JP7104967B2 - Surface treatment agent and bonding method using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a surface treatment agent mainly used when applying a moisture-curable composition, and an adhesion method using the same.

BACKGROUND ART Adhesives are widely used for bonding members of buildings, civil engineering structures, vehicles, industrial and consumer equipment, and the like. In particular, as an adhesive used for bonding between members of buildings and civil engineering structures, from the viewpoint of extending the life of buildings and civil engineering structures, adhesives with excellent adhesion to members are required. . That is, even if the performance of the adhesive (for example, adhesive strength) is good, if the adhesiveness to the member is not sufficient, it will cause poor bonding (peeling), making it difficult to predict the durability of the joint. . Therefore, if the bonding failure is due to interfacial peeling between the adhesive and the member in the preliminary adhesion test, the bonding reliability cannot be ensured, and the combination of the adhesive and the member may not be adopted at the design stage. many. For this reason, adhesives are required to have not only performance such as adhesive strength, but also excellent adhesiveness to members.

The adhesive is a one-component curable composition that cures by reacting with moisture in the air, and a two-component curable composition that cures by reacting the main agent and the curing agent by blending a curing agent into the main agent at the time of use. there is a thing Of these, the use of one-component moisture-curable compositions is increasing in order to prevent poor curing due to insufficient mixing of the main agent and the curing agent or an error in the mixing ratio of the main agent and the curing agent.

However, one-component moisture-curing compositions may be extremely slow to cure in winter (low temperature and low humidity) environments, and the curing period is prolonged, which delays or lengthens the working process. cause. Therefore, as a method for accelerating the curing of a one-component moisture-curable composition, a method of applying a water-containing coating agent has been proposed (eg, Patent Documents 1 to 4). These methods speed up the curing of the one-component moisture-curable composition and improve the tackiness of the surface, but improve the adhesion between the base material, the adhesive and the member.

Japanese Patent Application Laid-Open No. 2001-348806 JP-A-2001-354950 JP 2013-076065 A JP 2017-036399 A

In view of the above circumstances, an object of the present invention is to provide a moisture-curable composition by applying a surface treatment agent to the surface of a base material and then applying a moisture-curable composition to the surface of the base material to which the surface treatment agent has been applied. A base treatment that can accelerate the curing of the moisture-curable composition and improve the adhesion between the base material, the moisture-curable composition, and the member when the base material and the member are joined via the curable composition. It is to provide agents.

As a result of intensive studies by the present inventors, first, a surface treatment agent containing an organic solvent, water, and a curing catalyst within a specific range was applied to the surface of the base material, and the surface of the base material to which the surface treatment agent was applied was treated. The inventors have found that the above problems can be solved by applying a moisture-curable composition and bonding the base material and the member via the moisture-curable composition, and have completed the present invention. That is, the present invention provides the following (1) to (10).

(1) A surface treatment agent containing an organic solvent, water and a curing catalyst,
The compounding amount of the organic solvent is 50 to 99% by mass of the entire surface treatment agent, the compounding amount of the water is 0.1 to 5 parts by mass with respect to 100 parts by mass of the organic solvent, and the compounding amount of the curing catalyst is the organic solvent. 0.5 to 10 parts by mass of a surface treatment agent per 100 parts by mass of a solvent.
(2) The surface treatment agent according to (1), wherein the organic solvent is at least one selected from the group consisting of ester solvents, ether solvents, ketone solvents and carbonate solvents. .
(3) The surface treatment agent according to (1) or (2), wherein the curing catalyst contains a metal catalyst and an amine catalyst.
(4) The surface treatment agent according to (3), wherein the metal catalyst contains an organic tin compound.
(5) The surface treatment agent according to (3) or (4), wherein the amine catalyst contains a tertiary amine compound.
(6) The surface treatment agent according to any one of (1) to (5), which is a surface treatment agent for a moisture-curable composition.
(7) The surface treatment according to any one of (1) to (6), wherein the moisture-curable composition contains an isocyanate group-containing resin and/or a hydrolyzable silyl group-containing resin. agent.
(8) The surface treatment agent according to (6) or (7), wherein the moisture-curable composition is an adhesive composition.
(9) The surface treatment agent according to any one of (1) to (8), which is used for construction or civil engineering.
(10) A surface treatment agent containing an organic solvent, water, and a curing catalyst, wherein the amount of the organic solvent is 50 to 99% by mass of the total amount of the surface treatment agent, and the amount of water is 100% by mass of the organic solvent. a step of applying to the surface of the base material a surface treatment agent having a curing catalyst content of 0.1 to 5 parts by mass per part and a curing catalyst content of 0.5 to 10 parts by mass per 100 parts by mass of the organic solvent;
a step of applying a moisture-curable composition to the surface of the base material to which the base treatment agent has been applied;
including a step of bonding the base material and the member together via the moisture-curable composition;
Adhesion method.

After applying the surface treatment agent to the surface of the base material, by applying the moisture-curable composition to the surface of the base material to which the surface treatment agent has been applied, the base material and the member are bonded via the moisture-curable composition. When joining, the curing of the moisture-curable composition can be accelerated, and the adhesiveness between the base material, the moisture-curable composition and the member can be improved.

Hereinafter, the surface treatment agent of the present invention will be described in detail according to embodiments. The surface treatment agent of the present invention is a surface treatment agent containing an organic solvent, water, and a curing catalyst, wherein the compounding amount of the organic solvent is 50 to 99% by mass of the whole surface treatment agent, and the water content is The amount of the curing catalyst is 0.1 to 5 parts by mass with respect to 100 parts by mass of the organic solvent, and the amount of the curing catalyst is 0.5 to 10 parts by mass with respect to 100 parts by mass of the organic solvent. Each component will be described in detail below.

