JP4613522B2 - Primer composition - Google Patents

Description

  The present invention relates to a primer composition, and more particularly to a one-component primer composition that is excellent in storage stability and adhesiveness to various adherends and can suppress whitening phenomenon due to water.

In recent years, a sealing material (which may mean “sealant” in the present invention) is used to fill joints and gaps between various members in buildings, automobiles, etc., and to ensure watertightness and airtightness. Widely used. Therefore, the sealing material has good adhesion to various adherends that make up the window frame, automobile bodies, etc., for example, inorganic materials such as glass, ceramics, metals, cement, mortar, and organic materials such as plastic. Sex is required. Sealing materials used suitably for buildings, automobiles, etc. are frequently exposed to water such as rain, and adhesion to various adherends under such conditions is a very important required property for sealing materials. one of.
However, the adhesion of the sealing material itself often does not reach the desired target. In particular, there are many cases where the adhesiveness under water or conditions exposed to water is often poor. Therefore, when a sealing material is used, it is common to apply a primer before applying the sealing material.

  As such a primer, those suitable for each adherend and sealing material are used depending on the adherend and various sealing materials applied thereto, for example, silicone-based, modified silicone-based, polyurethane-based sealing materials, etc. It is done.

For example, as a primer for adhering silicone rubber to various adherends, (A) 100 parts by weight of a urethane prepolymer having one or more isocyanurate rings and two or more isocyanate groups in one molecule, (B ) Epoxy resin-modified silicone resin, 1 to 100 parts by weight as a solid component, (C) General formula HS (CH ₂ ) _n Si (OR) ₃ (wherein n is 2 or 3, and R is a monovalent hydrocarbon group) A film-forming composition comprising 1 to 50 parts by weight of a mercapto group-containing silane represented by (1) and 50 to 1000 parts by weight of (D) one or more organic solvents has been proposed (patent) Reference 1).

On the other hand, after the sealing material is constructed, it may be necessary to repair the construction portion due to deterioration of the sealing material or the like. At this time, after removing the existing sealing material, that is, the leading sealing material, a new sealing material (post-sealing sealing material) is applied, but the leading sealing material may not be completely removed. In some cases, a post-sealing sealant must be spliced.
In the joining of this sealing material, it is necessary that both sealing materials have good adhesiveness. However, as described above, the adhesiveness often does not reach a desired target, and a primer is also used. Is common.

  However, when sealing the sealing material, if both the leading sealing material and the trailing sealing material are silicone-based sealing materials, even if a primer is used, these sealing materials are inferior to each other or are jointed. The problem of not being able to occur may occur.

For example, the film-forming composition exemplified above is excellent in adhesiveness and water resistance after curing (curing) at room temperature on various adherends such as glass and mortar, but in the jointability between silicone-based sealing materials. May be inferior.
In addition, the film-forming composition is adhesive to various adherends such as a coated aluminum plate (low-temperature adhesiveness and initial adhesiveness), and is adhered to a coated aluminum plate after the composition has been prepared and stored (stored) for a certain period of time. In some cases (initial adhesion and water-resistant adhesion, hereinafter simply referred to as “storage adhesion”).
Furthermore, there may be a significant decrease in adhesion due to changes over time, which is strongly required for primer compositions and the like.
By the way, in general, compositions containing silyl compounds, silicone primer compositions, etc., when exposed to water, may gradually become white and deteriorate in appearance (whitening phenomenon). May be limited.

  Therefore, in the present situation where the properties required for the primer are advanced due to recent technological innovation, optimization of materials, etc., simplification and shortening of the manufacturing process, etc., the conventional primer (composition) is not stored. Stability, bondability to silicone sealants (initial adhesion, water-resistant adhesion and adhesion at low temperatures), and adhesion to various substrates such as aluminum coated plates (low-temperature adhesion, initial adhesion, There is no one that satisfies a high level of water-resistant adhesion and storage adhesion) and can suppress the whitening phenomenon, and further improvement of these characteristics is required.

