JP2007070571A - Primer composition for sealing material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a primer composition for a sealing material to be a primer layer having excellent toughness and adhesiveness. <P>SOLUTION: The primer composition for the sealing material comprises a reaction product (A) and a solvent. The reaction product (A) is prepared by carrying out an addition reaction of a polyisocyanate compound with a secondary amine having a hydrolyzable silyl group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a primer composition for a sealing material.

  Conventionally, in the construction field, a primer has been used to improve the adhesion between a building member and a sealing material. The primer composition usually contains an adhesive component for a building member and an adhesive component for a sealing material.

  However, the inventor applied the external primer to the building material after applying a conventional primer composition and post-curing the sealing material, and then applying the force from the outside, the primer was destroyed, or the building material or the sealing material. It was found that it would peel off from the material. The inventors inferred that this is due to (1) the conventional primer is hard and has low toughness, and (2) the adhesion (adhesiveness) of the primer to the building member or sealing material is low.

  Accordingly, an object of the present invention is to provide a primer composition for a sealing material that can be a primer layer having excellent toughness and adhesion.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventor includes a reaction product obtained by addition reaction of a polyisocyanate compound and a secondary amine having a hydrolyzable silyl group, and a solvent. The present inventors have found that the primer composition for sealing materials can be a primer layer having excellent toughness and adhesion, and completed the present invention.

That is, the present invention provides the following (1) to (6).
(1) A primer composition for a sealing material containing a reaction product (A) obtainable by addition reaction of a polyisocyanate compound and a secondary amine having a hydrolyzable silyl group, and a solvent.
(2) The primer composition for a sealing material according to the above (1), wherein the addition rate of the secondary amine with respect to all isocyanate groups in the polyisocyanate compound is 10 to 100 mol%.
(3) The sealing according to (1) or (2), further comprising a reaction product (B) obtainable by addition reaction of an epoxy resin and a secondary amine having a hydrolyzable silyl group. Primer composition for materials.
(4) The primer composition for a sealing material according to any one of (1) to (3), further containing a resin.
(5) The primer composition for a sealing material according to any one of (1) to (4), further comprising a silane coupling agent.
(6) The primer composition for a sealing material according to any one of (1) to (5), further containing a catalyst.

  The primer composition for a sealing material of the present invention can be a primer layer having excellent toughness and adhesion.

The present invention is described in detail below.
The primer composition for a sealant of the present invention is
It is a primer composition for a sealing material containing a reaction product (A) obtainable by addition reaction of a polyisocyanate compound and a secondary amine having a hydrolyzable silyl group, and a solvent.

The reaction product (A) will be described below.
The reaction product (A) is a reaction product that can be obtained by addition reaction of a polyisocyanate compound and a secondary amine having a hydrolyzable silyl group.

The polyisocyanate compound will be described below.
A polyisocyanate compound has two or more isocyanate groups in one molecule.

Examples of the polyisocyanate compound include a low molecular weight polyisocyanate compound and a urethane prepolymer.
Examples of the low molecular weight polyisocyanate compound include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4′-diphenylmethane diisocyanate (4 , 4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI) ) Aromatic hydrocarbon group-containing polyisocyanates such as xylylene diisocyanate; aralkyl group-containing polyisocyanates such as xylylene diisocyanate; hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), norbornene diiso Aliphatic hydrocarbon group-containing polyisocyanates such as Aneto (NBDI) and the like. As the aliphatic hydrocarbon group-containing polyisocyanate, for example, aromatic carbonization such as dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI) obtained by hydrogenating 4,4′-MDI. Examples include hydrogenated products of hydrogen group-containing polyisocyanates and hydrogenated products of aralkyl group-containing polyisocyanates.

  As a urethane prepolymer, the reaction material of said low molecular weight polyisocyanate compound and a polyol compound is mentioned, for example. The polyol compound is not particularly limited, and examples thereof include polyether polyols such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxypropylene triol, polyester polyols, acrylic polyols, polycarbonate polyols, other polyols, and mixtures thereof. A polyol is mentioned.

