JP5958061B2 - Urethane primer composition - Google Patents

Description

  The present invention relates to a urethane primer composition.

  Sealing materials are widely used in buildings and the like for filling joints and gaps between various members and ensuring watertightness and airtightness. Typical sealants for buildings include one-pack or two-pack sealants such as silicone sealants, modified silicone sealants, polyurethane sealants, and polysulfide sealants.

  Architectural sealing materials are required to exhibit adhesion to difficult-to-adhere coating surfaces such as acrylic electrodeposition coating surfaces and fluorine coating surfaces. A primer composition is used to improve the adhesion between the adherend and the sealing material (see, for example, Patent Document 1).

  Patent Document 1 shows good adhesion not only to various metal sashes with smooth surfaces, but also to porous adherends such as mortar, and adheres to urethane baked painted surfaces and acrylic electrodeposited painted surfaces. A primer composition with improved properties is disclosed. The primer composition described in Patent Document 1 contains at least one selected from the group consisting of a polyisocyanate compound and / or a reaction product or a mixture of a polyisocyanate compound and a silane coupling agent. A hexamethylene diisocyanate (HDI) burette body (hereinafter referred to as “HDI burette body”) is simply blended, and N-phenyl-γ-aminopropyltrimethoxysilane is simply blended with the silane coupling agent.

JP 2001-152080 A

  However, the primer composition described in Patent Document 1 is formed with a flexible film that alleviates curing shrinkage during application to an adherend, and can suppress skin separation from the adherend. Since the cohesive strength of the film is lowered, the hot water resistant adhesiveness is lowered.

  Moreover, although the primer composition of patent document 1 can improve the adhesiveness to a difficult-to-adhere coating surface, storage stability falls.

  Therefore, a primer composition having excellent storage stability and excellent adhesion to a difficult-to-adhere coating surface is required.

  In view of the above problems, an object of the present invention is to provide a urethane-based primer composition that has good storage stability and can improve resistance to hot water with respect to a difficult-to-adhere coating surface. .

The present invention includes the following (1) to ( 2 ).
(1) A coating surface having poor adhesion and a sealing material containing an adduct compound in which N-phenyl-3-aminopropyltrimethoxysilane is adducted in one of three functional groups in one molecule of a hexamethylene diisocyanate burette. urethane-based primer composition for use in adhesion.
(2) The urethane primer composition according to (1), further comprising a silane coupling agent having an epoxy group or a mercapto group .

  According to the present invention, the storage stability is good, and the hot water resistance can be improved with respect to a difficult-to-adhere coating surface.

FIG. 1 is a perspective view showing a state of a dropping test. FIG. 2 is a diagram showing a state of evaluation of the drop test.

  The present invention will be described in detail below. The present invention is not limited by the following modes for carrying out the invention (hereinafter referred to as embodiments). In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art, those that are substantially the same, and those in a so-called equivalent range. Furthermore, the constituent elements disclosed in the following embodiments can be appropriately combined.

  The urethane-based primer composition according to the present embodiment (hereinafter referred to as “the composition of the present embodiment”) has N— in one of three functional groups in one molecule of a buret body of an isocyanate compound and hexamethylene diisocyanate. And an adduct compound obtained by adducting phenyl-3-aminopropyltrimethoxysilane.

<Isocyanate compound>
The isocyanate compound (hereinafter referred to as “polyisocyanate compound”) contained in the composition of the present embodiment is not particularly limited as long as it has two or more isocyanate groups in the molecule. Specific examples of the polyisocyanate compound include TDI (for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI)), MDI ( For example, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diene Aromatic polyisocyanates such as isocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate; Aliphatic polyisocyanates such as socyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI); transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanatomethyl) cyclohexane (H ₆ XDI), cycloaliphatic polyisocyanates such as dicyclohexylmethane diisocyanate (H ₁₂ MDI); addition products of these polyisocyanates, for example, adducts using trimethylolpropane, glycol, etc .; these carbodiimide-modified poly Isocyanates; these isocyanurate-modified polyisocyanates; allophanate-modified polyisocyanates; Isocyanate, and the like. Such polyisocyanate compounds can be used singly or in combination of two or more.