JP 54-125248 A

  The present invention solves the above-mentioned problems. Specifically, it is excellent in storage stability, adhesiveness to various adherends and jointability to modified silicone sealants (initial and water-resistant adhesiveness). Another object of the present invention is to provide a one-component primer composition that can suppress the whitening phenomenon even when exposed to water for a longer time or under severe conditions.

  Another object of the present invention is to provide a one-component primer composition that is excellent in the jointing property (low-temperature adhesiveness) at a low temperature with respect to the modified silicone sealant in addition to the above properties.

As a result of intensive studies, the inventors of the present invention have improved adhesiveness and jointability (initial adhesiveness) to a modified silicone sealant by containing a condensate of alkoxysilane containing trialkoxysilane in the urethane primer. It has been found that the whitening phenomenon of the primer composition can be suppressed even when exposed to water for a long time or under severe conditions.
In addition, when the present inventors contain at least one silane compound of an aminosilane compound and a ketimine silane compound, the present invention exhibits excellent storage stability as a one-part composition, and further, a modified silicone-based sealing of the composition It was found that the jointability (initial and water-resistant adhesion) to the material can be improved.

  Furthermore, the present inventors have included an epoxy resin in the above composition, and without degrading excellent storage stability, adhesion to various adherends, and initial and water-resistant adhesion to a modified silicone sealant. It was found that the jointability to the modified silicone sealant at the time can also be improved.

  That is, this invention is made | formed based on the said knowledge, and provides the following (1)-(6).

(1) a) a polyisocyanate;
b) a condensate of alkoxysilane containing trialkoxysilane having a structure represented by the following general formula (1);
c) From an aminosilane compound having a structure represented by the following general formula (2), an aminosilane compound having a structure represented by the following general formula (3), and a ketimine silane compound having a structure represented by the following general formula (4) One or more silane compounds selected from the group consisting of:
d) A primer composition containing a film-forming resin.

（式中、Ｒ¹は炭素数１〜１２の炭化水素基、Ｒ²は炭素数１〜８の分岐していてもよいアルキル基である。）

(In the formula, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, and R ² is an optionally branched alkyl group having 1 to 8 carbon atoms.)

（式中、Ｒ³は炭素数１〜１２の分岐していてもよいアルキレン基であり、Ｒ⁴およびＲ⁵はそれぞれ炭素数１〜８の分岐していてもよいアルキル基であり同一でも異なっていてもよく、Ｒ⁶は炭素数１〜１２の分岐していてもよいアルキレン基であり、Ｒ⁷は水素原子、炭素数１〜８の分岐していてもよいアルキル基、炭素数７〜１８の分岐していてもよいアラルキル基または炭素数６〜１８のアリール基であり、Ｒ⁸およびＲ⁹は、それぞれ炭素数１〜１２の分岐していてもよい一価の有機基であり同一でも異なっていてもよく、Ｒ¹⁰は炭素数１〜１８の分岐していてもよい二価の有機基であり、ｎは０〜２の整数である。）

(Wherein R ³ is an alkylene group having 1 to 12 carbon atoms which may be branched, and R ⁴ and R ⁵ are each an alkyl group optionally having 1 to 8 carbon atoms which may be the same or different. R ⁶ is an optionally branched alkylene group having 1 to 12 carbon atoms, R ⁷ is a hydrogen atom, an optionally branched alkyl group having 1 to 8 carbon atoms, or 7 to 7 carbon atoms. 18 is an aralkyl group which may be branched or an aryl group having 6 to 18 carbon atoms, and R ⁸ and R ⁹ are each a monovalent organic group which may be branched having 1 to 12 carbon atoms. However, they may be different, R ¹⁰ is a divalent organic group having 1 to 18 carbon atoms which may be branched, and n is an integer of 0 to 2.)

  Here, the blending amount of each component with respect to 100 parts by mass of component a) is preferably 1 to 50 parts by mass of component b) and 5 to 50 parts by mass of component d).

  (2) The primer composition according to (1), wherein the a) polyisocyanate is a polyisocyanate having an isocyanurate ring.

  (3) The primer composition according to the above (2), wherein the polyisocyanate having an isocyanurate ring is an aliphatic or alicyclic polyisocyanate.