  The combination of the polyol compound and polyisocyanate compound used for the urethane prepolymer is not particularly limited. For example, each of the polyol compounds and each of the above low molecular weight polyisocyanate compounds can be used in any combination. Specifically, for example, at least one selected from the group consisting of polyoxyethylene glycol, polyoxypropylene glycol, and polyoxypropylene triol, and at least selected from the group consisting of hydrogenated HDI and MDI The urethane prepolymer obtained from one kind is preferable from the viewpoint of preventing the primer layer obtainable from the primer composition for sealing material from turning yellow, cost, and availability.

  As for the mixing ratio of the polyol compound and the polyisocyanate compound used in the urethane prepolymer, the molar ratio of the isocyanate group in the polyisocyanate compound to the hydroxy group in the polyol compound (NCO / OH) is 1.3 to 2.5. And is more preferably 1.5 to 2.0. In such a range, the viscosity of the urethane prepolymer is moderate and the elongation of the cured product is excellent.

  The reaction between the polyol compound and the polyisocyanate compound when producing the urethane prepolymer is not particularly limited. For example, the method of heating and stirring the polyol compound and polyisocyanate compound of the above-mentioned quantitative ratio at 50-160 degreeC is mentioned. If necessary, for example, a urethanization catalyst such as an organic tin compound, an organic bismuth, or an amine can be used.

  The urethane prepolymer is preferably liquid at room temperature from the viewpoint of handling. In addition to the isocyanate group, the urethane prepolymer can have a group such as a hydroxy group, an acid anhydride group, an amino group, a latent amino group, a mercapto group, or a carboxy group in the molecule. When having such a group that can be cross-linked by reacting with an isocyanate group, the crosslink density of the obtained cured product is improved and the physical properties are excellent.

In a preferred embodiment, the polyisocyanate compound is an aliphatic hydrocarbon group-containing polyisocyanate from the viewpoint of preventing the primer layer obtainable from the primer composition for a sealing material from turning yellow. Examples of the aliphatic hydrocarbon group-containing polyisocyanate include low molecular weight ones and urethane prepolymers. For example, the thing similar to the above is mentioned, respectively. Among these, HDI, IPDI, hydrogenated MDI, and NBDI are preferable.
A polyisocyanate compound can be used individually or in combination of 2 types or more, respectively.

The secondary amine will be described below.
The secondary amine used in the present invention has a hydrolyzable silyl group.
The hydrolyzable silyl group is not particularly limited as long as it is a silyl group having at least one hydrolyzable group. For example, an alkoxysilyl group can be mentioned. Examples of the alkoxy group in the alkoxysilyl group include a methoxy group, an ethoxy group, and a propoxy group. The alkoxysilyl group preferably has two or more alkoxy groups from the viewpoint of excellent physical properties of the cured product.

  In the alkoxysilyl group, the group other than the alkoxy group is not particularly limited. For example, a hydrogen atom; an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group; a vinyl group, an allyl group , An alkenyl group having 20 or less carbon atoms such as a propenyl group; an aralkyl group having 20 or less carbon atoms such as a benzyl group or a phenethyl group.

  Examples of the alkoxysilyl group include methyldimethoxysilyl group, dimethylmethoxysilyl group, trimethoxysilyl group, ethyldiethoxysilyl group, diethylethoxysilyl group, triethoxysilyl group, tris (2-methoxyethoxy) silyl group, ethyl Examples thereof include a dimethoxysilyl group and a methyldiethoxysilyl group. Of these, methyldimethoxysilyl group, trimethoxysilyl group, ethyldiethoxysilyl group, triethoxysilyl group, and tris (2-methoxyethoxy) silyl group are preferable in terms of curability and adhesiveness.