  In this embodiment, it is preferable that the said polyisocyanate compound has 3 or more isocyanate groups from a viewpoint that the adhesiveness with respect to a difficult-to-adhere coating surface becomes more favorable. Specific examples of the polyisocyanate compound having three or more isocyanate groups include tris (phenylisocyanate) thiophosphate, polymethylene polyphenylisocyanate, and a polyisocyanate compound having an isocyanurate ring. These may be used alone or in combination of two or more.

  In the present embodiment, the hard-to-adhere paint surface refers to paint surfaces that are difficult to adhere, such as an acrylic electrodeposition paint surface, an anodized paint surface, a fluorine-based paint surface, and a silicone-based paint surface.

  Among these, it is preferable to use a combination of one or both of tris (phenylisocyanate) thiophosphate and polymethylene polyphenylisocyanate and a polyisocyanate compound having an isocyanurate ring. It is also preferable to use a combination of tris (phenylisocyanate) thiophosphate and a polyisocyanate compound having an isocyanurate ring. By using these in combination, it is possible to improve adhesion to a difficult-to-adhere coating surface.

  As the polyisocyanate compound having an isocyanurate ring, an isocyanurate-modified product of a diisocyanate compound obtained by trimerizing a diisocyanate compound can be preferably used. Specific examples of the diisocyanate compound include the aromatic polyisocyanates exemplified above. Among these, a polyisocyanate compound having an isocyanurate ring obtained by reacting a mixture of TDI and HDI has a viewpoint that adhesion to a difficult-to-adhere coating surface becomes better and sufficient adhesion is obtained. To preferred.

  Examples of commercially available polyisocyanate compounds include tris (phenyl isocyanate) thiophosphate (Dismodule RFE, manufactured by Bayer), polyisocyanate compounds having an isocyanurate ring obtained by reacting a mixture of HDI and TDI (dis Module HL, manufactured by Bayer), polymethylene polyphenyl isocyanate (Sumijoule 44V-10, manufactured by Sumika Bayer Urethane Co., Ltd.), and the like. Among these, a polyisocyanate compound having an isocyanurate ring obtained by reacting a mixture of HDI and TDI (Dismodule HL, manufactured by Bayer) can be preferably used.

<Adduct compound>
The adduct compound contained in the composition of this embodiment is a compound in which N-phenyl-3-aminopropyltrimethoxysilane is adducted to one of three functional groups in one molecule of a hexamethylene diisocyanate burette. Hereinafter, the adduct compound is also referred to as an adduct body.

(HDI bullet body)
The HDI buret body contained in the composition of the present embodiment is a compound represented by the following formula (1).

(Adduct body)
The adduct body contained in the composition of this embodiment is a silane-modified product of an HDI burette body having one or more hydrolyzable alkoxysilyl groups in one molecule.

  As for the alkoxysilyl group which an adduct body has, the silyl group which has a C1-C18 branched C1-C3 alkoxy group is mentioned, for example. Examples of the alkoxy group having 1 to 18 carbon atoms which may be branched include a methoxy group and an ethoxy group.

  The residue bonded to the silyl group is not particularly limited, and examples thereof include 1 to 3 alkyl groups having 1 to 18 carbon atoms which may be branched. Examples of the alkyl group having 1 to 18 carbon atoms which may be branched include a methyl group and an ethyl group.

  The adduct body can have an isocyanate group. When the adduct has an isocyanate group, the number of isocyanate groups in one molecule of the adduct is determined from the viewpoint that the isocyanate group of the adduct reacts with the isocyanate group of the urethane prepolymer and the adduct is incorporated into the skeleton of the product. It is preferable that it is 1-2. In addition, when a highly reactive urethane prepolymer is used as the adduct body, it has an isocyanate group from the viewpoint that the urea bond formed by the reaction of such a urethane prepolymer and the adduct body is incorporated into the skeleton. You can use what you do not.

