JP2017095692A - Energy ray curable sealer composition for housing material, housing material with coated film and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an energy ray-curable sealer composition for housing material excellent in workability, blocking resistance, water resistance and freeze thawing resistance and capable of reducing volatile organic compounds (capable of making low VOC).SOLUTION: The energy ray-curable sealer composition contains an urethane (meth)acrylate resin (A) by reacting polyisocyanate (a1), low molecular diol with molecular weight of 60 to 620 (a2) and (meth)acrylate having a hydroxyl group (a3), polyisocyanate (B) which may be same as or different from the component (a1) and a photoinitiator (C).SELECTED DRAWING: None

Description

  The present invention is excellent in permeability to building materials, improves adhesion, water resistance, water permeability resistance, freeze-thaw resistance, etc., and strengthens a base material for building material sealer composition and cured formed from the composition The present invention relates to a building material having a coating.

  Conventionally, on the surface (front surface) of building materials widely used for interior and exterior, roofs, etc., sealer compositions for sealing, undercoat paints for concealing base materials, and topcoat paints for design purposes are generally used. It is painted. Moreover, the back surface (back surface) is generally unpainted or coated with a sealing sealer composition.

  Conventionally, as the sealer composition, organic solvent-based sealer compositions such as vinyl chloride resin-based, two-component urethane resin-based, polyisocyanate-based wet-curing type, epoxy resin-based emulsion, water-dispersible polyisocyanate, core Aqueous sealer compositions such as shell-type vinyl emulsions have been used.

However, since the conventional sealer composition requires time until the applied cured film is completely cured, there has been a problem in terms of workability when an undercoat paint is applied to the upper layer. Further, even when the undercoat paint is not applied like the back surface of the building material, there is a problem that blocking tends to occur when the base materials are stacked.
Therefore, an energy ray curable sealer composition has been invented that has better workability than conventional solvent-based and water-based sealer compositions (Patent Documents 1 and 2).

JP 2006-22172 A JP 2003-238844 A

  By the way, when building materials are used on the walls of structures in cold regions, the back of building materials is particularly susceptible to condensation due to the temperature difference between indoor and outdoor air. There is a problem that promotes. Therefore, building materials used in cold regions are particularly required to have water resistance, water permeability resistance, and freeze-thaw resistance.

  However, the sealer composition of Patent Documents 1 and 2 has a problem in terms of water resistance. Especially when the sealer composition is used on the back surface of the building material, when moisture is generated due to condensation or the like, the sealer layer alone has water resistance. Insufficient adhesion with the base material (building material) deteriorated, preventing moisture from seeping into the base material, and preventing base material deterioration in cold regions. In addition, when the moisture that has permeated into the base material is repeatedly frozen and thawed, cracks are generated in the base material, the sealer layer cannot follow and cracks occur, which further promotes deterioration of the base material.

  In addition, inorganic building materials such as ceramic building materials are widely used for interiors, exteriors and roofs as non-combustible building material plates. For this reason, with inorganic building materials, the above-described deterioration of the base material in cold regions becomes more problematic.

  The present invention is intended to solve the problems associated with the prior art as described above, and is excellent in workability, blocking resistance, water resistance, water permeability resistance, freeze-thaw resistance, and volatile organic compounds. An object of the present invention is to provide an energy ray curable sealer composition for building materials such as inorganic building materials, a building material with a film having a cured film formed from the sealer composition, and a method for producing the building material. It is said.

The gist of the present invention is as follows.
[1]
A urethane (meth) acrylate resin (A) obtained by reacting a polyisocyanate (a1), a low-molecular diol (a2) having a molecular weight of 60 or more and 620 or less, and a (meth) acrylate (a3) having a hydroxyl group;
Polyisocyanate (B);
An energy ray curable sealer composition for building materials, comprising a photopolymerization initiator (C).

[2]
The polyisocyanate (B) is contained in a range of 0.1 to 400 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate resin (A). Energy ray curable sealer composition for building materials.

[3]
The energy ray curable sealer composition for building materials according to [1] or [2], wherein the urethane (meth) acrylate resin (A) has a molecular weight of 500 or more and 20,000 or less.

[4]
Furthermore, it contains the monomer (D) which has a photopolymerizable unsaturated group, The energy-beam curable sealer composition for building materials in any one of said [1]-[3] characterized by the above-mentioned.

[5]
The energy beam curable sealer composition for building materials according to any one of [1] to [4], wherein the energy beam curable sealer composition for building materials is an energy beam curable sealer composition for inorganic building materials. Composition.

[6]
A building material with a coating, comprising a cured coating formed from the energy ray curable sealer composition for building materials according to any one of [1] to [5] on at least a part of the surface of the substrate.

[7]
After coating the building material energy ray curable sealer composition according to any one of [1] to [5] on at least a part of the surface of the substrate, the composition surface is irradiated with energy rays. The manufacturing method of the building material with a film characterized by hardening | curing and forming a cured film.

  The cured film obtained from the energy ray curable sealer composition for building materials such as the inorganic building material of the present invention is excellent in adhesion, water resistance, water permeability, freeze-thaw resistance, and blocking resistance. In particular, since it is an energy beam curable type, it is excellent in workability and contributes to improvement of productivity in the factory. Moreover, the VOC can be reduced, and a building material excellent in environmental response can be obtained.