First, the organic solvent will be explained. The organic solvent blended in the surface treatment agent of the present invention does not react with the base material, the moisture-curable composition, and other adherend members (for example, finishing materials, etc.), and does not react with water. As long as it is miscible and dissolves the curing catalyst, it can be used without any particular limitation. By adding an organic solvent to the surface treatment agent of the present invention, it becomes easy to adjust the concentration and viscosity of each component (including water and curing catalyst) in the surface treatment agent, and the surface treatment agent is applied (for example, by coating). application, application by spraying, etc.) can be improved. When the underlying material or member is an organic material, it is conceivable that the underlying material or member may slightly swell or dissolve due to contact with the organic solvent. For example, a surface treatment agent can be used.

Specific examples of the organic solvent blended in the surface treatment agent of the present invention include, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, and ethyl butyrate. , butyl butyrate, butyl stearate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, γ-butyrolactone, diethyl malonate, etc. Ester solvents; diethyl ether, dipropyl ether, dibutyl ether, dioxane, tetrahydrofuran Ether-based solvents such as N,N-dimethylacetamide, N-methylpyrrolidone and other amide-based solvents; Acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, isophorone, acetophenone Ketone-based solvents such as: ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl-1,3-butylene glycol acetate and other acetate-based solvents; dimethyl carbonate, diethyl carbonate and other carbonate-based solvents organic solvent. All of these can be used singly or in combination of two or more.

In addition to the ester-based solvents, ether-based solvents, amide-based solvents, ketone-based solvents, acetate-based solvents, and carbonate-based solvents, n-hexane, 2-methylpentane, n-heptane, n-octane, 2, Aliphatic hydrocarbon solvents such as 2,3-trimethylpentane, 2,2,4-trimethylpentane, n-nonane, 2,2,5-trimethylhexane, n-decane and n-dodecane; cycloaliphatic solvents such as cyclohexane Aromatic hydrocarbon solvents such as xylene, ethylbenzene, trimethylbenzene, isopropylbenzene, butylbenzene, diethylbenzene, pentylbenzene, dipentylbenzene, cyclohexylbenzene, naphthalene, tetralin, and biphenyl, petroleum naphtha, coal tar naphtha , an organic solvent such as solvent naphtha can be used in combination. All of these can be used singly or in combination of two or more.

Of these, ester-based solvents, ether-based solvents, ketone-based solvents, and carbonate-based organic solvents are preferred because of their excellent miscibility with water and solubility with curing catalysts. More preferred are an ester-based organic solvent having 2 to 10 carbon atoms, a ketone-based organic solvent having 2 to 10 carbon atoms, and a carbonate-based organic solvent having 2 to 10 carbon atoms. In addition, because of the excellent volatility after applying the surface treatment agent by coating or spraying, etc., ester organic solvents with 2 to 6 carbon atoms, ketone organic solvents with 2 to 6 carbon atoms, and 2 carbon atoms. A carbonate-based organic solvent of ∼6 is particularly preferred.

The amount of the organic solvent is not particularly limited as long as it is in the range of 50 to 99% by mass of the total amount of the surface treatment agent. Especially preferred.

Next, water will be explained. The water mixed in the surface treatment agent of the present invention is used in combination with the curing catalyst described later, so that after the surface treatment agent is applied to the surface of the base material by means such as coating or spraying, the surface treatment agent is applied to the surface. By applying the moisture-curable composition to the surface of the material by means such as coating, the curing speed of the applied moisture-curable composition can be improved. In addition, a surface treatment agent is applied to the surface of the base material or the member (for example, the finishing material) by means of coating or spraying, and the base material and the member (for example, the finishing material) are applied via the moisture-curable composition. By laminating them together, the adhesiveness between the base material, the moisture-curable composition, and the member can be improved.

Water can be used without particular restrictions. Specifically, tap water, underground water, distilled water, ion-exchanged water and the like can be mentioned.

The amount of water to be blended is not particularly limited as long as it is in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the organic solvent, but is preferably 0.1 to 3 parts by mass, and 0.1 to 1 part by mass. More preferably, 0.1 to 0.7 parts by mass is particularly preferable.

Next, the curing catalyst will be explained. Curing catalysts to be blended in the surface treatment agent of the present invention include those containing metal catalysts and amine catalysts.

Specific examples of metal catalysts include organic tin compounds, organic bismuth compounds, organic zirconium compounds, organic zinc compounds, organic iron compounds, organic manganese compounds, organic aluminum compounds, organic copper compounds, and organic titanium compounds. . All of these can be used singly or in combination of two or more.

Examples of organic tin compounds include salts of tin and organic acids such as tin octoate, tin neodecanoate, tin stearate, and tin naphthenate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dineodecanate, dibutyltin distearate, and dibutyltin. Salts of organic tin and organic acids such as dioctate, dioctyltin dilaurate, dioctyltin distearate, dioctyltin diacetate, dioctyltin dineodecanate, and tin chelate compounds such as dibutyltin bis(acetylacetonate). All of these can be used singly or in combination of two or more.

Organic bismuth compounds include salts of bismuth and organic acids such as bismuth octylate and bismuth neodecanoate, bismuth triacetate, bismuth tripropionate, bismuth triheptanate, bismuth tris (2-ethylhexanoate), bismuth tris ( neodecanate), bismuth trilaurate, bismuth trioleate, bismuth tristearate and the like. All of these can be used singly or in combination of two or more.

Organic zirconium compounds include salts of zirconium and organic acids such as zirconium octoate and zirconium naphthenate, and zirconium chelate compounds such as zirconium tetrakis (acetylacetonate). All of these can be used singly or in combination of two or more.

Examples of organic zinc compounds include salts of zinc and organic acids such as zinc octylate and zinc naphthenate, and zinc chelate compounds such as zinc bis(acetylacetonate). All of these can be used singly or in combination of two or more.

Organic iron compounds include salts of iron and organic acids such as iron octylate and iron naphthenate, and iron chelate compounds such as ferric tris (acetylacetonate). All of these can be used singly or in combination of two or more.