  The adduct body has an HDI burette body, a secondary amino group in which an aromatic ring is directly bonded to a nitrogen atom, and an alkoxysilyl group from the viewpoint that it is superior in hot water-resistant adhesion to a difficult-to-adhere coating surface. It is preferably obtained by reacting with a secondary aminoalkoxysilane.

  In addition, in this embodiment, hot water-resistant adhesiveness means the adhesiveness after immersing for a predetermined time in the warm water of predetermined temperature, after hardening on predetermined | prescribed hardening and curing conditions.

  The secondary aminoalkoxysilane is preferably an alkoxysilane represented by the following formula (2) from the viewpoint that it is superior in hot water-resistant adhesion with a difficult-to-adhere coating surface.

In the formula, R ¹ is an aromatic hydrocarbon group, R ² is an alkylene group which may be branched from 1 to 18 carbon atoms, and R ³ and R ⁴ are each independently branched from 1 to 18 carbon atoms. And n is an integer of 1 to 3.

  The HDI burette body used when manufacturing an adduct body is synonymous with the above.

In the alkoxysilane represented by the above formula (2) used when the adduct body is produced, R ¹ is an aromatic hydrocarbon group, and specifically includes, for example, a phenyl group, a p-toluyl group, and the like. Can be mentioned. R ² is an alkylene group having 1 to 18 carbon atoms which may be branched, preferably an alkylene group having 2 to 6 carbon atoms.

R ³ and R ⁴ are each independently an alkyl group having 1 to 18 carbon atoms which may be branched, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group. n is an integer of 1 to 3, and a plurality of R ³ or R ⁴ may be the same or different. Here, the alkylene group and the alkyl group may be linear or branched, and may have a hetero atom (O, N, S, etc.).

  In addition, since the secondary alkoxysilane has an aromatic ring directly bonded to a nitrogen atom, the obtained adduct body has a rigid structure, and the composition of the present embodiment contains such an adduct body. Good adhesion can be exhibited with respect to a difficult-to-adhere coating surface.

  Preferable examples of the secondary alkoxysilane include N-phenyl-3-aminopropyltrimethoxysilane represented by the following formula (3).

  The reaction between the HDI burette and the secondary aminoalkoxysilane is an isocyanate group / amino group (the ratio of the isocyanate group in the polyisocyanate to the amino group in the secondary aminoalkoxysilane, hereinafter referred to as NCO / NH). Is preferably 3.0 / 2.0 to 3.0 / 0.2, more preferably 3.0 / 2.0 to 3.0 / 0.5. At this time, an unreacted HDI burette body may remain. When NCO / NH is within this range, the effect of improving the adhesion of the adduct body is sufficiently exhibited, which is preferable.

  The adduct body can be produced, for example, by reacting the HDI burette body and the secondary aminoalkoxysilane in a solvent under conditions of 40 ° C. or higher and 60 ° C. or lower. Moreover, catalysts, such as an organic tin compound, organic bismuth, an amine, can be used as needed.

  The adduct body has an average of one or more hydrolyzable alkoxysilyl groups in one molecule. Among them, the adduct body has an average of one or more isocyanate groups and an average of two or more hydrolyzable alkoxysilyl groups in one molecule from the viewpoint that it is superior in hot water-resistant adhesion with a hardly adhesive coating surface. It is preferable to have an average of 1 or more isocyanate groups and an average of 3 hydrolyzable alkoxysilyl groups in one molecule.

  As an adduct body contained in the composition of the present embodiment, one of three functional groups in one molecule of the HDI burette body represented by the above formula (1) has an N-phenyl group represented by the above formula (3). A reaction product obtained by adducting -3-aminopropyltrimethoxysilane can be preferably exemplified.