  Examples of the secondary amine include a compound represented by the following formula (1) and a compound represented by the formula (2).

The compound represented by Formula (1) is demonstrated below.
In formula (1), R ¹ is an optionally branched alkylene group having 1 to 12 carbon atoms, and R ² and R ³ are each independently an optionally branched alkyl group having 1 to 8 carbon atoms. Yes, n is an integer of 0-2.

  Examples of the alkylene group having 1 to 12 carbon atoms which may be branched include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a 2-methyl-1,3-trimethylene group (isobutylene group), and a pentamethylene group. , Hexamethylene group, octamethylene group, decamethylene group, dodecamethylene group, and 3,3-dimethylbutylene group. A trimethylene group, a 2-methyl-1,3-trimethylene group, and a 3,3-dimethylbutylene group (3,3-dimethyl-1,4-butylene group) are preferable because they are easily available and have excellent adhesion.

Examples of the alkyl group having 1 to 8 carbon atoms which may be branched include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -Pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group . These groups can contain double or triple bonds. Of these, a methyl group and an ethyl group are preferable. R ² and R ³ may be the same or different.
n is preferably 0 or 1.

  Examples of the compound represented by the formula (1) include N, N-bis [(3-trimethoxysilyl) propyl] amine, N, N-bis [(3-triethoxysilyl) propyl] amine, N, N-bis [(3-tripropoxysilyl) propyl] amine (made by Toray Dow Corning) is mentioned.

The compound represented by Formula (2) is demonstrated below.
In formula (2), R ² and R ³ have the same meanings as R ² and R ³ of formula (1), R ⁴ has the same meaning as R ¹ in formula (1), R ⁵ is 1 to carbon atoms 8 is an optionally branched alkyl group or aromatic hydrocarbon group, and n is an integer of 0-2.

R ⁴ is an alkylene group having 1 to 6 carbon atoms, such as a methylene group, a trimethylene group, or a 3,3-dimethylbutylene group (3,3-dimethyl-1,4-butylene group). Is preferred.

In R ⁵ , the optionally branched alkyl group having 1 to 8 carbon atoms has the same meaning as R ^{2 in} formula (1). Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a benzyl group, a styryl group, a tolyl group, a xylyl group, and a hydroxyphenyl group. Of these, a phenyl group and an optionally branched alkyl group having 2 to 4 carbon atoms (ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group) are preferable.
n is preferably 0 or 1.

Examples of the compound represented by the formula (2) include N-methyl-γ-aminopropyltrimethoxysilane, N-methyl-γ-aminopropyltriethoxysilane, N-ethyl-γ-aminopropyltrimethoxysilane, N-ethyl-γ-aminopropyltriethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N- (n-butyl) -γ-aminopropyltrimethoxysilane, N- (n-butyl) -γ-aminopropyltri Ethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, N-phenylaminomethyldimethoxymethylsilane, N-phenyl-γ-aminopropyltrimethoxy Examples include silane.
Among these, the secondary amine is preferably N-ethylaminoisobutyltrimethoxysilane or N-phenyl-γ-aminopropyltrimethoxysilane.

Moreover, a commercial item can be used as a secondary amine. Examples of commercially available products include A-Link15, Y-9669, A1170 manufactured by Toray Dow Corning, Inc .; XL-924, XL-926, XL-972, and XL-973 manufactured by Asahi Kasei Wacker Silicone.
A secondary amine can be used individually or in combination of 2 or more types, respectively.

  The addition reaction between the polyisocyanate compound and the secondary amine is not particularly limited. For example, it can be performed according to a conventionally known method. Specifically, for example, a method in which a polyisocyanate compound and a secondary amine are mixed in an amount ratio that preferably gives an addition rate described later, and stirred at room temperature (usually around 20 ° C.) to cause an addition reaction.