(4) Furthermore, e) The primer composition in any one of said (1)-(3) containing an epoxy resin.
Here, with respect to component a) 100 parts by mass, the amount of each component is 5-50 parts by mass for component b), 5-50 parts by mass for component d), and 0.5-30 parts by mass for component e). Preferably there is.

The primer compositions (1) to (4) preferably further contain f) an organic solvent in order to improve ease of preparation and workability of the coating process.
Here, it is preferable that the compounding quantity of this organic solvent is 100-1000 mass parts with respect to 100 mass parts of total solid in a composition.
In addition, even if it uses this organic solvent, the adhesiveness to the to-be-adhered body of this composition, the splicing property with respect to a modified silicone type sealing material, and storage stability are not affected at all.

(5) The equivalent ratio (NH ₂ / NCO or NH / NCO) of amino groups (including amino groups generated by hydrolysis) of the silane compound c) to all isocyanate groups in the composition is 0.05 to 0 The primer composition according to any one of (1) to (4), which is .35.

  (6) Any of the above (1) to (5), wherein the alkoxysilane condensate is an alkoxysilane condensate containing 20 mol% or more of trialkoxysilane having a structure represented by the following general formula (1): A primer composition according to claim 1.

（式中、Ｒ¹は炭素数１〜１２の炭化水素基、Ｒ²は炭素数１〜８の分岐していてもよいアルキル基である。）

(In the formula, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, and R ² is an optionally branched alkyl group having 1 to 8 carbon atoms.)

According to the present invention, it is excellent in storage stability, adhesion to various adherends and jointability (initial and water-resistant adhesion) to a modified silicone sealant, and even when exposed to water for a long time or under harsh conditions. A one-component primer composition that does not cause whitening can be provided.
Furthermore, when it contains an epoxy resin, it can provide a one-component primer composition having the above-mentioned characteristics and having excellent jointability (low-temperature adhesion) at low temperatures for a modified silicone sealant.

As described above, the primer composition of the present invention is required for storage stability, adhesion to various adherends, jointability to modified silicone sealants, and whitening phenomenon, which are required by the above-described recent technological innovations. Suppression can be sufficiently satisfied, and its usefulness is very high.
Further, the primer composition of the present invention can be prepared simply by blending the above components a) to d), and has an advantage that it is easy to produce.

Hereinafter, the primer composition of the present invention (hereinafter referred to as “the composition of the present invention”) will be described in detail.
The composition of the present invention comprises: a) a polyisocyanate; b) a condensate of an alkoxysilane containing a trialkoxysilane having a structure represented by the general formula (1); and c) a general formula (2). At least one selected from the group consisting of an aminosilane compound having a structure represented by the formula, an aminosilane compound having a structure represented by the general formula (3), and a ketimine silane compound having a structure represented by the general formula (4). A primer composition containing a silane compound and d) a film-forming resin, preferably e) a primer composition containing an epoxy resin.

  First, each component used for the composition of this invention is demonstrated.

  The polyisocyanate a) used in the composition of the present invention is not particularly limited as long as it is a compound having two or more isocyanate groups. Specifically, for example, aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. It may be an isocyanate or a mixture thereof.

  Examples of the aromatic polyisocyanate include 2,4- or 2,6-tolylene diisocyanate (TDI), 1,4-phenylene diisocyanate, 4,4′- or 2,4′-diphenylmethane diisocyanate (MDI), 1 , 5-naphthalene diisocyanate, tolidine diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, and the like.

Aliphatic polyisocyanates include ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethyl. Hexamethylene diisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI) and the like can be mentioned.
Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), bicycloheptane triisocyanate, and hydrogenated compounds of the above-described aromatic polyisocyanates.

As the polyisocyanate a) used in the composition of the present invention, a urethane oligomer or a urethane prepolymer can be used in addition to the above-described polyisocyanate.
The urethane prepolymer is not particularly limited as long as it is obtained from one or more of the polyisocyanates described above and a compound having two or more active hydrogen atoms usually used in the urethane prepolymer. Weight average molecular weight, number of functional groups Etc. are not particularly limited.
Here, the compound having two or more active hydrogen atoms is not particularly limited, and examples thereof include polyols and polyamines.

