurea, 1,6-hexamethylenebis-N, N'-ethyleneurea, 2,4 , 6- (Triethyleneimino)- yn- triazine, bis [1- (2-ethyl) aziridinyl] benzene-1,3-carboxylic acid amide and the like can be used.

The aqueous epoxy compound is an epoxy compound generally called a polyhydric alcohol glycidyl ether, such as ethylene glycol glycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, and these are used in combination of one or more. can do.
Examples of organosilicon compounds include γ-aminopropyltriethoxysilane, aminoalkylsilanes such as N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxy. Epoxy silanes such as propylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, chloro-based silanes such as γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldichlorosilane, γ-methacryloxypropylmethyldimethoxysilane, There are γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, aminoepoxysilane, and the like, and these can be used alone or in combination.

Isocyanate compounds include aromatic polyisocyanates such as diphenylmethane diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, xylene diisocyanate, hydrogenated xylylene diisocyanate, block type polyisocyanate, etc. These can be used alone or in combination of two or more, but polymethylene polyphenyl polyisocyanate is preferably used from the viewpoints of economy and environmental hygiene.
These crosslinking agents are blended in an amount of 0.01 to 15 parts by weight, preferably 0.1 to 7 parts by weight, based on 100 parts by weight of the aqueous emulsion and / or aqueous latex of the main agent.

As a filler (a filler) in the present invention, generally clay, talc, aluminum hydroxide, glass powder, white clay, abrasive powder, silica, barium sulfate, mica, titanium oxide, iron oxide, white carbon, aluminum silicate, calcium carbonate , Inorganic substances such as magnesium carbonate, alumina (Al2O3), cellulosin, pulp, coconut shell powder, wheat flour, rapeseed meal, konjac powder, corn starch, potato starch, corn gluten, milk casein, wood powder, egg white powder, soybean protein, etc. Other diatomaceous earth and bone meal can be used.
In addition, although content of these fillers needs to be 30% or more by the weight ratio in a repair agent main ingredient, Preferably it is 80% or less, More preferably, it is a ratio of 40 to 75%. When it is 30% or less, the hardness of the repair agent after curing becomes low, and sanding properties and the like deteriorate. Moreover, although it changes with fillers to be used, when it becomes 80% or more, water resistance and heat resistance deteriorate by the relative fall of a binder component, and also applicability | paintability may become difficult.

As the surfactant, a so-called foam stabilizer such as polysiloxane, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct can be used in addition to a silicone-based or non-ionic surfactant.
In addition, polyacrylic acid soda, cellulose ether, polyvinyl alcohol, and the like can be used as a viscosity imparting agent. Further, by blending the isocyanate compound as described above, the coating composition can be foamed to improve the filling effect, but it is also possible to add a foaming agent other than the isocyanate compound to obtain the same effect. Examples of blowing agents that can be used for this purpose include chlorofluorocarbon compounds such as trichloromonofluoromethane and trichlorotrifluoroethane, volatile liquids such as methylene chloride, trichloroethane, acetone, and isopropyl ether, sodium bicarbonate, calcium carbonate, guanidine carbonate, and the like. There are substances that generate carbon dioxide.
The repairing agent of the present invention can of course also use other components than those described above, and as long as the hardness of the cured product of the repairing agent, which is the gist of the present invention, satisfies the above specified conditions, it is usually used in the coating composition. Agents, additives and the like can be used.

Although the Example of this invention is shown below, the meaning of this invention is not limited to this from the first.
The repair composition was prepared by sufficiently mixing and stirring the composition shown in Tables 1 and 2, and the hardness recovery rate, repair agent volume residual ratio, and repair agent viscosity of each repair composition were measured. The results are shown in Tables 1 and 2, respectively.
The plywood was repaired using the repair agent composition according to the following procedure.

1. Manual Repair The repair composition prepared with the formulation shown in Table 1 was applied to the surface of a 5-ply laver plywood with a thickness of 12 mm using a spatula. The plywood coated with the repair agent composition was dried, sanded, and stuck to the veneer under the same conditions as those for the entire surface repair described below.
The state after sanding and the state of veneer adhesion were observed and are shown in Table 1.

2. Full surface repair The mixed repair agent composition was transferred from the tank to the traverser by a snake pump, and was uniformly discharged onto the line from the traverser.
The discharge liquid was uniformly applied to the surface of a 12 mm-thick 5-ply one plywood with a knife coater under predetermined conditions, and then dried and deposited for 2 minutes with a 90 ° C. drier. Sanding was performed on the plywood that had been deposited for 24 hours.
A veneer was bonded to the plywood after the sander treatment under the following conditions.
Base plate 12mm thickness 5 ply la one plywood veneer veneer 0.2mm thickness White oak adhesive Melamine resin (ML-045 manufactured by Honen Corporation)
40 copies
Styrene butadiene latex (JSR-2420 manufactured by JSR Corporation)
60 copies
30 parts flour
Malic acid 0.4 parts coating amount 9g / 900cm ²
Open assembly time
Within 10 minutes Hot pressure condition 120 ° C. 7 Kg / cm ² 60 seconds The state after sanding and the state of veneer adhesion were observed and listed in Table 2.