In addition reaction, it is preferable from the viewpoint of the toughness of a primer layer and adhesiveness that the addition rate of the secondary amine with respect to all the isocyanate groups in a polyisocyanate compound is 10-100 mol%. Since such an effect is further excellent, the addition rate is more preferably 50 to 100 mol%.
The reaction product (A) that can be obtained by adding a secondary amine to an isocyanate group of a polyisocyanate compound is mainly composed of a urea bond (—NH—CO—) containing a hydrolyzable silyl group and a tertiary nitrogen atom. N ¹ <, N ¹ represents a tertiary nitrogen atom derived from a secondary amine).

The solvent will be described below.
The solvent is not particularly limited as long as it is inert to the components of the primer composition for a sealing material and can dissolve and / or disperse the components of the primer composition for a sealing material. For example, aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; chain aliphatic hydrocarbons such as n-hexane; acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as; esters such as methyl acetate, ethyl acetate and butyl acetate; ethers such as diethyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane. . A solvent can be used individually or in combination of 2 types or more, respectively.
Among these, from the viewpoints of solubility in components, dispersibility, and drying properties, the solvent is preferably ethyl acetate, toluene, butyl acetate, and mixtures thereof.

  The amount of the reaction product (A) is preferably 0.1 to 20 parts by mass and more preferably 3 to 9 parts by mass with respect to 100 parts by mass of the solvent. In such a range, the solvent can dissolve or disperse the reaction product (A), and is excellent in solution stability and coating properties of the composition.

The primer composition for a sealing material of the present invention preferably further contains a reaction product (B) that can be obtained by addition reaction of an epoxy resin and a secondary amine having a hydrolyzable silyl group. one of.
The secondary amine having a hydrolyzable silyl group used is the same as the secondary amine described above.

The epoxy resin is not particularly limited as long as it has two or more epoxy groups. For example, epoxy compounds having a bisphenyl group such as bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, biphenyl type, polyalkylene glycol type, alkylene glycol Type epoxy compounds, epoxidized resins having a naphthalene ring, and bifunctional glycidyl ether type epoxy resins such as epoxy compounds having a fluorene group.
Examples of the tri- or higher functional epoxy resin include glycidyl ether type epoxy resins such as phenol novolak type, orthocresol novolak type, trishydroxyphenylmethane type and tetraphenylolethane type; synthetic fatty acids such as dimer acid Glycidyl ester type epoxy resin; glycidylamino such as N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM), triglycidyl isocyanurate, tetraglycidyl-m-xylylenediamine, triglycidyl-p-aminophenol Type epoxy resin. Furthermore, epoxy-modified resins such as epoxy-modified silicone, epoxy-modified acryl, and epoxy-modified polybutadiene into which an epoxy functional group has been introduced may be mentioned.

  Among these, bisphenol F type and bisphenol A type are preferable from the viewpoint of toughness and adhesion of the primer layer. The epoxy resin is preferably in a liquid state from the viewpoint of handling. An epoxy resin can be used individually or in combination of 2 types or more, respectively.

  The addition reaction between the epoxy resin and the secondary amine is not particularly limited. For example, it can be performed according to a conventionally known method. Specifically, for example, a method in which an epoxy resin and a secondary amine are mixed preferably in an amount ratio that gives an addition rate described later, and heated to 60 to 100 ° C. (usually around 80 ° C.) to cause an addition reaction. It is done.

In addition reaction, it is preferable from a viewpoint of toughness and adhesiveness that the addition rate of the secondary amine with respect to all the epoxy groups in an epoxy resin is 10-100 mol%. Since such an effect is further excellent, the addition rate is more preferably 50 to 100 mol%.
The reaction product (B) that can be obtained by adding a secondary amine to the epoxy group of the epoxy resin is mainly a tertiary amine having a hydrolyzable silyl group and a hydroxy group.

  The amount of the reaction product (B) is preferably 0.1 to 20 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the solvent. In such a range, the solvent can dissolve or disperse the reaction product (B), and is excellent in solution stability and coating properties of the composition.