  When the polyisocyanate a) is a polyisocyanate having an isocyanurate ring, the polarity of the polyisocyanate becomes very high, and when it is made into a composition, it exhibits strong adhesiveness, and various adherends (for example, aluminum It has effective adhesion to porous materials such as mortar as well as inorganic materials such as coated plates, glass, ceramics, metals and cement, and organic materials such as plastic. In particular, it is preferable because adhesion to an aluminum coated plate and mortar can be remarkably improved.

  The polyisocyanate having an isocyanurate ring is a polyisocyanate having a ring formed by polymerization of three isocyanate groups. The isocyanate group to be polymerized is not particularly limited, and may be any isocyanate group contained in the aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate exemplified above, or a mixture thereof. May be.

  Among these, it is preferable to have an isocyanurate ring formed by polymerizing any one of the polyisocyanates exemplified above. Specifically, for example, an isocyanurate body of TDI, an isocyanurate body of HDI, IPDI, Preferred is an isocyanurate body.

  Furthermore, as the polyisocyanate having an isocyanurate ring, the storage stability of the composition and the reactivity of the isocyanate group of the polyisocyanate (adhesion of the composition) can be compatible at a high level, and the weather resistance is also excellent. A polyisocyanate having an isocyanurate ring having an aliphatic substituent or a polyisocyanate having an isocyanurate ring having an alicyclic substituent is more preferable, and examples thereof include HDI isocyanurate, IPDI isocyanurate, and the like. It is done.

These polyisocyanates having an isocyanurate ring may be produced by an ordinary method, or commercially available products may be used.
Specific examples of commercially available products include, for example, Coronate series (Coronate 2030, EH, etc.) manufactured by Nippon Polyurethane Industry Co., Ltd., Sumijoule series (Sumijoule IL, etc.) manufactured by Sumitomo Bayer Urethane Co., Ltd. Module system (Desmodule HL, Deathmodule N3390, Z4370, etc.), Takenate (Takenate 204, D170N, etc.) manufactured by Mitsui / Takeda Chemical Industries, Ltd., Bernock D800 (Bernock D800, manufactured by Dainippon Ink & Chemicals, Inc. , DN980, etc.), VESTANAT system (VESTANAT T1890 / 100, etc.) manufactured by Degussa Huls.

  In the composition of the present invention, one type of polyisocyanate having an isocyanurate ring may be used, or two or more types may be used in combination.

When using the above-mentioned polyisocyanate having an isocyanurate ring, a polyisocyanate (such as a urethane prepolymer) usually used in the above-described urethane-based primer composition can be blended as a polyisocyanate other than the polyisocyanate.
Preferred examples of such polyisocyanates include biuret bodies of the low molecular weight polyisocyanates exemplified above, adducts of low molecular weight polyisocyanates and polyhydric alcohols, and the like.

As an adduct of a low molecular weight polyisocyanate and a polyhydric alcohol, an adduct using trimethylolpropane as the polyhydric alcohol is preferably exemplified. Specifically, an HDI-TMP adduct formed from 1,1,1-trimethylolpropane (TMP) and HDI, a TMXDI-TMP adduct formed from TMP and TMXDI, and formed from TMP and XDI Preferred examples include XDI-TMP adducts and IPDI-TMP adducts formed from TMP and IPDI.
These adducts are preferred because they can maintain the excellent storage stability of the composition of the present invention.

  As such an adduct, for example, a commercially available product such as Saissen 3160 (Mitsui Cytec Co., Ltd.) can be used.

  The blending amount of these polyisocyanates with respect to the polyisocyanate having an isocyanurate ring is not particularly limited as long as the object of the present invention is not impaired.