Hereinafter, an embodiment of the present invention will be described.
In the present invention, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. Moreover, a photopolymerizable unsaturated group means the unsaturated group which participates in a polymerization reaction with light.

[Energy beam curable sealer composition for building materials]
The building material energy ray curable sealer composition according to the present embodiment reacts a polyisocyanate (a1), a low molecular diol (a2) having a molecular weight of 60 or more and 620 or less, and a (meth) acrylate (a3) having a hydroxyl group. The urethane (meth) acrylate resin (A), the polyisocyanate (B) that may be the same as or different from the component (a1), and the photopolymerization initiator (C) are essential components. To do. Since the energy ray curable sealer composition for building materials of the present invention is an energy ray curable type, it is excellent in blocking resistance and workability and can be reduced in VOC. Hereinafter, each component will be described.

<Urethane (meth) acrylate resin (A) (component (A))>
Urethane (meth) acrylate resin (A) (hereinafter also referred to as component (A) or resin (A)) is at least a polyisocyanate (a1), a low molecular diol (a2) having a molecular weight of 60 to 620, and a hydroxyl group. It is a resin obtained by reacting a mixture of compounds containing (meth) acrylate (a3) having an essential component. In the present specification, the resin (A) includes an oligomer. The molecular weight of the resin (A) refers to the weight average molecular weight measured by gel permeation chromatography (GPC). The molecular weight of the resin (A) is not particularly limited, but is usually 500 or more and 20,000 or less, preferably 600 or more and 8,000 or less, and particularly preferably 650 or more and 4,000 or less.

  The component (A) has a photopolymerizable unsaturated group ((meth) acryloyl group) and a urethane bond. The component (A) has a structural unit composed of a low molecular diol (a2) having a molecular weight of 60 or more and 620 or less, and has a higher urethane bond amount than when a higher molecular diol is used. When such a component (A) is used, the cured film has a good balance between hardness and flexibility, and is excellent in water resistance, adhesion, water permeability, freeze-thaw resistance, and blocking resistance. When the amount of urethane bonds is large, it is considered that the above characteristics are improved because the crosslink density becomes high when a cured film is formed.

(Polyisocyanate (a1) (component (a1)))
As polyisocyanate (a1) (component (a1)), a conventionally known polyisocyanate compound having two or more isocyanate groups in one molecule can be used.

Specific examples of the component (a1) include diphenylmethane diisocyanate [MDI], tolylene diisocyanate [TDI], xylene diisocyanate [XDI], p-phenylene diisocyanate [PPDI], 3,3′-dimethyldiphenyl-4,4. Aromatic diisocyanates such as' -diisocyanate [TODI], dianisidine diisocyanate [DADI], tetramethylxylene diisocyanate [TMXDI], naphthalene diisocyanate [NDI];
Cycloaliphatic diisocyanates such as hydrogenated diphenylmethane diisocyanate [HMDI], hydrogenated xylene diisocyanate [HXDI], hydrogenated toluene diisocyanate [HTDI], isophorone diisocyanate [IPDI], norbornane diisocyanate;
Aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate [HDI], trimethylhexamethylene diisocyanate [TMHMDI], etc.
Triisocyanates such as triphenylmethane triisocyanate;
Examples of these polyisocyanate compounds include isocyanurates, burettes, adducts and the like, and polymeric isocyanates, but are not limited to these examples. The isocyanurate body refers to a trimer of the above diisocyanate, the burette body refers to a reaction product of the diisocyanate and water or a tertiary alcohol, and the adduct body refers to a polyol such as diisocyanate and trimethylolpropane. And adducts. Polymeric isocyanate refers to polymeric MDI (polymethylene polyphenyl polyisocyanate).

Among the above-mentioned polyisocyanates, aromatic diisocyanates and alicyclic diisocyanates are preferable from the viewpoint of improving the water resistance, adhesion, water permeability, and freeze-thaw resistance of the cured film. Tolylene diisocyanate, diphenylmethane diisocyanate, isophorone Diisocyanate is more preferred.
Such polyisocyanates may be used singly or in combination of two or more.

(Low molecular weight diol (a2) having a molecular weight of 60 or more and 620 or less (component (a2)))
As the low molecular diol (a2) (component (a2)) having a molecular weight of 60 or more and 620 or less, a conventionally known diol compound having two hydroxyl groups can be used. The molecular weight can be measured by a conventionally known method, and is determined by, for example, gel permeation chromatography (GPC). In addition, when the component (a2) is a substance having a molecular weight distribution such as polyether glycol, the molecular weight indicates a weight average molecular weight measured by gel permeation chromatography (GPC).
The upper limit of the molecular weight of component (a2) is preferably 550, more preferably 450, still more preferably 400, even more preferably 350, particularly preferably 200.