The primer composition for a sealing material of the present invention is further mentioned as one of preferred embodiments containing a resin. Thereby, since the primer layer can be flexible, the toughness is more excellent. In addition, the primer layer tends to be a film, and adhesion can be stabilized.
Examples of the resin include polyester, chlorinated polymer, polysiloxane, acrylic, and styrene acrylic. Among these, a chlorinated polymer is preferable from the viewpoint of toughness, adhesion, solubility, and dispersibility of the primer layer.

  Examples of the chlorinated polymer include chlorinated rubber and compounds similar thereto. Specifically, for example, chlorinated products of isoprene-based synthetic rubber, chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene / propylene copolymer, chlorinated polybutadiene, chlorinated polystyrene, chlorinated styrene / butadiene copolymer. Examples thereof include a polymer, chlorosulfonated polyethylene, and chlorosulfonated ethylene / vinyl acetate copolymer.

The chlorination rate of the chlorinated polymer is preferably 5 to 70% and more preferably 10 to 70% from the viewpoint of adhesion. Moreover, it is preferable that the chlorination rate of a chlorinated polymer is 40 to 70% from a viewpoint of adhesiveness and workability | operativity.
The molecular weight of the chlorinated polymer is not particularly limited, and is preferably about 10,000 to 1,000,000 as the number average molecular weight. From the viewpoint of having appropriate strength and stability and stable adhesion, it is preferably 20,000 to 500,000.
The resins can be used alone or in combination of two or more.
The amount of the resin is preferably 0.1 to 30 parts by mass and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the solvent from the viewpoint of adhesion.

The primer composition for a sealing material of the present invention is further cited as one of preferred embodiments that further contains a silane coupling agent. Thereby, adhesiveness with a to-be-adhered body can be made more excellent.
The silane coupling agent is not particularly limited. For example, (meth) acryloyloxy group-containing silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; polymethoxysiloxane, silicates such as polyethoxysiloxane; N- (1 , 3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine, ketimine silanes such as N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine; Isocyanurate silanes such as 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate; epoxy group-containing silane coupling agents such as γ-glycidoxypropyltrimethoxysilane; methyltrimethoxysilane , Methyltriethoxysilane, vinyltri Setokishishiran, .gamma.-chloropropyl trimethoxy silane, hexamethyldisilazane, vinyltrimethoxysilane, .gamma.-chloropropyl methyl dimethoxy silane, methyl trichlorosilane, dimethyl dichlorosilane, include trimethylchlorosilane.

Among these, polymethoxysiloxane and 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate are preferable from the viewpoint of adhesion. A silane coupling agent can be used individually or in combination of 2 types or more, respectively.
The amount of the silane coupling agent is preferably 0.1 to 40 parts by mass, and more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the solvent. In such a range, the adhesion of the primer layer is more excellent.

The primer composition for a sealing material of the present invention is further mentioned as one of the preferred embodiments containing a catalyst. Thereby, hardening of the primer composition for sealing materials can be accelerated | stimulated.
Examples of the catalyst include tertiary amine compounds such as N, N, N ′, N′-tetramethylpropylenediamine and triethylenediamine; metals such as tin, zinc, bismuth, zirconium, cobalt, calcium and cerium. Examples include carboxylates; alkylates of metals such as titanium and zirconium; and chelates of metals such as titanium, aluminum, zirconium, iron, and cobalt. Among these, titanate (titanium alkylate) is preferable from the viewpoints of curability, adhesiveness, and film-forming property. Examples of titanates include tetrapropoxy titanium, tetrabutoxy titanium, and condensates thereof. A catalyst can be used individually or in combination of 2 or more types, respectively.

  The amount of the catalyst is preferably 0.01 to 20 parts by mass and more preferably 0.5 to 8 parts by mass with respect to 100 parts by mass of the solvent from the viewpoint of curability.