Organic manganese compounds include salts of manganese with organic acids such as manganese octylate and manganese naphthenate, and manganese chelate compounds such as manganese bis(acetylacetonate). All of these can be used singly or in combination of two or more.

Examples of organic aluminum compounds include aluminum chelate compounds such as aluminum tris(acetylacetonate).

Examples of organic copper compounds include acetylacetone copper and the like.

Examples of organic titanium compounds include titanium chelate compounds such as titanium tetrakis (acetylacetonate).

Of these, organic tin compounds, organic bismuth compounds, organic iron compounds, and organic zinc compounds are preferred, and organic tin compounds, organic bismuth compounds, and organic iron compounds are particularly preferred, since they further improve the curing speed of the moisture-curable composition. preferable.

As the amine catalyst, a tertiary amine compound is preferred because it further improves the curing speed of the moisture-curable composition. Tertiary amine compounds include triethylamine, tributylamine, triethylenediamine, hexamethylenetetramine, dimethyldecylamine, dimethyllaurylamine, dimethylmistyrylamine, dimethylpalmitylamine, dimethylstearylamine, dimethylbehenylamine, dilaurylmonomethylamine, trioctylamine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1,4-diazabicyclo[2,2,2]octane (DABCO), N-methylmorpholine, N-ethylmorpholine, N,N-dimethylbenzylamine, tetramethylpropanediamine, 1-isobutyl-2-methyl-1H-imidazole, N,N,N',N',-tetramethylhexanediamine, N,N,N',N' ,-tetramethylethylenediamine and the like. All of these can be used singly or in combination of two or more.

The amount of the curing catalyst is not particularly limited as long as it is in the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of the above organic solvent, but is preferably 1 to 8 parts by mass, particularly 2 to 6 parts by mass. preferable.

The mixing ratio of the metal catalyst and the amine catalyst is not particularly limited, but the weight ratio (metal catalyst/amine catalyst) is preferably 0.2 to 5, particularly preferably 0.5 to 2.

The surface treatment agent of the present invention may further contain an antifoaming agent, if desired. By blending the antifoaming agent, it is possible to reduce the foam generated when the surface treatment agent is applied to the surface of the base material, the moisture-curable composition, or the member by coating or spraying. Antifoaming agents include silicone antifoaming agents, mineral oil antifoaming agents, polymer antifoaming agents and the like. All of these can be used singly or in combination of two or more. The amount of the antifoaming agent is not particularly limited, but is preferably 0.01 to 5% by mass based on the total amount of the surface treatment agent.

The surface treatment agent of the present invention may further contain a surface conditioner (leveling agent), if necessary. By blending the surface conditioner, it is possible to improve the wettability when applying the surface treatment agent to the surface of the base material, the moisture-curable composition, or the member by coating or spraying. Examples of surface conditioners include silicone surface conditioners, acrylic surface conditioners, and fluorine-based surface conditioners. All of these can be used singly or in combination of two or more. The amount of the surface conditioner to be blended is not particularly limited, but is preferably 0.01 to 5% by mass based on the total amount of the surface treatment agent.

As a method for preparing the surface treatment agent, conventionally known methods can be used without particular limitation. Specifically, a mixing vessel made of glass, stainless steel, or the like is charged with an organic solvent, water, a curing catalyst, and optional ingredients such as an antifoaming agent and a surface conditioner as necessary, and stirred to form a uniform mixture. is mentioned. The order of charging each raw material can be arbitrarily set. In addition, each raw material can be charged all at once or sequentially.

Next, the moisture-curable composition to be applied to the surface of the base material to which the base treatment agent of the present invention has been applied will be described. A moisture-curable composition is a composition containing a curable resin that cures by reacting with water such as moisture. The moisture-curable composition can be used as an adhesive composition, a sealant composition, a waterproof material composition, a coating material composition, and the like. Moisture-curable compositions include urethane-based moisture-curable compositions, modified silicone-based moisture-curable compositions, and the like.

A urethane-based moisture-curable composition is a composition containing an isocyanate group-containing resin as a curable resin. As the isocyanate group-containing resin, an isocyanate group-containing urethane prepolymer (hereinafter sometimes simply referred to as "urethane prepolymer") can be preferably used.

The isocyanate group-containing urethane prepolymer is prepared by charging the isocyanate group of the organic isocyanate compound in batches or sequentially so that the isocyanate group is excessive with respect to the active hydrogen (group) of the active hydrogen-containing compound, and the charged organic isocyanate compound and the active hydrogen It can be obtained by reacting with a contained compound. The molar ratio (isocyanate group/active hydrogen) of the isocyanate group of the organic isocyanate compound to the active hydrogen (group) of the active hydrogen-containing compound (isocyanate group/active hydrogen) prevents excessive viscosity increase of the urethane prepolymer while preventing the isocyanate group from being exposed to water such as moisture. It is preferably from 1.2 to 10, particularly preferably from 1.2 to 5, from the viewpoint of suppressing the amount of carbon dioxide generated during the reaction and preventing foaming during curing.

In addition, the isocyanate group content in the isocyanate group-containing urethane prepolymer prevents an excessive increase in the viscosity of the urethane prepolymer, while suppressing the amount of carbon dioxide generated when the isocyanate group reacts with water such as moisture. 0.3 to 15% by mass is preferable, and 0.5 to 5% by mass is particularly preferable, from the viewpoint of preventing foaming during curing.

As a method for producing an isocyanate group-containing urethane prepolymer, an organic isocyanate compound and an active hydrogen-containing compound are charged in a reaction vessel made of glass, stainless steel, or the like, and if necessary, a reaction catalyst or an organic solvent is further added. A method of reacting while stirring at 120° C. may be mentioned. At this time, if the isocyanate group reacts with water such as moisture, the reaction product, urethane prepolymer, may thicken. It is preferable to carry out the above reaction at.