Specific examples of the component (a2) include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3- Butanediol, dibutylene glycol, tributylene glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, 1, 6-hexanediol, 2-ethyl-1,3-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, other alkanes Diol, polyethylene glycol, polypropylene Glycol, aliphatic diols and polyether glycol polybutylene glycol and the like;
Cycloaliphatic aliphatic diols such as cyclohexanediol and cyclohexanedimethanol;
Aromatic diols such as xylene glycol, bishydroxyethoxybenzene, bishydroxyethyl terephthalate, bisphenol A;
Among polycaprolactone diols and the like, those having a molecular weight in the range of 60 to 620 can be mentioned, but are not limited to such examples.

  Among the above diols, alkanediol (C2-C9) is used from the viewpoint of maintaining a good balance between hardness and flexibility of the cured coating film and improving water resistance, adhesion, water permeability, freeze-thaw resistance, and blocking resistance. ), (Poly) ethylene glycol, and (poly) propylene glycol are preferred. Such diols may be used singly or in combination of two or more.

((Meth) acrylate having hydroxyl group (a3) (component (a3)))
As the (meth) acrylate (a3) (component (a3)) having a hydroxyl group, (meth) acrylate having one or more hydroxyl groups can be used.

  Specific examples of the component (a3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3- Hydroxyalkyl (meth) acrylates having 2 to 7 carbon atoms in the alkyl group, such as hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, Hydroxyl-terminated (meth) acrylates such as polypropylene glycol mono (meth) acrylate, N-methylol (meth) acrylamide, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-chloropropi (Meth) acrylate, although ε- caprolactone monomer ring-opening polymerization was caprolactone-modified hydroxyl group-containing obtained by (meth) acrylate and the like, are not limited only to those exemplified.

Among the hydroxyl group-containing (meth) acrylates described above, 2-hydroxyethyl acrylate is preferable from the viewpoints of hardness and curability of the cured coating film.
Such hydroxyl group-containing (meth) acrylates may be used singly or in combination of two or more.

(Ratio of components (a1) to (a3))
In order to synthesize the component (A), the number of moles (NCO) of the isocyanate group of the polyisocyanate (a1), the number of moles of the hydroxyl group of the low molecular diol (a2), and the (meth) acrylate (a3 ) In the ratio of the total number of moles of hydroxyl groups (OH) to [OH] / [NCO] = 0.8 to 1.4, preferably 1.0 to 1.2 It is more preferable to make it react by the ratio used as this range.

Such a urethane (meth) acrylate resin (A) can improve the water resistance, adhesion, water permeability, freeze-thaw resistance, and blocking resistance of the cured coating film in a well-balanced manner.
When the component (a1) is a diisocyanate and the component (a3) is a (meth) acrylate having one hydroxyl group, the urethane (meth) acrylate resin (A) has, for example, a structure composed of repeating units of the formula (1). including. The terminal of the molecule of the component (A) is bonded to the structural unit of the formula (2) on the * side of the formula (1), for example, and the ** side of the formula (1) is the structural unit of the formula (3), for example. Are connected. The above repeating unit is repeated so that the molecular weight of the component (A) is in the above-described range.

In the formulas (1) to (3), X to Z are divalent groups. X is a deOH residue of diol (HO-X-OH), Y is a deNCO residue of diisocyanate (OCN-Y-NCO), and Z is a (meth) acrylate (HO-) having one hydroxyl group. Z-OC (= O) is de (meth) acryloyloxy and de OH residues of -CR = CH _2). R represents a hydrogen atom or a methyl group.

The structural unit (1) is derived from the component (a1) and the component (a2), the structural unit (2) is derived from the component (a1) and the component (a3), and the structural unit (3) is derived from the component (a3). Therefore, diisocyanate (OCN-Y-NCO) is selected from the examples of diisocyanate for component (a1), diol (HO-X-OH) is selected from the examples for component (a2), and the hydroxyl group is 1 The (meth) acrylate having one (HO—Z—OC (═O) —CR═CH ₂ ) is selected from the examples of (meth) acrylate having one hydroxyl group for the component (a3).

<Polyisocyanate (B) (Component (B))>
The polyisocyanate (B) (component (B)) may be the same as or different from the component (a1).

  It is considered that the NCO group of the polyisocyanate (B) reacts with moisture in the substrate or air when the sealer composition is cured to form a cured film, thereby forming a urea bond to strengthen the substrate. Thereby, in the cured film obtained from the sealer composition of this invention, it is thought that adhesiveness, water resistance, water permeability resistance, and freeze-thaw resistance improve.

  In addition, when building materials are used on the walls of structures in cold regions, the backside of the building materials is particularly susceptible to condensation due to the temperature difference between the indoor and outdoor air. There is a problem that promotes. On the other hand, if a cured film is formed on a base material using a sealer composition containing polyisocyanate (B) as in the present invention, moisture will permeate the base material and the base material is repeatedly frozen and thawed. Even if cracks occur, the cured coating follows the cracks, and therefore it is considered that the deterioration of the base material can be suppressed (excellent in water permeability resistance and freeze-thaw resistance).

Specific examples of the polyisocyanate (B) include those described in the description of the component (a1).
Among the above-mentioned polyisocyanates, tolylene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate from the viewpoints of adhesion of cured film, water resistance, water permeability resistance, freeze-thaw resistance, coating workability, and pot life of sealer composition. Hydrogenated diphenylmethane diisocyanate and isocyanurates, burettes, and adducts of these polyisocyanates are preferred.
Such polyisocyanates may be used singly or in combination of two or more.