  The primer composition for a sealing material of the present invention has the object of the invention in addition to the reaction product (A), the solvent, and the reaction product (B), resin, silane coupling agent, and catalyst that can be used as necessary. A compounding agent can be contained in the range which does not impair. As a compounding agent, for example, an adhesion promoter, a tackifier, a rust inhibitor, a filler, a plasticizer, a thickener, an antioxidant, an ultraviolet absorber, an anti-aging agent, an inorganic pigment, an organic pigment, a flame retardant, Examples include dehydrating agents, thixotropic agents, and antistatic agents. The amount of the compounding agent is not particularly limited, and an amount that can be generally used in the primer composition can be blended.

Examples of the adhesion imparting agent include an epoxy resin, a polyisocyanate compound, a phenol resin, and an acrylic polymer. Examples of the epoxy resin and the polyisocyanate compound include the same ones as described above.
Examples of the tackifier include rosin resins, terpene resins, terpene phenol resins, coumarone indene resins, petroleum resins, and modified resins using these aromatic hydrocarbons.

  Examples of the rust preventive include zinc phosphate, tannic acid derivative, phosphate ester, and basic sulfonate.

  The production of the primer composition for a sealing material of the present invention is not particularly limited. For example, the reaction product (A), a solvent, and components that can be used as necessary can be put in a reaction vessel and sufficiently mixed using a mixing device such as a ball mill. It is one of the preferred embodiments that each component is prepared after being thoroughly dried. The obtained primer composition for a sealing material is preferably stored in a sealed state by replacing the inside of the container with nitrogen gas.

Examples of the adherend that can be used for the primer composition for a sealing material of the present invention include glass; various metals such as aluminum, anodized aluminum, iron, galvanized steel, copper, and stainless steel; mortar and stone. Porous materials: Fluorine electrodeposition, acrylic electrodeposition and fluorine coating, urethane coating, acrylic urethane coating materials; cured products of sealing materials such as silicone, modified silicone, urethane, polysulfide, and polyisobutylene ; Vinylo chloride resin, acrylic resin; rubbers such as NBR and EPDM.
Examples of the sealing material that can be used for the primer composition for a sealing material of the present invention include silicone-based, modified silicone-based, polysulfide-based, polyurethane-based, acrylic urethane-based, acrylic-based, SBR-based, butyl rubber-based, and polyisobutylene. System.
Since the primer composition for a sealing material of the present invention has excellent adhesion, the combination of the adherend and the sealing material is not particularly limited. Can be used for a wide range of combinations.

As described above, the reaction product (A) contained in the primer composition for a sealing material of the present invention can be obtained by an addition reaction between a polyisocyanate compound and a secondary amine. The secondary amine undergoes an addition reaction with the isocyanate group of the polyisocyanate compound, and the reaction product (A) obtained thereby has a urea bond (—N ² ) mainly containing a hydrolyzable silyl group and a tertiary nitrogen atom. H-CO-N ¹ <, N ¹ represents a tertiary nitrogen atom derived from a secondary amine). In such a urethane compound, a hydrogen atom bonded to N ² which is a nitrogen atom has low activity, and thus the reaction product (A) can be stable. On the other hand, when a primary amine and a polyisocyanate compound are subjected to an addition reaction, the primary amine has two active hydrogens, so only one of the active hydrogens of the primary amine is the isocyanate of the polyisocyanate compound. The present inventors have found that it is difficult to selectively react with a group.
Further, the reaction product (A) can be formed by itself and can adhere to the adherend and the sealing material. Therefore, it can be said that the reaction product (A) has the functions of a film-forming component and a silane coupling agent.
Further, since the reaction product (A) is difficult to crosslink on the nitrogen atom, the primer layer becomes flexible and tough, and the molecular weight of the cured product of the primer composition does not become too large. Further, since the flexible and tough primer layer can disperse and absorb external force, it can be difficult to peel off from the adherend and / or the sealing material.
Thus, the primer composition for sealing materials of the present invention can be a primer layer having excellent toughness and adhesion.
In addition, when the primer composition for a sealing material of the present invention further contains a reaction product (B), it has been considered difficult to use because the adhesion to the primer or the adherend is unstable so far. It can have excellent adhesion to the sealing material.
The mechanism as described above is only an estimation of the present inventor, and even if the mechanism is different, it is within the scope of the present invention.

  EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

1. Preparation of adducts A1 to A4 The components shown in Table 1 were mixed in the amounts shown in Table 1 (units are parts by mass), and reacted at room temperature (20 ° C.) for 24 hours with stirring. A4 was prepared respectively. Regarding the obtained adducts Al to A4, the addition rate of secondary amine to the total isocyanate groups in the polyisocyanate compound (silanization rate of adduct A in Table 1, unit: mol%) is shown in Table 1. .

The detail of each component of Table 1 is as follows.
・ HDI: Desmodule H, manufactured by Sumika Bayer Urethane Co., Ltd. ・ Hydrogenated MDI: Desmodule W, manufactured by Sumika Bayer Urethane Co., Ltd. ・ N-ethylaminoisobutyltrimethoxysilane: A-Link15, manufactured by Toray Dow Corning Co., Ltd.

2. Preparation of adducts Bl to B2 The components shown in Table 2 were mixed in the amounts shown in Table 2 (units are parts by mass), heated to 80 ° C. and allowed to react for 24 hours. Prepared. Regarding the adducts B1 to B2, the addition rate of secondary amines to the total epoxy groups in the epoxy resin (silanization rate of adduct B in Table 2 in units: mol%) is shown in Table 2.

Details of each component of Table 2 are as follows.
-Bis F type epoxy: YDF-170, manufactured by Tohto Kasei Kogyo Co., Ltd.-N-ethylaminoisobutyltrimethoxysilane: as in Table 1-N-phenyl-γ-aminopropyltrimethoxysilane: Y9669 (Toray Dow Corning Co., Ltd.) Made)

3. Peeling test of primer composition for sealing material on different adherends (1) Preparation of primer composition for sealing material Each component shown in Table 3 is mixed in the amount shown in Table 3 (unit is part by mass), A primer fine product for a sealant was prepared.
(2) Preparation of test body As an adherend, one glass plate having a length of 50 cm and a width of 50 cm was prepared. The primer composition for a sealing material obtained on one side of the glass plate was uniformly applied, and this was air-dried for 60 minutes. Next, a polyisobutylene-based sealing material (MILEX-Z, Yokohama Rubber Co., Ltd.) was applied on the primer layer. Manufactured) was applied so as to have an adhesion area of 10 mm × 50 mm and a coating thickness of 5 mm, and this was cured at 20 ° C. for 7 days, and then cured at 50 ° C. for 7 days to prepare a test specimen.
In addition, as a adherend, a cured product of a two-component silicone sealant (silicone 70, manufactured by Yokohama Rubber Co., Ltd.) having a length of 50 cm and a width of 50 cm was prepared, and a test body was prepared in the same manner as described above.
(3) Evaluation of Specimen Each of the obtained specimens was subjected to a 90 ° peeling test to evaluate the breaking condition. The results are shown in Table 3. CF indicates cohesive failure, TCF indicates thin layer failure (a state where the primer is partially interfaced with the adherend), and AF indicates interface failure between the primer and the adherend. .