An organic polyisocyanate can be mentioned as an organic isocyanate compound. An organic polyisocyanate is a compound having two or more isocyanate groups in one molecule. Specific examples include toluene polyisocyanates such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate; Polyisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4,6-trimethylphenyl-1,3-diisocyanate, 2,4,6-triisopropylphenyl-1 phenylene polyisocyanates such as ,3-diisocyanate, naphthalene polyisocyanates such as 1,4-naphthalene diisocyanate and 1,5-naphthalene diisocyanate, chlorophenylene-2,4-diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3' aromatic polyisocyanates such as -dimethyldiphenylmethane-4,4'-diisocyanate and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate. In addition, 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl- Aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, decamethylene diisocyanate and lysine diisocyanate, araliphatic polyisocyanates such as o-xylylene diisocyanate, m-xylylene diisocyanate and p-xylylene diisocyanate, 1,4- Alicyclic polyisocyanates such as cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate can be mentioned. Furthermore, polymeric isocyanates such as polymethylene polyphenyl polyisocyanate and crude toluene diisocyanate are included. As the organic polyisocyanate, a uretdione bond, an isocyanurate bond, an allophanate bond, a burette bond, a uretonimine bond, a carbodiimide bond, a urethane bond or a urea bond obtained by modifying the above-described various organic polyisocyanates is contained in one molecule. Examples include modified organic polyisocyanates having one or more. All of these can be used singly or in combination of two or more.

Organic monoisocyanates can also be used together with the various organic polyisocyanates described above. That is, a mixture of organic polyisocyanate and organic monoisocyanate can be used as the organic isocyanate compound. An organic monoisocyanate is a compound having one isocyanate group in one molecule. Specific examples include n-butyl monoisocyanate, n-hexyl monoisocyanate, n-hexadecyl monoisocyanate, n-octadecyl monoisocyanate, p-isopropylphenyl monoisocyanate and p-benzyloxyphenyl monoisocyanate.

An active hydrogen-containing compound is a compound having one or more active hydrogens (groups) in one molecule. Specific examples include high-molecular polyols, low-molecular-weight polyols, high-molecular-weight polyamines, low-molecular-weight polyamines, high-molecular-weight aminoalcohols, low-molecular-weight aminoalcohols, high-molecular-weight monools, and low-molecular-weight monools. All of these can be used singly or in combination of two or more. Here, the "polymer" of the active hydrogen-containing compound is a compound having a number average molecular weight of 1,000 or more, and the "low molecule" of the active hydrogen-containing compound is a compound having a number average molecular weight of less than 1,000. is. Moreover, the number average molecular weight in the present invention is a value converted to polystyrene by GPC (gel permeation chromatography) measurement.

Examples of polymer polyols include polyester polyols, polycarbonate polyols, polyoxyalkylene polyols, hydrocarbon polyols, poly(meth)acrylate polyols, and animal and plant polyols. All of these can be used singly or in combination of two or more. In addition, in this invention, the said "(meth)acrylate" means "acrylate and/or methacrylate." The number average molecular weight of the polymer polyol is not particularly limited as long as it is 1,000 or more, but 1,000 to 20,000 is preferable.

Polyester polyols include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, and trimellitic acid. and one or more carboxylic acids including polycarboxylic acids, anhydrides of the above polycarboxylic acids, or alkyl esters such as methyl esters and ethyl esters, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1 , 2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1 ,8-octanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide adducts of bisphenol A, trimethylolpropane, glycerin, pentaerythritol, etc. Included are polyester polyols obtained by reaction with one or more of the polyols.

Examples of polycarbonate polyols include polycarbonate polyols obtained by dehydrochlorination reaction of low-molecular-weight polyols used in the synthesis of polyester polyols and phosgene, low-molecular-weight polyols described above and diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like. Polycarbonate polyol obtained by transesterification with.

Polyoxyalkylene-based polyols include low-molecular-weight polyols, low-molecular-weight polyamines, low-molecular-weight aminoalcohols, polycarboxylic acids, sorbitol, mannitol, sucrose (sucrose), glucose, etc., which are used in the synthesis of the polyester polyols described above. saccharide-based low-molecular-weight polyhydric alcohols; using one or more low-molecular-weight polyhydric phenols such as bisphenol A and bisphenol F as an initiator, and one or more cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran Polyoxyethylene-based polyol, polyoxypropylene-based polyol, polyoxybutylene-based polyol, poly Oxytetramethylene-based polyols, poly-(oxyethylene)-(oxypropylene)-random copolymer-based polyols, poly-(oxyethylene)-(oxypropylene)-block copolymer-based polyols, and the polyester polyols described above as initiators Polycarbonate ether polyols obtained by using the above-described polycarbonate polyols as initiators, and the like. In addition, polyols having hydroxyl groups at the molecular ends by reacting the hydroxyl groups of the various polyols described above with the isocyanate groups of the organic isocyanate compound in an excess of hydroxyl groups are also included.

The number of alcoholic hydroxyl groups of the polyoxyalkylene-based polyol is not particularly limited as long as it averages 2 or more per molecule, but preferably 2 to 4 per molecule, and 2 to 3 per molecule. is particularly preferred.

In addition to polyoxyalkylene-based polyols, for modifying urethane prepolymers, low-molecular-weight monoalcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol are used as initiators to open ring-opening compounds of cyclic ether compounds such as propylene oxide described above. Addition-polymerized polyoxyalkylene monools such as polyoxypropylene monools can also be used.

Regarding the polyol component, which is the raw material of the urethane prepolymer, the "system" in the above-mentioned polyoxyalkylene-based polyols, polyoxyalkylene-based monools, etc. means 50% by mass or more of the portion excluding hydroxyl groups in 1 mol of the molecule. is composed of a main component such as polyoxyalkylene, the remaining part is a component other than the main component such as polyoxyalkylene (e.g., ester, urethane, polycarbonate, polyamide, poly (meth) acrylate, polyolefin, etc.) It means that it may be denatured with The main component such as polyoxyalkylene accounts for preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more of the portion excluding hydroxyl groups.