  The number average molecular weight of the adduct body is preferably less than 1500, more preferably 600 or more and 1200 or less, and more preferably 600 or more and 1000 from the viewpoint of superior warm water resistance with a difficult-to-adhere coating surface. More preferably, it is as follows.

  The content of the adduct body contained in the composition of the present embodiment is good in storage stability and excellent in hot water-resistant adhesion with a difficult-to-adhere coating surface, from the adduct body and the isocyanate compound. Preferably they are 20 mass% or more and 100 mass% or less with respect to the total amount 100, More preferably, they are 20 mass% or more and 80 mass% or less, More preferably, they are 20 mass% or more and 60 mass% or less.

  The adduct compound contained in the composition of the present embodiment may be a mixture of an HDI burette body and an adduct body.

<Silane coupling agent>
The composition of this embodiment can further contain a silane coupling agent. Examples of silane coupling agents include epoxy groups, mercapto groups, ureido groups (amino groups), amino groups, (poly) sulfide groups, vinyl groups, methacryloxy groups, carboxy groups, isocyanate groups, halogens, and cyclopropyl groups. Examples include silane coupling agents having at least one organic functional group selected from the group. The silane coupling agent contained in the composition of the present embodiment is preferably one having an epoxy group or a mercapto group in the molecule.

  Specific examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4). -Epoxycyclohexyl) Epoxy group-containing silane compounds such as ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane , Mercapto group-containing silane compounds such as γ-mercaptopropylmethyldiethoxysilane;

  γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N- amino group-containing silane compounds such as β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; γ-ureido Ureido group-containing silane compounds such as propyltrimethoxysilane and 3-ureidopropyltriethoxysilane;

  (Poly) sulfide group-containing silane compounds such as bis (triethoxysilylpropyl) tetrasulfide and bis (triethoxysilylpropyl) disulfide; vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) Silane-containing vinyl group-containing silane compounds; γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, etc. Silane compounds;

  Carboxysilane compounds such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; Trimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatoethyltrimethoxysilane, γ-isocyanatoethyltriethoxysilane, γ-isocyanateethylmethyl Isocyanate group-containing silane compounds such as diethoxysilane and γ-isocyanatoethylmethyldimethoxysilane; N- (1,3-dimethylbutylidene) -3- (trimethoxy) Silyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (methyldimethoxy) Silyl) -1-propanamine, ketimine group-containing silane compounds such as N- (1,3-dimethylbutylidene) -3- (methyldiethoxysilyl) -1-propanamine; γ-chloropropyltrimethoxysilane and the like; Halogen-containing silane compounds; silyl esters such as methyl silyl esters; silane compounds such as orthosilicate esters and the like. These silane coupling agents may be used singly or in combination of two or more.

  Among the above silane coupling agents, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, In particular, it is preferable because it is excellent in the effect of improving the adhesion to a difficult-to-adhere coating surface.

  The silane coupling agent is preferably selected and used as appropriate according to the type of the coated surface of the adherend. A commercial item may be used for the said silane coupling agent, and you may manufacture it. Manufacturing conditions are not particularly limited, and can be performed by known methods and conditions. As a commercial item of the said silane coupling agent, A-187, A-183, etc. made from Momentive Performance Materials Japan GK can be used conveniently, for example.

  The silane coupling agent is preferably contained in an amount of 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the total amount of the adduct body and the isocyanate compound. Within this range, the storage stability is good without adversely affecting the physical properties of the cured product, and the adhesion of the primer composition to the difficult-to-adhere coating surface can be further improved.

  Since the composition of this embodiment contains the silane coupling agent which has an epoxy group or a mercapto group, it can further improve the adhesiveness with respect to a difficult-to-adhere coating surface.

  Moreover, the composition of this embodiment can contain film forming resin other than the said component. The film-forming resin is not particularly limited as long as it is a resin having a low activity or inactivity with respect to the NCO group and has a film-forming property, and generally used resins can be used. Specifically, an acrylic resin, a polyester polyurethane resin, a chlorinated rubber, a terpene resin and the like are preferably exemplified.