The condensate b) of alkoxysilane containing trialkoxysilane having a structure represented by the following general formula (1) used in the composition of the present invention (hereinafter also simply referred to as “alkoxysilane condensate (b)”). Any of a polymer compound or an oligomer of alkoxysilane containing the trialkoxysilane as a monomer may be used.
In the composition of the present invention, the alkoxysilane condensate (b) improves the jointability to the modified silicone sealant and the adhesion to various adherends, and is compatible with the component c) described later. Has an effect of improving solubility. Furthermore, when the alkoxysilane condensate is used, the whitening phenomenon of the primer composition can be suppressed even when exposed to water for a long time or under severe conditions. It also has an effect of improving water-resistant adhesion to mortar.

In the general formula (1), R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, R ² is an alkyl group which may have a branched structure having 1 to 8 carbon atoms.
Specific examples of the hydrocarbon group having 1 to 12 carbon atoms of R ¹ include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, and a dodecyl group; an isopropyl group Branched alkyl groups such as isobutyl, s-butyl, t-butyl, isopentyl, neopentyl, t-pentyl, 1-methylbutyl, 1-methylheptyl and 2-ethylhexyl; benzyl And aralkyl groups such as phenethyl group; aryl groups such as phenyl group, tolyl group (o-, m-, p-), dimethylphenyl group and mesityl group. These groups may contain a double bond or a triple bond, and may contain a hetero atom. Each of these may have a substituent. Among these, a methyl group, an ethyl group, a propyl group, and a phenyl group are preferable. R ¹ does not include an amino group (imino group) or a ketimine group.

Examples of the optionally branched alkyl group having 1 to 8 carbon atoms of R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. N-pentyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, etc. And these groups may contain a double bond or a triple bond. Among these, a methyl group and an ethyl group are preferable. A plurality of R ² may be the same or different.

  The alkoxysilane condensate (b) is particularly preferably obtained by condensing an alkoxysilane containing at least one trialkoxysilane having a structure represented by the general formula (1) as a monomer. Although not limited, it is preferable that it is a condensate of the alkoxysilane which contains 20 mol% or more of trialkoxysilane which has a structure represented by the said General formula (1). When the trialkoxysilane is contained in an amount of 20 mol% or more, the jointability to the above-described modified silicone sealant, adhesion to various adherends, suppression of whitening phenomenon, water-resistant adhesion to mortar, etc. are further improved. Can do.

  The alkoxysilane condensate (b) may contain an alkoxysilane other than a trialkoxysilane having a structure represented by the general formula (1), and a tetraalkoxysilane, a structure represented by the general formula (1). It is possible to use trialkoxysilanes and dialkoxysilanes other than trialkoxysilanes having Specific examples include dimethyldimethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, and tetraethoxysilane. The content of these compounds is preferably 80 mol% or less of the alkoxysilane as a monomer of the alkoxysilane condensate (b).

  The amount of alkoxy groups in the alkoxysilane condensate (b) is preferably 5 to 70% by mass of the alkoxysilane condensate (b) in that whitening when exposed to water can be suppressed. More preferably, it is -55 mass%.

  The production method of the alkoxysilane condensate (b) may be a normal method and is not particularly limited. For example, 0.1 to 2.0 equivalents, preferably 0 with respect to the silyl group of the alkoxysilane. .2 to 1.5 equivalents of water were allowed to coexist and condensed at 10 to 60 ° C., preferably 10 to 50 ° C. for 5 to 30 hours, preferably 10 to 20 hours. It can be obtained by removing with The trialkoxysilane represented by the general formula (1) may be used singly or in combination of two or more, and may be used in combination with an alkoxysilane other than the trialkoxysilane.

  At this time, a catalyst such as an acid catalyst or a base catalyst may be used. Specific examples of the acid catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, n-butylphosphoric acid; tin-based acid catalysts such as dibutyltin dilaurate and dioctyltin; tetraisopropoxytitanium, titanium acetylacetonate and the like. Specific examples of the base catalyst include amine catalysts such as triethylamine, pyridine, and 2,4,6-tris (dimethylaminomethyl) phenol. Of these, triethylamine and pyridine are preferably used because the base catalyst can be easily removed by desolvation after the condensation reaction.