Hydrocarbon-based polyols include polyolefin polyols such as polybutadiene polyol and polyisoprene polyol; polyalkylene polyols such as hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol; and halogenated polyalkylene polyols such as chlorinated polypropylene polyol and chlorinated polyethylene polyol. etc.

Poly(meth)acrylate-based polyols include (meth)acrylate monomers having hydroxyl groups such as hydroxyethyl (meth)acrylate and other acrylic acid and/or methacrylic acid (hereinafter referred to as "(meth)acrylic acid"). ) and an alkyl ester monomer, optionally using a radical polymerization initiator, and the like.

Animal and plant polyols include castor oil polyols and silk fibroin.

Among the various active hydrogen-containing compounds described above, polymer polyols are preferred in terms of improving the curing speed of the moisture-curable composition and the adhesiveness between the base material, the moisture-curable composition and the member. Among the polymer polyols, poly Oxyalkylene-based polyols and poly(meth)acrylate-based polyols are more preferable, and polyoxyalkylene-based polyols are particularly preferable.

A urethane-based moisture-curable composition contains, in addition to an isocyanate group-containing urethane prepolymer, a compound that reacts with water to generate active hydrogen (group) (hereinafter referred to as a "latent curing agent"). There is.) can also be blended. When the isocyanate group-containing urethane prepolymer comes into contact with water such as moisture, the isocyanate groups of the isocyanate group-containing urethane prepolymer react with water to form urea bonds and cure. During the reaction to form the urea bond, carbon dioxide gas is generated, and the carbon dioxide gas causes foaming in the cured product. On the other hand, when a latent curing agent is added to the isocyanate group-containing urethane prepolymer, the latent curing agent reacts with water before the isocyanate group of the isocyanate group-containing urethane prepolymer reacts with water to generate carbon dioxide gas. to generate active hydrogen (groups) such as alcoholic hydroxyl groups, primary amino groups, and secondary amino groups. The active hydrogen (group) generated from this latent curing agent reacts preferentially with the isocyanate group of the isocyanate group-containing urethane prepolymer over water to crosslink and cure. For this reason, the moisture-curable composition cures while reducing foaming due to carbon dioxide gas, resulting in a cured product with good appearance and adhesiveness.

Specific examples of latent curing agents include silicate esters of polyols, ketimine compounds, aldimine compounds, and oxazolidine compounds, which are compounds having primary and/or secondary amino groups. Among these, silicate esters of polyols and oxazolidine compounds are preferable from the viewpoint of storage stability and antifoaming properties of the moisture-curable composition.

A modified silicone moisture-curable composition is a composition containing a hydrolyzable silyl group-containing resin as a curable resin. The hydrolyzable silyl group-containing resin is crosslinked and cured by reacting the hydrolyzable silyl group with water such as moisture to form a siloxane bond.

Specifically, the modified silicone resin contains one or more hydrolyzable silyl groups in one molecule, and the main chain is a polyoxyalkylene-based polymer, a vinyl-modified polyoxyalkylene-based polymer, or a vinyl-based polymer. Examples thereof include coalescence, diene polymers such as polyisoprene and polybutanediene, polyester polymers, and (meth)acrylic acid ester polymers. As the main chain of the modified silicone resin, polyoxyalkylene polymers and vinyl-modified polyoxyalkylene polymers are preferable, and polyoxypropylene-based polymers and (meth)acrylic-modified polyoxypropylene-based polymers are particularly preferable.

Although the number of hydrolyzable silyl groups is not particularly limited, it preferably contains 1 to 4 groups, particularly preferably 1.5 to 3 groups, on average per molecule. The number average molecular weight of the modified silicone resin is not particularly limited, but is preferably 1,000 or more, particularly preferably 6,000 to 30,000.

Moreover, the hydrolyzable silyl group preferably has a structure represented by the following general formula (1) from the viewpoints of ease of cross-linking curing and productivity.

(In the formula, R is a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and particularly preferably a methyl group. X is a reaction selected from the group consisting of a halogen atom, a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, a mercapto group, an alkenyloxy group and an aminooxy group, wherein X is plural In the case of , X may be the same group or different groups, wherein X is preferably an alkoxy group, particularly preferably a methoxy group or an ethoxy group, a is an integer of 0, 1 or 2 and preferably 0 or 1.)

In addition to the curable resin and latent curing agent described above, the moisture-curable composition to be applied to the surface of the base material to which the base treatment agent of the present invention has been applied may optionally contain various additives. can be blended. Additives are blended in order to further improve various performances such as acceleration of curing and adhesiveness of the moisture-curable composition. Specific examples include curing acceleration catalysts, plasticizers, weather stabilizers, fillers, thixotropic agents, adhesion improvers, storage stability improvers (dehydrating agents), colorants, organic solvents, and the like. can. All of these can be used singly or in combination of two or more.

Curing acceleration catalysts are used to accelerate the cross-linking curing of the curable resin of the moisture-curable composition by reacting with active hydrogen-containing compounds (and/or water such as moisture). As the curing acceleration catalyst, the above curing catalyst that can be blended in the surface treatment agent of the present invention can be used.

The plasticizer is used to reduce the viscosity of the moisture-curable composition to improve workability, and to adjust rubber physical properties such as tensile stress and elongation after curing of the moisture-curable composition. Plasticizers include low molecular weight plasticizers with a number average molecular weight of less than 1,000 and high molecular weight plasticizers with a number average molecular weight of 1,000 or more. Low molecular weight plasticizers include phthalates such as dioctyl phthalate, diisononyl phthalate, dibutyl phthalate and butyl benzyl phthalate; aliphatic compounds such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate and butyl oleate carboxylic acid esters; phosphate esters such as trioctyl phosphate and tricresyl phosphate; and chlorinated paraffin. Examples of high-molecular-weight plasticizers include polyester resins made from dicarboxylic acids and glycols; alkyl-etherified derivatives and alkyl-esterified derivatives of polyoxyalkylene glycol such as polyoxyethylene glycol and polyoxypropylene glycol; A liquid polymer having no isocyanate group or active hydrogen group in the molecule, obtained by reacting the polyoxyalkylene polyol or polyoxyalkylene monool mentioned in the synthesis of the urethane prepolymer with an organic monoisocyanate or an organic polyisocyanate. urethane-based plasticizers; low-viscosity (meth)acrylic acid alkyl ester (co)polymer resins; polyolefin resins such as polybutadiene and polyisoprene; and polyalkylene resins such as hydrogenated polybutadiene and hydrogenated polyisoprene.