  Of these, a chlorinated rubber is preferable. Chlorinated rubber is a rubber obtained by dissolving raw materials such as natural rubber and synthetic rubber in a chlorine-based solvent inert to chlorine such as carbon tetrachloride, or by chlorinating rubber latex. It is. A commercial item can also be used as a chlorinated rubber. Specifically, for example, Pergut S20 and Pergut S170 (both manufactured by Sumika Bayer Co., Ltd.) are preferable because they can particularly improve the adhesion to difficult-to-adhere coating surfaces and are easily available. It is done.

  The composition of the present embodiment is, as necessary, a solvent, a dehydrating agent, an adhesion-imparting agent, a curing catalyst, a filler, a plasticizer, an ultraviolet absorber, a dispersant, as long as the effects of the present embodiment are not impaired. Various additives such as pigments, dyes, antioxidants, antioxidants, antistatic agents and flame retardants can be contained. Two or more of these may be contained.

  The method for producing the composition of the present embodiment is not particularly limited. For example, each of the above components may be used under a reduced pressure or an inert gas atmosphere such as nitrogen using a stirring device such as a ball mill, a universal agitator, or a mixing mixer. Examples of the method include mixing by sufficiently kneading and uniformly dispersing.

  As described above, the composition of the present embodiment includes an adduct compound in which N-phenyl-3-aminopropyltrimethoxysilane is adducted to one of three functional groups in one molecule of an HDI burette. The primer composition. The adduct compound of the composition of the present embodiment can introduce a hydrophobic group by adducting N-phenyl-3-aminopropyltrimethoxysilane to one of three functional groups in one molecule of the HDI burette body. Therefore, hydrolysis of the primer composition can be suppressed, and hot water resistant adhesiveness can be improved.

  Moreover, since the adduct compound of the composition of this embodiment is a compound in which N-phenyl-3-aminopropyltrimethoxysilane is adducted, the composition is simply formulated with N-phenyl-3-aminopropyltrimethoxysilane. In comparison, the storage stability can be improved.

  Therefore, the composition of the present embodiment has good storage stability and can have excellent hot water-resistant adhesion to a difficult-to-adhere coating surface.

  Moreover, since the adduct compound of the composition of the present embodiment is a compound in which N-phenyl-3-aminopropyltrimethoxysilane is adducted to one of three functional groups in one molecule of the HDI burette body, And the silane coupling agent can be blended together, so that the adhesion can be further improved with respect to the difficult-to-adhere coating surface.

  Examples of the adherend to which the composition of the present embodiment is applied include glass, metal, wood, plastic, and those whose surfaces are coated. In addition, examples of the hardly-adhesive coating plate include an acrylic coating plate, an epoxy coating plate, and a silicone coating plate.

  The composition of this embodiment can be suitably used as a primer for a difficult-to-adhere adhesive coating member. Examples of the material of the hardly adhesive coating member that can suitably use the composition of the present embodiment include an acrylic electrodeposition coating member, a fluorine baking coating member, and an anodized coating member. These hardly adhesive coating members are used in, for example, automobiles, vehicles, buildings, electronic parts, and the like. Moreover, the composition of this embodiment can be used also for members other than the coating member of difficulty adhesion.

  In addition, since the composition of the present embodiment has the excellent characteristics as described above, it is suitable for use as a sealing material for construction, civil engineering, concrete, wood, metal, glass, plastic and the like. Are also preferably used.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<Preparation of adduct compound>
Each component shown in Table 1 is blended in the blending amount (parts by mass) shown in the same table, and these are uniformly mixed and stirred and reacted for 4 hours under conditions of a reaction temperature of 40 ° C. or more and 60 ° C. or less, An adduct compound was prepared. Table 1 shows the amount of each component. In addition, about Example 4-6, 9, 10, the compounding quantity of an adduct compound and an unreacted HDI burette body is shown in Table 2.