Claims (8)

An aqueous resin emulsion and / or aqueous latex comprising a polymer having a functional group having active hydrogen at its terminal, an aqueous latex, a filler, a surfactant, and a main agent having a filler content of 30% by weight or more; (1) molecules A polyfunctional aziridine compound having two or more aziridinyl groups, (2) an aqueous epoxy compound, (3) an organosilicon compound, and (4) a cross-linking agent consisting of one or more selected from the group of isocyanate compounds Of the cured product obtained by immersing the cured product of the repair agent in boiling water for 4 hours, drying under a temperature condition of 60 ° C., and measuring with a type D durometer (JIS K7215) every constant time X. A repairing agent characterized in that the D hardness Y is within the range of the value Y ₁ obtained by the following formula (1) and the value Y ₂ obtained by the following formula (2) (Y ₁ ≦ Y ≦ Y ₂ ).
(1) Y ₁ = 7X + 20
(2) Y ₂ = 7X + 60
Y ₁ , Y ₂ = D hardness, X = drying time after boiling water treatment (hours) The repair agent according to claim 1, wherein a volume residual ratio after hot pressing by the following method is larger than a value represented by the following formula.
Y ₃ = -3X ₃ +100
Y ₃ = Volume remaining rate (%), X ₃ = Moisture content of repaired base plate (%)
Measurement method Applying a repair agent to the defects on the surface of the plywood (base plate), drying, and smoothing with a sandpaper. After adjusting the moisture content of the plywood, a decorative sheet is placed on the surface and hot pressed at 150 ° C. for 5 minutes. Although the volume of the repair agent filled in the repaired defect portion varies depending on the heat pressure, the ratio of the volume after the change to the volume before the heat pressure is defined as the volume residual ratio. Viscosity V measured by a B-type viscometer is within the range of values V ₁ and V ₂ defined by the following formulas (1) and (2) (V ₁
≦ V ≦ V ₂ ), the repair agent according to claim 1 or 2.
(1) V ₁ = -4T + 180
(2) V ₂ = -4T + 1080
V ₁ , V ₂ = viscosity (Pa · s), T = temperature (° C.) Viscosity v by visco tester is within the range defined by the following formulas (1) and (2) (v ₁ ≦ v
≦ v ₂ ), the repair agent according to claim 1 or 2.
(1) v ₁ = −0.045t + 1.9
(2) v ₂ = −0.045t + 80.9
v ₁ , v ₂ = viscosity (Pa · s), t = temperature (° C.) When manually applying a plate-like object using the repair agent according to claim 3, 1) a spatula made of metal or synthetic resin having a width of 5 to 150 mm, a length of 50 to 300 mm, and a thickness of 10 mm or less. Pressed diagonally against the painted surface of the plate-like object, 2) the length of the spatula with respect to the coated surface of the plate-like object is 15 degrees or less, and the pressure width is uniform, and 3) the spatula is plate-like The relationship between the moving speed N on the painted surface of the object and the time M during which the uniform pressure width is applied is within the range defined by the following equations (1) and (2) (M ₁
≦ M ≦ M ₂ ) The spatula is manually moved so as to fall within the range.
(1) M ₁ = −0.002N + 0.062
(2) M ₂ = −0.1N + 3.1
M ₁ , M ₂ = the time during which the uniform pressure width is uniformly pressurized (seconds)
N = speed of moving the spatula against the plate (m / min) When a plate-like object is coated with a knife coater using the repair agent according to claim 4, 1) a knife coater having a knife having a width of 300 to 1800 mm, a length of 50 to 300 mm, and a thickness of 5 mm or less. 2) The pressure is applied to the coated material diagonally, 2) the length at which the angle of the knife tip with respect to the coating surface of the plate-like material is 15 degrees or less is defined as the uniform pressure width, and 3) the uniform pressure is applied. The relationship between the time m during which the width is pressed and the feed speed n of the plate is within the range defined by the following equations (1) and (2) (m ₁ ≦ m ≦ m ₂ ). A characteristic method for painting plate-like objects.
(1) m ₁ = −0.0005n + 0.035
(2) m ₂ = −0.005n + 0.35
m ₁ , m ₂ = the time (in seconds) during which the uniform pressure range is uniformly pressurized,
n = Plate-shaped object feed speed with knife coater (m / min) The plate-shaped object formed by repairing using the repair agent in any one of Claims 1-4. A plate-like object obtained by repairing using the repairing method according to claim 5 or 6.