Weather stabilizers are used to prevent oxidation, light deterioration, and heat deterioration of the moisture-curable composition and improve weather resistance and heat resistance. Examples of light stabilizers include hindered amine light stabilizers, hindered phenol antioxidants, and ultraviolet absorbers.

A filler is used to increase the weight of the moisture-curable composition and to reinforce the physical properties of the cured product. Fillers include mica, kaolin, zeolite, graphite, diatomaceous earth, clay, clay, talc, slate powder, silicic anhydride, fine quartz powder, aluminum powder, zinc powder, synthetic silica such as precipitated silica, calcium carbonate, and carbonate. inorganic powdery fillers such as magnesium, alumina, calcium oxide and magnesium oxide; fibrous fillers such as glass fiber and carbon fiber; inorganic balloon fillers such as glass balloons, Shirasu balloons, silica balloons and ceramic balloons; Inorganic filler; Filler obtained by treating the surface of the above inorganic filler with an organic substance such as fatty acid; Wood flour, walnut flour, rice husk powder, pulp powder, cotton chips, rubber powder, fine powder of thermoplastic resin, Thermosetting resin fine powder, organic powder filler such as polyethylene powder; organic filler such as polyethylene hollow body, organic balloon filler such as saran microballoon, magnesium hydroxide, aluminum hydroxide, etc. Flame-retardant-imparting fillers may be mentioned.

The thixotropic agent is used to prevent sagging (slump) of the moisture-curable composition and to maintain the applied shape. Examples of thixotropic agents include inorganic thixotropic agents such as finely divided silica and fatty acid-treated calcium carbonate; and organic thixotropic agents such as organic bentonite and fatty acid amides.

The adhesion improver is used to further improve the adhesion of the moisture-curable composition to the base material and/or the member when bonding the base material and the member via the moisture-curable composition. Adhesion improvers include coupling agents. Examples of the coupling agent include various coupling agents such as silane-based, aluminum-based, and zirco-aluminate-based coupling agents, and partial hydrolysis condensates thereof.

A storage stability improver (dehydrating agent) is used to improve the storage stability of a moisture-curable composition by reducing the amount of water in the moisture-curable composition. Examples of storage stability improvers include vinyltrimethoxysilane, calcium oxide, and p-toluenesulfonyl isocyanate, which can reduce the amount of water in the moisture-curable composition by reacting with moisture present in the moisture-curable composition. mentioned.

The colorant is used to color the moisture-curable composition and impart a design to the cured product. The coloring agent can be appropriately selected depending on the desired color, and examples thereof include inorganic pigments such as carbon black, titanium oxide and iron oxide, and organic pigments such as copper phthalocyanine.

The organic solvent is used to adjust the viscosity of the moisture-curable composition to improve the extrudability and workability during placement and coating. Any organic solvent can be used without particular limitation as long as it has good compatibility with other components in the moisture-curable composition and does not react with other components. Specifically, carbonate solvents such as dimethyl carbonate, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate and butyl acetate, aliphatic solvents such as n-hexane, and alicyclic solvents such as cyclohexane. Examples include solvents, aromatic solvents such as toluene and xylene, and organic solvents such as petroleum fraction solvents such as mineral spirits and industrial gasoline.

Next, a bonding method using the surface treatment agent of the present invention will be described. The bonding method using the surface treatment agent of the present invention contains an organic solvent, water and a curing catalyst, the amount of the organic solvent is 50 to 99% by weight of the total, and the amount of water is 100 parts by weight of the organic solvent. 0.1 to 5 parts by mass of a surface treatment agent containing 0.5 to 10 parts by mass of a curing catalyst per 100 parts by mass of an organic solvent is applied or sprayed onto the surface of the base material to be adhered. A step of applying at, a step of applying a moisture-curable composition to the surface of the substrate to which the surface treatment agent has been applied by means of coating, etc., through the moisture-curable composition, the substrate and It is an adhesion method including a step of bonding a member to be another adherend. By the above bonding method, the base material, which is an adherend, is adhered to a member, which is another adherend, via the moisture-curable composition.

First, the step of applying the surface treatment agent of the present invention to the surface of the base material by means of coating, spraying, or the like will be described in detail. The surface treatment agent of the present invention is applied by coating or spraying on the surface of the base material (surface to be adhered) in contact with the moisture-curable composition. As a method of coating or spraying, a conventionally known method can be used. Specific examples include a method of coating or spraying using tools such as a brush, felt, sponge, spatula, roller, spray gun, air brush, and aerosol spray. The coating amount of the surface treatment agent is not particularly limited as long as it does not impair the objects of the present invention, but is preferably 20 to 500 g/m ² , particularly preferably 20 to 300 g/m ² . A curing sheet or curing tape may be used in advance so as not to apply or spray the surface treatment agent to unnecessary areas. The surface treatment agent of the present invention does not require an open time (drying time) unlike conventionally known primers for surface treatment, so that the working time can be shortened.