  Moreover, as a component (B), you may use the polyisocyanate marketed as a mixture with a solvent. In order to reduce VOC, it is preferable to use the component (B) that is not a mixture with a solvent from the viewpoint of making the sealer composition of the present invention a solvent-free type.

  The polyisocyanate (B) is preferably contained in the sealer composition in an amount of 0.1 to 400 parts by weight, more preferably 1 to 300 parts by weight with respect to 100 parts by weight of the component (A). desirable.

<Photopolymerization initiator (C) (component (C))>
A conventionally well-known thing can be used as a photoinitiator (C) (component (C)).
Specific examples of the component (C) include benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether;
Benzyldimethyl ketal (also known as 2,2-dimethoxy-2-phenylacetophenone), diethoxyacetophenone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, 2-hydroxy- 2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2- Methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl]- Acetophenone-based light weight such as 2-morpholinopropane-1 Initiator;
Benzophenone light such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone A polymerization initiator;
Thioxanthone photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc.
Such photopolymerization initiators (C) may be used singly or in combination of two or more.

  The photopolymerization initiator (C) as described above is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight in the sealer composition with respect to 100 parts by weight of the component (A). It is desirable that it be included.

<Monomer (D) having photopolymerizable unsaturated group (component (D))>
The energy beam curable resin composition for building materials of the present invention may further contain a monomer (D) (component (D)) having a photopolymerizable unsaturated group. Component (D) has a role as a reactive diluent, can lower the viscosity of the sealer composition, and improve the workability.

  Examples of the component (D) include tripropylene glycol diacrylate, acryloyl morpholine, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like. It is not limited.

  Component (D) may be added to the aforementioned components (a1) to (a3) when synthesizing component (A). In that case, (meth) acrylate having no hydroxyl group is selected and used. In other words, in the case of the component (D) having no hydroxyl group, it may be blended with other components after the synthesis of the component (A), but when synthesizing the component (A), the components (a1) to You may mix | blend with (a3). On the other hand, in the case of the component (D) having a hydroxyl group, it is desirable to blend after the synthesis of the component (A).

  Among the above-mentioned monomers having a photopolymerizable unsaturated group, a trifunctional or less functional monomer such as tripropylene glycol diacrylate, acryloyl morpholine, pentaerythritol triacrylate or the like is preferable from the viewpoint of viscosity adjustment (handling) and curability.

The monomer (D) having such a photopolymerizable unsaturated group may be used alone or in combination of two or more.
When the monomer (D) having a photopolymerizable unsaturated group as described above is used, it is preferably more than 0 parts by weight and 180 parts by weight or less, more preferably 0 parts by weight with respect to 100 parts by weight of the component (A). It is desirable to mix in the sealer composition in an amount of more than 100 parts by weight and less.

<Other ingredients>
In the sealer composition for building materials of the present invention, in addition to the above components (A) to (D), if necessary, extender pigments, color pigments, dispersants, anti-settling agents, leveling agents, antifoaming agents A polymerization inhibitor, a solvent, or the like can be used.

(External pigment, colored pigment)
The extender pigment also has a role as a filler, and talc, nepheline syenite, calcium carbonate, clay, silica, mica, and the like can be used. Color pigments include titanium oxide, carbon black, iron oxide ( Petals) or the like can be used, but is not limited thereto. Such extender pigments and colored pigments may be used singly or in combination of two or more.

These extender pigments and colored pigments have an effect of improving the water permeability of the cured film, in addition to the role of hiding the base.
When the extender pigment and the color pigment are used, the sealer composition is preferably used in an amount of more than 0 part by weight and 180 parts by weight or less, more preferably more than 0 part by weight and 120 parts by weight or less with respect to 100 parts by weight of component (A) It is desirable to mix in the product.

(Polymerization inhibitors, etc.)
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, benzoquinone, p-tert-butyl carbitol, 2,6-di-tert-butyl-4-methylphenol, and the like.

Each of the dispersant, the anti-settling agent, the leveling agent, the antifoaming agent, and the polymerization inhibitor may be used alone or in combination of two or more.
When a dispersant, an anti-settling agent, a leveling agent, an antifoaming agent, or a polymerization inhibitor is used, it is preferably more than 0 parts by weight and 4 parts by weight or less, more preferably 0 with respect to 100 parts by weight of component (A). It is desirable to mix in the sealer composition in an amount of more than 0.5 parts by weight and less than 0.5 parts by weight.

(solvent)
Although it does not specifically limit as a solvent, For example, ethyl acetate, butyl acetate, xylene, methoxypropyl acetate, etc. are mentioned. Such solvents may be used singly or in combination of two or more.

A solvent may be mix | blended with a sealer composition as a mixture of a component (B) as mentioned above.
When a solvent is used, it is preferably incorporated in the sealer composition in an amount of more than 0 parts by weight and 100 parts by weight or less, more preferably more than 0 parts by weight and 20 parts by weight or less with respect to 100 parts by weight of the component (A). It is desirable to do.
In order to reduce the VOC, it is preferable not to use a solvent from the viewpoint of making the sealer composition of the present invention a solvent-free type.