Details of each component of Table 3 are as follows.
Solvent: Ethyl acetate Dehydrating agent: Zeolum A3, manufactured by Tosoh CorporationResin: Chlorinated polyethylene (Z200, manufactured by Daiso Corporation)
・ HDI: Death Module HL, manufactured by Sumika Bayer Urethane Co., Ltd. ・ Adducts Al to A4, Adducts Bl to B2: Adduct prepared as described above ・ Polyisocyanate: Death Module HL, manufactured by Sumika Bayer Urethane Co., Ltd. ・ Silane cup Ring agent A: 3-methacryloxypropyltrimethoxysilane (KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.)
Silane coupling agent B: polymethoxysiloxane (MS51, manufactured by Mitsubishi Chemical Corporation)
Silane coupling agent C: N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine (S340, manufactured by Chisso Corporation)
Silane coupling agent D: 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate (Y11597, manufactured by Toray Dow Corning)
Silane coupling agent E: γ-glycidoxypropyltrimethoxysilane (A187, manufactured by Toray Dow Corning)
Catalyst: Tetra-n-butoxy titanium (B-1, manufactured by Nippon Soda Co., Ltd.)

  As is clear from the results shown in Table 3, Examples 1 to 4 containing the adducts Al to A4 are superior in adhesion to glass as compared with Comparative Examples 1 and 2. In addition, the primer compositions of Comparative Examples 1 and 2 are unstable in adhesion to the cured product of the two-component silicone sealant, and the interface breaks, whereas the additive Al or the additive A3 and the additive Bl Or Examples 5-8 containing adduct B2 are excellent in the adhesiveness with respect to the hardened | cured material of a 2 component type silicone type sealing material.

4). Peeling test of primer composition for sealing material against different sealing materials (1) Preparation of primer composition for sealing material Each component shown in Table 4 is mixed in the amount shown in Table 4 (unit is part by mass), and each sealing A primer composition for a material was prepared. Each component in Table 4 is the same as that in Table 3.
(2) Preparation of test body As an adherend, one glass plate having a length of 50 cm and a width of 50 cm was prepared. The obtained primer composition for a sealing material was uniformly applied to one entire surface of the glass plate, and was air-dried for 60 minutes. Next, three kinds of sealing materials are applied on the primer layer so that each has an adhesion area of 10 mm × 50 mm and a coating thickness of 5 mm, and this is cured at 20 ° C. for 7 days, and then cured at 50 ° C. for 7 days. Thus, a test body was produced.
(3) Evaluation of Specimen Each of the obtained specimens was subjected to a 90 ° peeling test to evaluate the breaking condition. The results are shown in Table 4. CF indicates cohesive failure, and TCF indicates thin layer failure (a state where the primer is partially broken at the interface with the sealing material).

The components used in the composition for sealing materials in Table 4 are the same as those in Table 3.
The details of each sealing material in Table 4 are as follows.
-Urethane sealant: UH-01 NB, manufactured by Yokohama Rubber Co., Ltd.-Modified silicone sealant: Super II, manufactured by Yokohama Rubber Co., Ltd.-Polysulfide-based sealant: SC-M500, manufactured by Yokohama Rubber Co., Ltd.

  As is apparent from the results shown in Table 4, Examples 9 to 14 show excellent adhesion to the modified silicone sealant. In addition, Examples 11 to 14 including the adduct Al or the adduct A3 and the adduct B1 or the adduct B2 are excellent in adhesion to the urethane-based sealing material and the polysulfide-based sealing material.

Claims (6)

  A primer composition for a sealing material comprising a reaction product (A) obtainable by addition reaction of a polyisocyanate compound and a secondary amine having a hydrolyzable silyl group, and a solvent.   The primer composition for a sealing material according to claim 1, wherein an addition ratio of the secondary amine to all isocyanate groups in the polyisocyanate compound is 10 to 100 mol%.   Furthermore, the primer composition for sealing materials of Claim 1 or 2 containing the reaction product (B) obtained by addition-reacting an epoxy resin and the secondary amine which has a hydrolyzable silyl group.   Furthermore, the primer composition for sealing materials in any one of Claims 1-3 containing resin.   Furthermore, the primer composition for sealing materials in any one of Claims 1-4 containing a silane coupling agent.   Furthermore, the primer composition for sealing materials in any one of Claims 1-5 containing a catalyst.