Next, the step of applying the moisture-curable composition to the surface of the base material by means of coating or the like will be described in detail. After applying the surface treatment agent of the present invention to the surface of the base material (adherence surface), the moisture-curable composition is applied to the coated surface by coating or the like. That is, a layer of a surface treatment agent and a layer of a moisture-curable composition are laminated on the surface of the base material (adherence surface). As a method for applying the moisture-curable composition, a conventionally known method can be used. Specifically, the moisture-curable composition is taken out from a container such as a cartridge, bag, can, or the like filled and sealed with the moisture-curable composition, and applied to the coating surface of the base material. If necessary, tools such as a brush, a spatula, a trowel, and a roller can be used to adjust the coating amount of the moisture-curable composition and smooth the coated surface. The coating amount of the moisture-curable composition is not particularly limited as long as it does not impair the objects of the present invention, but is preferably 100 to 1,000 g/m ² , particularly preferably 200 to 800 g/m ² .

Next, the step of bonding the base material and the member together via the moisture-curable composition will be described in detail. After applying the surface treatment agent and moisture-curable composition of the present invention to the surface of the substrate (adherence surface), various members (for example, finishing materials) are laminated to the moisture-curable composition, and if necessary clamp or secure. Here, if necessary, the surface of the moisture-curable composition facing various members (eg, finishing material, etc.) before bonding various members (eg, finishing material, etc.) to the moisture-curable composition And/or the surface (adherence surface) of various members (eg, finishing material, etc.) may be previously applied (eg, by coating, spraying, etc.) with the surface treatment agent of the present invention. That is, the surface treatment agent is applied not only between the base material and the moisture-curable composition, but also between the moisture-curable composition and various members (for example, finishing materials, etc.). It may be applied (for example, coating by painting, spraying, etc.). By applying a surface treatment agent between the moisture-curable composition and various members (for example, finishing materials, etc.), the curing speed of the moisture-curable composition is further increased, and the curing of the moisture-curable composition is improved. Time can be shortened. In addition, by applying a surface treatment agent between the moisture-curable composition and various members (for example, finishing materials), the substrate, the moisture-curable composition, and various members (for example, finishing materials) etc.) can be further improved, leading to a further improvement in the adhesion reliability of the joint.

As the base material to which the base treatment agent of the present invention is applied (coated or sprayed, etc.), any known base material can be used without particular limitation as long as the problems of the present invention can be solved. Specifically, inorganic materials such as mortar, concrete, slate, plaster, ALC (Autoclaved Lightweight Concrete), glass, marble, granite, siding, tiles, roof tiles, bricks; iron, copper, stainless steel, steel, tin, aluminum, Synthetic resin organic materials such as metallic materials such as titanium, (meth) acrylic resins, polyester resins, polycarbonate resins, vinyl chloride resins, polystyrene resins, ABS (Acrylonitrile-Butadiene-Styrene copolymer), FRP (Fiber Reinforced Plastic); Wooden materials such as solid wood, plywood and laminated wood can be mentioned. Among these, mortar, concrete, slate, iron, steel, aluminum, vinyl chloride resin, solid wood, plywood, and laminated wood are preferred because of their good adhesion to the moisture-curable composition. The base material to which the base treatment agent of the present invention is applied can be used for bonding with any member via the moisture-curable composition. That is, the base material, which is an adherend, may be the same member as various members (for example, finishing materials, etc.), which are other adherends, or may be a different member. In addition, the surface treatment agent of the present invention can improve not only the base material but also the adhesion between various members (for example, finishing materials, etc.) and the moisture-curable composition, so its use is limited to the base material treatment. It can be widely used for bonding various members and moisture-curable compositions. As described above, the surface treatment agent of the present invention has a wide range of applications because it can be used when various members are joined together via the moisture-curable composition.

Examples of the present invention will now be described, but the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.

[Preparation Example 1]
A mixing vessel equipped with a stirrer was charged with 1,000 g of ethyl acetate and 5 g of distilled water, and while stirring, 20 g of an organic tin compound (dibutyltin dilaurate, Neostan U-100, manufactured by Nitto Kasei Co., Ltd.), which is a metal catalyst, was mixed with an amine catalyst. 20 g of a certain tertiary amine compound (N,N,N',N'-tetramethylhexanediamine, Kaolizer No. 1, manufactured by Kao Corporation) was charged and stirred at room temperature for 1 hour to prepare a surface treatment agent.

[Example 1]
The ground treatment agent of Preparation Example 1 was used.

[Comparative Example 1]
No primer was used.

[Comparative Example 2]
Distilled water was used in place of the surface treatment agent in Preparation Example 1.

<Test method>
After the surface treatment with the surface treatment agents of Example 1 and Comparative Example 2 (the surface treatment with the surface treatment agent was not performed in Comparative Example 1), the following adhesion test was performed. Table 1 summarizes the compositions and test results of Example 1 and Comparative Examples 1 and 2.

[Adhesion test]
<Substrate: Anodized aluminum>
Normal care
Alumite aluminum A with a length of 30 mm × width of 25 mm × thickness of 10 mm was prepared, and the surface treatment agent of Preparation Example 1 (Example 1) or distilled water (Comparative example 2) was applied at about 100 g/m ² . Next, without taking open time, a urethane moisture-curable composition (product name: Orton Adher 777, urethane resin 30-40 wt%, inorganic filler 50-60 wt%, high boiling point hydrocarbon 1 to 10 wt %, manufactured by Auto Kagaku Kogyo Co., Ltd.) was applied to about 500 g/m ² .
Alumite aluminum B with a length of 30 mm × width of 25 mm × thickness of 10 mm is prepared, and the surface treatment agent of Preparation Example 1 (Example 1) or distilled water (Comparative example 2) was applied at about 100 g/m ² . Next, the coated surface of anodized aluminum B was adhered and fixed to the urethane-based moisture-curable composition on the coated surface of anodized aluminum A without taking an open time to prepare a test specimen. Also, as Comparative Example 1, a test piece was prepared in which the adherend was alumite aluminum in the same manner as in Example 1, except that the surface treatment agent was not applied. The shape of the specimen conformed to JIS K 6852 (1994): Test method for compressive shear strength of adhesives, 6.3 Preparation of test piece. The specimens were cured at 23° C. and 50% RH for 8 hours, 16 hours, 24 hours, and 48 hours, which was defined as normal curing.