<Viscosity>
Although the viscosity of the sealer composition for building materials of the present invention is not particularly limited, from the viewpoint of coating workability, it is usually preferably in the range of 100 to 15,000 mPa · s at a composition temperature of 20 ° C. The viscosity is determined by a B-type viscometer.

<Method for preparing energy ray curable sealer composition for building material>
The building material energy ray curable sealer composition of this embodiment comprises a urethane (meth) acrylate resin (A), a polyisocyanate (B), a photopolymerization initiator (C), and a photopolymerizable unsaturated group as required. It can be prepared by adding and mixing the monomer (D) having other components.

In addition, from the viewpoint of pot life of the sealer composition, a component other than the polyisocyanate (B) is mixed to prepare a resin composition, and then the component (B) is mixed during coating to prepare a sealer composition. Is desirable.
The energy beam curable sealer composition for building materials described above is particularly suitably used as an energy beam curable sealer composition for inorganic building materials.

[Building material with coating and method for producing the same]
The building material with a film of the present invention has a cured film formed from the above-described energy ray curable sealer composition for building material on at least a part of the surface of the base material. In the building material with a film according to the present embodiment, the energy beam curable sealer composition for building material described above is applied to at least a part of the surface of the base material and cured to form a cured film. That is, in the method for producing a coated material according to the present invention, at least one surface of a base material is coated with the above-mentioned energy ray curable sealer composition for building materials, and then the composition surface is irradiated with energy rays. It hardens | cures and forms a hardened film.

The building material with a coating obtained by the method for producing a building material with a coating according to the present invention and the building material with a coating according to the present invention only needs to have a cured coating on at least a part of the substrate surface. In addition, the surface here refers to the main surface or end surface of a base material, Preferably it is a main surface. A main surface refers to the front surface or the back surface (back surface) of a base material in a plate-shaped base material.
Although the film thickness of a cured film is not specifically limited, 3-60 micrometers is preferable.

<Base material>
Base materials include calcium silicate board, slate board, fiber cement board, lightweight concrete board, mortar board, gypsum board, stone, glass, tile, tile, brick, ceramic siding material, etc., metal siding material Metal base materials such as steel, stainless steel and aluminum, organic base materials such as synthetic resin, wood and paper, and composite base materials obtained from these plural base materials. In the present invention, any conventionally known building materials are suitably used as the base material, and inorganic building materials are more suitably used.

<Coating method>
Conventionally known methods can be used as a method for coating the sealer composition for building materials, such as sponge roll coater, natural roll coater, reverse roll coater, curtain flow coater, knife coater, die coater, air spray, airless spray, A roller, brush application, immersion, etc. are mentioned, It can select suitably. Among these, the use of a sponge roll coater is preferable because the coating amount on the substrate can be increased and the coating performance such as water resistance and water permeability is improved.
The application amount of the sealer composition is usually 1.0 to 220 g / m ² , and the sealer composition may be applied a plurality of times.

<Energy beam irradiation>
The sealer composition for building materials according to the present invention can be cured by irradiation with energy rays after being coated on a substrate. Examples of energy rays include electromagnetic waves such as X-rays and γ rays, electron rays, proton rays, neutron rays, etc., in addition to rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays. From the viewpoint of easy availability and price, ultraviolet rays are preferable.

As a method of curing with energy rays, a method of irradiating about 30 to 3,000 mJ / cm ² using a high pressure mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp or the like that emits light in a wavelength range of 75 to 2,600 nm. Is mentioned.

<Other sealer compositions, base coats and top coats>
After the sealer composition of the present invention is applied and cured to form a cured film, other sealer compositions, undercoat paints, topcoat paints and the like can be appropriately selected and applied as necessary. Moreover, you may paint the sealer composition of this invention on the building material which has the cured film formed from the other sealer composition.

  The building material with a coating thus obtained (for example, an inorganic building material with a coating) has a cured coating formed from the above-mentioned energy ray curable sealer composition for building materials, and therefore has adhesion, water resistance, water permeability resistance, Excellent freeze-thaw resistance and blocking resistance.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.
The synthesis example of urethane (meth) acrylate resin (A) is demonstrated below.

<Synthesis Example 1>
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling tube and air gas introduction tube, 1,4-butanediol (manufactured by Mitsubishi Chemical Corporation) was used as a component (a2) in the reaction vessel. , Molecular weight 90) 45.0 parts by weight, as component (a3), 2-hydroxyethyl acrylate (molecular weight 116) 121.8 parts by weight, and as component (D), TPGDA (manufactured by Daicel Ornex Co., Ltd.) Propylene glycol diacrylate, molecular weight 300) 85.2 parts by weight, hydroquinone monomethyl ether 0.1 part by weight and GREC TL (manufactured by DIC, dibutyltin dilaurate) 0.2 part by weight were charged, and the temperature was raised to 75 ° C. Keep at -80 ° C, and as component (a1), Coronate T-80 (manufactured by Tosoh Corporation, tolylene diisocyanate, molecular weight 174) 74.0 parts by weight evenly added dropwise to react for 3 hours.