  In addition, the alkoxysilane condensate (b) contains, in addition to the trialkoxysilane having the structure represented by the general formula (1), a compound having a hydrolyzable silyl group, such as alkenyloxysilane. It may be used as a body. The content of the compound at this time is preferably 20% by mass or less of the alkoxysilane condensate (b).

A commercial item can also be used for the said alkoxysilane condensate (b).
Specific examples of commercially available products include, for example, methyltrimethoxysilane / dimethyldimethoxysilane cocondensate (X-40-9246, alkoxy group content 12% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.), methyltrimethoxysilane. / Dimethyldimethoxysilane co-condensate (X-40-9250, alkoxy group content 25% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.), dimethyldimethoxysilane / phenyltrimethoxysilane co-condensate (X-40-9227, alkoxy group) 15 mass%, manufactured by Shin-Etsu Chemical Co., Ltd.), phenyltrimethoxysilane condensate (KR-217, alkoxy group content 25 mass%, manufactured by Shin-Etsu Chemical Co., Ltd.), dimethyldimethoxysilane / phenyltrimethoxysilane Condensates (X-40-9247, alkoxy group content 16% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.) That.

  In the composition of the present invention, one kind of the alkoxysilane condensate (b) may be used, or two or more kinds may be used in combination.

The silane compound c) used in the composition of the present invention will be described.
The silane compound c) has an aminosilane compound having a structure represented by the general formula (2), an aminosilane compound having a structure represented by the general formula (3), and a structure represented by the general formula (4). It is selected from the group consisting of ketimine silane compounds.
These compounds not only function as curing agents for a) and b) above, but also have excellent compatibility with the modified silicone sealant and improve the jointability (initial and water-resistant adhesion) to the sealant. Furthermore, it contributes to the improvement of storage stability.
In the present invention, these compounds may contain at least one kind.

  The silyl group in the aminosilane compound and the ketimine silane compound preferably has at least one hydrolyzable substituent, and more preferably has two or more. When it has two or more, the adhesion imparting effect of the aminosilane compound and the ketimine silane compound is further enhanced. It is particularly preferable to have three or more.

  Specific examples of the hydrolyzable substituent include a hydrogen atom, an alkoxy group, an acyloxy group (RCO-O-), an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Of these, mildly hydrolyzable alkoxy groups are preferred. In addition, by selecting a hydrolyzable substituent, the hydrolysis rate and the adhesive expression time can be adjusted according to the application.

The aminosilane compound will be described.
The aminosilane compound is not particularly limited as long as it has an amino group and the silyl group described above, but is preferably an aminosilane compound represented by the following general formula (2).

In general formula (2), R ³ is an alkylene group having 1 to 12 carbon atoms which may be branched, and R ⁴ and R ⁵ are each an alkyl group having 1 to 8 carbon atoms which may be branched. They may be the same or different, and n is an integer of 0-2.

Here, the alkylene group having 1 to 12 carbon atoms of R ³ may be, for example, a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, decamethylene. Group, dodecamethylene group, 3,3-dimethylbutylene group and the like, and trimethylene group and 3,3-dimethylbutylene group (especially 3,3-dimethyl-1,4- Butylene group) is more preferred.
R ⁴ and R ⁵ are basically the same as those described for R ² in the general formula (1). n is preferably 0 or 1.

  Examples of the compound represented by the general formula (2) include N, N-bis [(3-trimethoxysilyl) propyl] amine, N, N-bis [(3-triethoxysilyl) propyl] amine, N , N-bis [(3-tripropoxysilyl) propyl] amine (manufactured by Nihon Unicar).

  Moreover, as an aminosilane compound, the aminosilane compound represented by following General formula (3) other than the compound represented by above-described General formula (2) is also preferable.

In the general formula (3), R ⁴ and R ⁵ are each an alkyl group having 1 to 8 carbon atoms which may be branched and may be the same or different, and R ⁶ is a branched chain having 1 to 12 carbon atoms. R ⁷ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be branched, an aralkyl group having 7 to 18 carbon atoms which may be branched, or 6 to 6 carbon atoms. 18 is an aryl group, and n is an integer of 0-2.