A test specimen similar to that for low- temperature curing and normal curing was prepared. The specimens were cured at 0° C. for 24 hours and 96 hours, which was referred to as low-temperature curing.

<Substrate: hard PVC>
Low temperature curing
Prepare a hard vinyl chloride A with a length of 30 mm × width of 25 mm × thickness of 5 mm, and apply the surface treatment agent of Preparation Example 1 (Example 1) or distilled water (Comparative example 2) was applied at about 100 g/m ² . Next, a urethane moisture-curable composition (product name: Orton Adher 777, urethane resin 30-40 wt%, inorganic filler 50-60 wt%, high boiling point hydrocarbon 1 to 10 wt %, manufactured by Auto Kagaku Kogyo Co., Ltd.) was applied to about 500 g/m ² .
Prepare hard PVC B with a length of 30 mm × width of 25 mm × thickness of 5 mm, and apply the surface treatment agent of Preparation Example 1 (Example 1) or distilled water (Comparative Example 2) was applied at about 100 g/m ² . Next, without taking an open time, the coated surface of hard vinyl chloride B was adhered to the urethane-based moisture-curable composition on the coated surface of hard vinyl chloride A and fixed to prepare a test specimen. Also, as Comparative Example 1, a test specimen was prepared in which the adherend was rigid PVC in the same manner as in Example 1, except that the surface treatment agent was not applied. The shape of the specimen conformed to JIS K 6852 (1994): Test method for compressive shear strength of adhesives, 6.3 Preparation of test piece. The specimens were cured at 0° C. for 24 hours and 96 hours, which was referred to as low-temperature curing.

Adhesive strength Test specimens under normal and low temperature curing were measured for adhesive strength during compressive shearing according to JIS K 6852 (1994) Test method for compressive shearing adhesive strength of adhesives, "8. Operation".

Adhesive Failure Status Visually observe the failure status (fracture surface) of the test piece during compression shearing, and when the cohesive failure rate of the moisture-curable composition is 75% or more, ○, and the cohesive failure rate of the moisture-curable composition is A case of 50% or more and less than 75% was evaluated as Δ, and a case where the cohesive failure rate of the moisture-curable composition was less than 50% was evaluated as x.
CF: cohesive failure of the moisture-curable composition (CF100 has a cohesive failure rate of the moisture-curable composition of 100% (i.e., the interfacial peeling rate of the adherend and the moisture-curable composition described below is 0%))
AF: interfacial peeling of adherend and moisture-curable composition (AF100 has an adherend-humidity-curable composition interfacial peeling rate of 100% (i.e., CF0))

From the results in Table 1, in Example 1 using the surface treatment agent of Preparation Example 1, curing at 23° C., 50% RH and 0° C. was accelerated, and the curing time could be shortened. Further, in Example 1, the state of adhesion failure (visual observation) is not interfacial peeling between the adherend and the adhesive, but cohesive failure of the moisture-curable composition. It was found that the adhesion was improved. Furthermore, in Example 1, it was found that there was no need to take an open time (drying time) after applying the surface treatment agent, and the workability was excellent.

On the other hand, in Comparative Example 1, in which the surface treatment agent was not applied, curing was slower than in Example 1 in normal curing and low-temperature curing. I didn't. Moreover, in Comparative Example 1, the adhesion failure (visual observation) was interfacial peeling between the adherend and the moisture-curable composition, and good adhesion between the adherend and the moisture-curable composition was not obtained. In Comparative Example 2, in which distilled water was applied in anticipation of a curing acceleration effect, the distilled water was repelled by the surfaces of the aluminum and hard PVC, and the distilled water could not be applied uniformly. could not do

The surface treatment agent of the present invention can improve the adhesiveness between the base material and the moisture-curable composition, and can also accelerate the curing of the moisture-curable composition. Since the surface treatment agent of the present invention exhibits the excellent effects as described above, it can be suitably used for construction and civil engineering. In particular, it can be suitably used as a surface treatment agent when applying a moisture-curable composition to the surface of a base material.

Claims (9)

A surface treatment agent containing an organic solvent, water and a curing catalyst,
The compounding amount of the organic solvent is 50 to 99% by mass of the entire surface treatment agent, the compounding amount of the water is 0.1 to 5 parts by mass with respect to 100 parts by mass of the organic solvent, and the compounding amount of the curing catalyst is the organic solvent. A surface treatment agent for a moisture-curable composition, which is 0.5 to 10 parts by mass per 100 parts by mass of a solvent. 2. The surface treatment agent according to claim 1, wherein the organic solvent is at least one selected from the group consisting of ester solvents, ether solvents, ketone solvents and carbonate solvents. 3. The surface treatment agent according to claim 1, wherein the curing catalyst contains a metal catalyst and an amine catalyst. 4. The surface treatment agent according to claim 3, wherein the metal catalyst contains an organic tin compound. 5. The surface treatment agent according to claim 3, wherein the amine catalyst contains a tertiary amine compound. The surface treatment agent according to any one of claims 1 to 5 , wherein the moisture-curable composition contains an isocyanate group-containing resin and/or a hydrolyzable silyl group-containing resin. The surface treatment agent according to any one of claims 1 to 6, wherein the moisture-curable composition is an adhesive composition. The surface treatment agent according to any one of claims 1 to 7 , which is used for construction or civil engineering. A surface treatment agent containing an organic solvent, water, and a curing catalyst, wherein the amount of the organic solvent is 50 to 99% by mass of the surface treatment agent, and the amount of water is 100 parts by mass of the organic solvent. a step of applying to the surface of the base material a surface treatment agent having 0.1 to 5 parts by mass and a curing catalyst content of 0.5 to 10 parts by mass with respect to 100 parts by mass of the organic solvent;
A step of applying a moisture-curable composition to the surface of the base material to which the base treatment agent has been applied; and a step of bonding the base material and the member together via the moisture-curable composition.
Adhesion method.