Each component shown in Table 1 is as follows.
・ HDI burette: Trade name “Takenate D-165N”, manufactured by Takeda Pharmaceutical Co., Ltd. ・ Silane coupling agent: N-phenyl-3-aminopropyltrimethoxysilane, trade name “KBM-573”, Shin-Etsu Chemical Co., Ltd. Made by company-Solvent: Ethyl acetate, manufactured by Kanto Chemical Co., Inc.

<Preparation of primer composition>
Each component shown in Table 2 was blended in the blending amount (parts by mass) shown in the same table, and these were uniformly mixed to prepare each primer composition shown in Table 2. Table 2 shows the amount of each component in each example and comparative example.

<Drip test>
FIG. 1 is a perspective view showing a state of a dropping test. Each obtained primer composition 10 is dripped at the anodized coating aluminum plate (adhered body 1) 11 and various anodized coating composite coating aluminum plates (adhered bodies 2 to 5) 11, and the following curing and curing conditions are shown. And cured to obtain a test body. In addition, the adherends 1 to 5 are anodized composite film aluminum plates of each sash manufacturer, and the manufacturer of the composite paint and the conditions of the manufacturing process are different.
(Curing and curing conditions)
-Initial adhesion: left at 23 ° C for 3 days-Warm water resistant adhesion: left at 23 ° C for 3 days, then left at 50 ° C for 4 days, and then immersed in warm water at 50 ° C for 7 days

About each obtained test body, the adhesiveness of each primer composition was evaluated by the method shown below. As shown in FIG. 1, each primer composition 10 was cross-cut with a cutter knife and played with a cutter to visually observe the state of the cured film. The evaluation results are shown in Table 2. FIG. 2 is a diagram showing a state of evaluation of the drop test. As shown in FIG. 2, the evaluation criteria of 1-5 in Table 2 are as follows.
(Evaluation criteria)
・ Evaluation 5: No abnormality such as cracking or peeling in the cured film is observed. ・ Evaluation 4: There is no cracking in the cured film, and partly peeling occurs when played. ・ Evaluation 3: The cured film is broken along the cross part Peeling occurs on the entire surface when flipped. Evaluation 2: The cured film is cracked along the cross portion, and peeling occurs on the entire surface when flipped. Evaluation 1: When the cutter is inserted, peeling occurs on the entire surface of the cured film. “Evaluation 3” If it was above, it evaluated that it was excellent in adhesiveness.

<Peel test (peel test)>
Each primer composition obtained was applied to an anodized coated aluminum plate (adhered body 1) and various anodized coated composite film aluminum plates (adhered bodies 2 to 5), left at 20 ° C. for 30 minutes, and then polysulfide. A system sealant (trade name: Hamatite SC-M500, manufactured by Yokohama Rubber Co., Ltd.) was applied and cured under the following curing and curing conditions to obtain a test specimen. In addition, the adherends 1 to 5 are the same as those in the dropping test described above.
(Curing and curing conditions)
-Initial adhesion: left at 23 ° C for 3 days-Warm water resistant adhesion: left at 23 ° C for 3 days, then left at 50 ° C for 4 days, and then immersed in warm water at 50 ° C for 7 days

About each obtained test body, the 90 degree peeling test (peel test) of each primer composition was done by the method shown below, and the destruction state was evaluated. Table 2 shows the evaluation results of the destruction state. The evaluation criteria in Table 2 are as follows. If it was CF and TCF, it was evaluated that it was excellent in adhesiveness.
(Evaluation criteria)
-CF: Area ratio of cohesive fracture of sealant-TCF: Area ratio of thin-layer fracture of sealant composition-AF: Area ratio of interface fracture between adherend and primer composition-PS: Primer composition and sealing Area ratio of interface fracture with material

<Storage stability>
Each composition obtained in Table 2 was cured at 50 ° C. for 14 days, and then the state of each primer composition was confirmed. The state in which the adhesive can be applied to the adherend is indicated as “◯”, and the state in which the increase in viscosity is severe and difficult to apply is indicated as “x”. Table 2 shows the evaluation results of the storage stability.