The reaction was continued for about 2 hours after completion of the dropping, and the reaction was terminated after confirming that the isocyanate had disappeared by IR measurement, and a resin composition containing a urethane acrylate resin having a solid content of about 100% was obtained. Among them, the urethane acrylate resin (A) excluding the component (D) as the reactive diluent was 89.7% by weight. The weight average molecular weight measured by gel permeation chromatography (GPC) of the urethane acrylate resin (A) was 979. The measurement conditions are as follows.
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column: Super H2000 + H4000 manufactured by Tosoh Corporation (each inner diameter 6 mm, length 15 cm)
Developing solvent: THF
Column bath temperature: 40 ° C
Flow rate: 0.5 ml / min
Control: monodisperse polystyrene

  The ratio of the number of moles of isocyanate groups (NCO) of component (a1) to the total number of moles of hydroxyl groups of component (a2) and the number of moles of hydroxyl groups of component (a3) is [OH] / [ NCO] = 1.025.

<Synthesis Example 2>
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling tube and air gas introduction tube, ethylene glycol (Mitsubishi Chemical Co., Ltd., molecular weight 62) was used as the component (a2) in this reaction vessel. 31.0 parts by weight, as component (a3), 121.8 parts by weight of 2-hydroxyethyl acrylate (molecular weight 116), and as component (D), TPGDA (manufactured by Daicel Ornex Co., Ltd., tripropylene glycol diacrylate) , Molecular weight 300) 81.7 parts by weight, 0.1 part by weight of hydroquinone monomethyl ether and 0.2 part by weight of GREC TL (DIC, dibutyltin dilaurate) were charged, heated to 75 ° C. and then heated to 75-80 ° C. Insulate, and as component (a1), Coronate T-80 (manufactured by Tosoh Corporation, tolylene diisocyanate, molecular weight 174) 17 .0 parts by weight evenly added dropwise to react for 3 hours.

  The reaction was continued for about 2 hours after completion of the dropping, and the reaction was terminated after confirming that the isocyanate had disappeared by IR measurement, and a resin composition containing a urethane acrylate resin having a solid content of about 100% was obtained. Among them, the urethane acrylate resin (A) excluding the component (D) which is a reactive diluent was 80.0% by weight. The weight average molecular weight of the urethane acrylate resin (A) measured by gel permeation chromatography (GPC) was 780. The measurement conditions are the same as those in Synthesis Example 1.

  The ratio of the number of moles of isocyanate groups (NCO) of component (a1) to the total number of moles of hydroxyl groups of component (a2) and the number of moles of hydroxyl groups of component (a3) is [OH] / [ NCO] = 1.0.

<Synthesis Example 3>
After introducing air gas into a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe and an air gas introduction pipe, as a component (a2) in this reaction vessel, Sanix PP-400 (manufactured by Sanyo Chemical Industries, Ltd.) , Polypropylene glycol, molecular weight 400) 204.0 parts by weight, component (a3) as 2-hydroxyethyl acrylate (molecular weight 116) 121.8 parts by weight, and component (D) as TPGDA (Daicel Ornex Co., Ltd.) Made of tripropylene glycol diacrylate, molecular weight 300) 124.8 parts by weight, 0.3 part by weight of hydroquinone monomethyl ether and 0.3 part by weight of GREC TL (DIC, dibutyltin dilaurate) After warming, the mixture was kept at 75-80 ° C., and as component (a1), Coronate T-80 (manufactured by Tosoh Corporation Diisocyanate, molecular weight 174) and 174.0 parts by weight was uniformly added dropwise to react for 3 hours.

  The reaction was continued for about 2 hours after completion of the dropping, and the reaction was terminated after confirming that the isocyanate had disappeared by IR measurement, and a resin composition containing a urethane acrylate resin having a solid content of about 100% was obtained. Among them, the urethane acrylate resin (A) excluding the component (D) which is a reactive diluent was 80.0% by weight. The weight average molecular weight of the urethane acrylate resin (A) measured by gel permeation chromatography (GPC) was 1,383. The measurement conditions are the same as those in Synthesis Example 1.

  The ratio of the number of moles of isocyanate groups (NCO) of component (a1) to the total number of moles of hydroxyl groups of component (a2) and the number of moles of hydroxyl groups of component (a3) is [OH] / [ NCO] = 1.0.

<Comparative Synthesis Example 1>
After introducing air gas into a reaction vessel equipped with a stirrer, a thermometer, a cooling tube and an air gas introduction tube, PTG-650 (manufactured by BASF, polytetramethylene was used as a comparison of the component (a2). Glycol, molecular weight 650) 325 parts by weight, as component (a3), 121.8 parts by weight of 2-hydroxyethyl acrylate, as component (D), 155.2 parts by weight of TPGDA, and 0.2 parts by weight of hydroquinone monomethyl ether And 0.3 g by weight of GREC TL, heated to 75 ° C. and then kept at 75 to 80 ° C., and as a component (a1), 174.0 parts by weight of Coronate T-80 were dropped evenly over 3 hours and reacted. It was.

The reaction was continued for about 2 hours after completion of the dropping, and the reaction was terminated after confirming that the isocyanate had disappeared by IR measurement, and a resin composition containing a urethane acrylate resin having a solid content of about 100% was obtained. Among them, the urethane acrylate resin excluding the component (D) which is a reactive diluent was 80.0% by weight. The weight average molecular weight of the urethane acrylate resin measured by gel permeation chromatography (GPC) was 4,628. The measurement conditions are as follows.
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column: Super H2000 + H4000 manufactured by Tosoh Corporation (each inner diameter 6 mm, length 15 cm)
Developing solvent: THF
Column bath temperature: 40 ° C
Flow rate: 0.5 ml / min
Control: monodisperse polystyrene

The ratio of the number of moles of isocyanate groups (NCO) of component (a1) to the number of moles of hydroxyl groups of comparative component of component (a2) and the total number of moles of hydroxyl groups of component (a3) (OH) is [OH ] / [NCO] = 1.005.
Production examples of the energy beam curable sealer composition for building materials will be described below.

<Example 1>
50 parts by weight of the resin composition obtained in Synthesis Example 1 [45 parts by weight of urethane acrylate resin as component (A), 5 parts by weight of TPGDA as component (D)], DAROCURE 1173 (BASF) as component (C) 2-hydroxy-2-methylpropiophenone) 5.2 parts by weight and Irgacure 651 (BASF, 2,2-dimethoxy-1,2-diphenylethane-1-one) 1.8 parts by weight, Ingredient pigment in a container containing 8 parts by weight of ACMO (manufactured by KJ Chemicals, acryloylmorpholine) and 10 parts by weight of TPGDA (manufactured by Daicel Ornex Co., Ltd.) as component (D) MINEX10 (manufactured by UNIMIN CORPORATION, nepheline syenite) 30 parts by weight Fine Himicron G (Fuji Talc Kogyo Co., Ltd., talc) 5 parts by weight, and the mixture was stirred to obtain a resin composition. Furthermore, 10 parts by weight of Duranate TPA-100 (produced by Asahi Kasei Chemicals Co., Ltd., isocyanurate of hexamethylene diisocyanate) was added as a component (B) to prepare an energy ray curable sealer composition for building materials.

<Examples 2 to 10, Comparative Examples 1 and 2>
In Examples 2 to 8 and Comparative Example 1, a building material energy ray curable sealer composition was obtained in the same manner as in Example 1 except that the component (B) was changed to the components and blending amounts shown in Table 1.
In Examples 9 and 10, the resin composition obtained in Synthesis Example 1 was mixed with 50 parts by weight of the resin composition obtained in Synthesis Example 2 or 3 [of which, urethane acrylate resin as component (A) 40 parts by weight, component ( D) TPGDA 10 parts by weight] was obtained in the same manner as in Example 1 to obtain an energy ray curable sealer composition for building materials.

  In Comparative Example 2, the resin composition obtained in Synthesis Example 1 was added to 50 parts by weight of the resin composition obtained in Comparative Synthesis Example [including 40 parts by weight of urethane acrylate resin and 10 parts by weight of TPGDA as component (D)]. Except for the change, an energy ray curable sealer composition for building materials was obtained in the same manner as in Example 1. The components used are shown below.

Ingredient (B)
"Coronate HL" (Tosoh Co., Ltd., hexamethylene diisocyanate adduct) has a solid content of 75% and is a mixture with 25% ethyl acetate.
“Sumijoule N75” (manufactured by Sumika Bayer Urethane Co., Ltd., hexamethylene diisocyanate burette) has a solid content of 75% and is a mixture of 12.5% xylene and 12.5% methoxypropyl acetate.
“Cosmonate T-80” (Mitsui Chemicals, Tolylene Diisocyanate)
"SBU Isocyanate J243" (manufactured by Sumika Bayer Urethane Co., Ltd., mixture of diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate (polymeric MDI))
“Takenate D110N-75” (manufactured by Mitsui Chemicals, Inc., trimethylolpropane adduct of xylene diisocyanate)

<Preparation of coated inorganic building materials>
The energy ray curable sealer composition for building materials obtained in Examples 1 to 10 and Comparative Examples 1 and 2 was applied to an inorganic building material plate (calcium silicate plate) at a coating amount of 44 g / m ² using a sponge roll coater. Painted. Further, using a high-pressure mercury lamp (80 W / cm) manufactured by Igraphic, ultraviolet rays were irradiated in an amount such that the integrated light amount was 100 mJ / cm ^2, and the coating film was cured to obtain a coated inorganic building material. At the time of this ultraviolet irradiation, the distance between the light source and the coating film was 15 cm, and the moving speed of the inorganic building material plate was 5 m / min. The film thickness of the cured film was 40 μm.

<Evaluation method>
The obtained inorganic substrate with a coating was cut into a size of 200 × 100 mm with a diamond cutter to produce a test piece, and the evaluation test shown below was performed.