Each component shown in Table 2 is as follows.
・ Solvent: Ethyl acetate, manufactured by Kanto Chemical Co., Ltd. ・ Membrane resin: Chlorinated rubber, trade name “Pergut S170”, manufactured by Sumika Bayer Co., Ltd. ・ Dehydrating agent: Trade name “Zeoram A3”, manufactured by Tosoh Corporation ・ Isocyanate compound : Adduct body of HDI (hexamethylene diisocyanate) and TDI (tolylene diisocyanate), manufactured by Yokohama Rubber Co., Ltd. • HDI burette body: Trade name “Takenate D-165N”, manufactured by Takeda Pharmaceutical Co., Ltd. • Silane coupling agent 1: 3-glycidoxypropyltrimethoxysilane, trade name “A-187”, manufactured by Momentive Performance Materials Japan GK ・ Silane coupling agent 2: 3-mercaptopropyltrimethoxysilane, trade name “A-183” ”Momentive Performance Materials Manufactured by Bread Godo Co., Ltd. ・ Adhesiveness imparting agent: N-phenyl-3-aminopropyltrimethoxysilane, trade name “KBM-573”, manufactured by Shin-Etsu Chemical Co., Ltd. ・ Catalyst: amine catalyst, trade name “Farmin DM4098”, Manufactured by Kao Corporation • Adduct compound: Adduct compound obtained by preparing in Table 1 above

  From the results shown in Table 2, in the drop test, in Examples 1 to 10, both the initial adhesion and the hot water adhesion to the adherends 1 to 5 are “evaluation 3” or more, and any adhesion It was confirmed that it was excellent in initial adhesion and hot water-resistant adhesion to the body. Further, in Examples 1 to 10, the peel test was performed with respect to the adherends 1 to 5 in which both the initial adhesiveness and the hot water-resistant property are CF and TCF. Was also confirmed to be excellent in initial adhesiveness and hot water resistant adhesiveness.

  On the other hand, in the drop test, in Comparative Example 1, the initial adhesiveness was “Evaluation 2” or less for any adherend, and the hot water resistance was not measurable. In Comparative Example 2, the initial adhesiveness was adhered. It was "Evaluation 2" with respect to the body 5, and it was confirmed that it was inferior to initial adhesiveness. In addition, since the hot water adhesiveness was “evaluation 2” or less except for the adherends 2 and 5 of Comparative Example 4, it was confirmed that Comparative Examples 1 to 5 were all inferior in hot water adhesiveness. .

  Further, in the peeling tests, in Comparative Examples 1 to 5, the initial adhesiveness is CF or TCF for any adherend, but since there are many adherends whose hot water resistance is AF or PS, It was confirmed that all of Examples 1 to 5 were inferior in resistance to hot water.

  The storage stability was “◯” in each of Examples 1 to 10, and it was confirmed that the storage stability was good. On the other hand, although it was "(circle)" in Comparative Examples 1-3, it was "x" in Comparative Examples 4 and 5, and it was confirmed that it is inferior to storage stability.

  Therefore, the primer composition containing an adduct compound in which N-phenyl-3-aminopropyltrimethoxysilane is adducted to one of the three functional groups in one molecule of the HDI burette body does not contain the adduct compound. Compared to products, the storage stability is good, and the adhesion to difficult-to-adhere coating surfaces can be improved. Moreover, since it is excellent in initial adhesiveness and hot water-resistant adhesiveness, it can be suitably used as a primer composition for a hardly adhesive coated surface.

10 primer composition 11 adherends 1 to 5

Claims (2)

Adhesion of difficult-to-adhere coating surface and sealant containing adduct compound in which N-phenyl-3-aminopropyltrimethoxysilane is adducted in one of three functional groups in one molecule of hexamethylene diisocyanate burette. urethane-based primer composition used.   Furthermore, the urethane-type primer composition of Claim 1 containing the silane coupling agent which has an epoxy group or a mercapto group.

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