(Adhesion)
In order to evaluate the adhesion of the cured coating to the inorganic building material, a cross-cut test was performed based on JIS K5400. Specifically, after making a 4 mm wide and 25 square wound with a cutter on the cured coating of the test piece to produce a test piece with a grid, and attaching “Cello Tape (registered trademark)” to the test piece The tape was peeled off, and the adhesion was evaluated by the area of the peeled cured film. Those whose evaluation criteria were Δ or more were regarded as acceptable.
Evaluation criteria (initial adhesion / cross-cut test)
○ ・ ・ ・ Peeling area less than 6% △ ・ ・ ・ Peeling area of 6% or more and less than 10% × ・ ・ ・ Peeling area of 10% or more

(water resistant)
In order to evaluate the water resistance of the cured coating, a hot water resistance test was conducted. Specifically, the test piece was immersed in warm water at 60 ° C. for 240 hours, and then the appearance of the cured film was visually evaluated. Further, a cross-cut test (a method similar to the above-described test) was performed on the test piece after immersion for 240 hours, and the adhesion after the hot water resistance test was evaluated. Those whose evaluation criteria were Δ or more were regarded as acceptable.
Evaluation criteria (appearance / visual)
○ ・ ・ ・ Good with no peeling, cracking, or swelling △ ・ ・ ・ Slight peeling, cracking, or blistering, but good × ・ ・ ・ Many peeling, cracking, or blistering failure Evaluation criteria (Adhesion after 240 hours of water resistance test) / Cross-cut test)
◎ ・ ・ ・ Peeling area less than 3% ○ ・ ・ ・ Peeling area 3% or more and less than 6% △ ・ ・ ・ Peeling area 6% or more and less than 10% × ・ ・ ・ Peeling area 10% or more

(Freeze-thaw resistance)
In order to evaluate the freeze-thaw resistance of the cured coating, a freeze-thaw resistance test was performed. Specifically, after the test piece was cooled in air at −20 ° C. for 2 hours and then immersed in 20 ° C. water for 2 hours, one cycle was performed, and the appearance of the cured film appearance at the time after 100 cycles and 200 cycles was obtained. Visual evaluation was performed. Further, a cross-cut test (the same method as the above test) was performed on the test pieces after 100 cycles and 200 cycles, and the adhesion after the freeze-thaw resistance test was evaluated. Those whose evaluation criteria were Δ or more were regarded as acceptable.
Evaluation criteria (appearance / visual)
○ ・ ・ ・ Good with no peeling, cracking, or swelling △ ・ ・ ・ Slight peeling, cracking, or swelling is good, but good × ・ ・ ・ Many peeling, cracking, and swelling are bad Evaluation criteria (100 cycles after freeze-thaw test and Adhesion after 200 cycles / cross-cut test)
○ ・ ・ ・ Peeling area less than 6% △ ・ ・ ・ Peeling area of 6% or more and less than 10% × ・ ・ ・ Peeling area of 10% or more

<Test results>
Table 1 shows the test evaluations of Examples 1 to 10 and Comparative Examples 1 and 2.
As shown in Table 1, all of the cured films made of the building material sealer compositions obtained in Examples 1 to 10 were excellent in adhesion, water resistance, and freeze-thaw resistance.

  On the other hand, in Comparative Example 1 not containing the component (B), the freeze-thaw resistance was poor. Further, in Comparative Example 2 using a polymer diol instead of the low-molecular diol as the component (a2), the water resistance and freeze-thaw resistance were poor. By combining the component (A) obtained from the component (a2) and the component (B) as in the present invention, it is considered that a cured film excellent in water resistance and freeze-thaw resistance is formed.

※１ 合成例１〜３、比較合成例１において、樹脂合成時に添加した成分（Ｄ）である。

* 1 Component (D) added during resin synthesis in Synthesis Examples 1 to 3 and Comparative Synthesis Example 1.

  The energy ray curable sealer composition for building materials according to the present invention is used for various interiors and exteriors of buildings such as inorganic base materials, organic base materials, composite base materials and the like used for various applications such as wall materials, floor materials, and roofing materials. It can be applied to building material substrates. Moreover, according to this invention, the building material with a film which can use suitably as various building materials for interior and exterior which formed the cured film with the said sealer composition can be provided.

Claims (7)

A urethane (meth) acrylate resin (A) obtained by reacting a polyisocyanate (a1), a low-molecular diol (a2) having a molecular weight of 60 or more and 620 or less, and a (meth) acrylate (a3) having a hydroxyl group;
Polyisocyanate (B);
An energy ray curable sealer composition for building materials, comprising a photopolymerization initiator (C).   The building material according to claim 1, wherein the polyisocyanate (B) is contained within a range of 0.1 to 400 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate resin (A). Energy ray curable sealer composition.   The molecular weight of the urethane (meth) acrylate resin (A) is 500 or more and 20,000 or less, and the energy ray curable sealer composition for building materials according to claim 1 or 2.   Furthermore, the monomer (D) which has a photopolymerizable unsaturated group is contained, The energy-beam curable sealer composition for building materials of any one of Claims 1-3 characterized by the above-mentioned.   The energy beam curable sealer composition for building materials according to any one of claims 1 to 4, wherein the energy beam curable sealer composition for building materials is an energy beam curable sealer composition for inorganic building materials. object.   A building material with a film, comprising a cured film formed from the energy ray curable sealer composition for building material according to any one of claims 1 to 5 on at least a part of a surface of a base material.   After coating the building material energy ray curable sealer composition according to any one of claims 1 to 5 on at least a part of the surface of the base material, the composition surface is irradiated with energy rays. A method for producing a building material with a coating, characterized by curing to form a cured coating.