R ⁴ and R ⁵ are basically the same as those described for R ² in the general formula (1). n is preferably 0 or 1.
The optionally substituted alkylene group having 1 to 12 carbon atoms of R ⁶ is preferably any one of the alkylene groups exemplified for the alkylene group R ³ of the general formula (2). More preferably, it is an alkylene group having 2 to 6 carbon atoms, which is exemplified in the general formula (2).

Specific examples of the compound represented by the general formula (3) in which R ⁷ is a hydrogen atom include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-aminopropylmethyldimethoxy. Examples thereof include silane, γ-aminopropylmethyldiethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane (manufactured by Nihon Unicar).

Examples of the optionally branched alkyl group having 1 to 8 carbon atoms of R ⁷ include the alkyl groups exemplified for R ² in the general formula (1). Among these, a C2-C4 alkyl group which may be branched is preferable.
In R ⁷ , one or more hydrogen atoms of the alkyl group may be substituted with a substituent. The substituent is not particularly limited, but is preferably an amino group or an aminoalkyl group (having 1 to 8 carbon atoms), more preferably an amino group, an aminomethyl group, an aminoethyl group, or an aminobutyl group.
Specific examples of the compound represented by the above general formula (3), wherein R ⁷ is an optionally branched alkyl group having 1 to 8 carbon atoms, include, for example, 3- (n-butylamino) propyltri And methoxysilane (Dynasilane 1189 (manufactured by Degussa Huls)).

Examples of the optionally branched aralkyl group having ⁷ to 18 carbon atoms of R ⁷ include a benzyl group and a phenethyl group.

Examples of the aryl group having 6 to 18 carbon atoms of R ⁷ include a phenyl group, a methylphenyl group (toluyl group), a dimethylphenyl group, and an ethylphenyl group. In addition to the alkyl group described above, examples of the substituent for the aryl group include an alkoxy group such as a methoxy group and an ethoxy group, and a group composed of a halogen atom such as a fluorine atom and a chlorine atom. These substituents may have 1 or 2 or more, and their substitution positions are not limited.

Specific examples of the compound represented by the above general formula (3) in which R ⁷ is an aryl group having 6 to 18 carbon atoms include, for example, N-phenyl-γ-aminopropyltrimethoxysilane (manufactured by Nippon Unicar Co., Ltd.). ) And the like.

  In the composition of the present invention, one type of aminosilane compound may be used, or two or more types may be used in combination.

  Among these, N, N-bis [(3-trimethoxysilyl) propyl] amine, γ-aminopropyltrimethoxysilane, 3-butyl are preferable in that the above functions of the composition can be exerted in a balanced manner at a higher level. Aminosilane compounds such as aminopropyltrimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane are preferred.

The ketimine silane compound will be described.
The ketimine silane compound is not particularly limited as long as it has a ketimine group (ketimine bond) and the silyl group described above, but is preferably a ketimine silane compound represented by the following general formula (4).

In the general formula (4), R ⁴ and R ⁵ are each optionally branched alkyl group having 1 to 8 carbon atoms may be the same or different, R ⁸ and R ⁹ are each 1 to carbon atoms 12 is a monovalent organic group which may be branched and may be the same or different, R ¹⁰ is a divalent organic group which may be branched having 1 to 18 carbon atoms, and n is 0 to 0. It is an integer of 2.
Here, R ⁴ and R ⁵ are basically the same as those described for R ² in the general formula (1). n is preferably 0 or 1.
R ⁸ and R ⁹ are each a monovalent organic group having 1 to 12 carbon atoms which may be branched and may be the same or different, and may be a monovalent organic group having 1 to 6 carbon atoms which may be branched. An organic group (aliphatic group, alicyclic group, aromatic group) is preferable, and an alkyl group having 1 to 6 carbon atoms which may be branched is more preferable. Examples of the monovalent organic group which may be branched having 1 to 12 carbon atoms and the alkyl group which may be branched having 1 to 6 carbon atoms include the alkyl groups exemplified as R ² in the general formula (1). Preferably, it can be mentioned.
R ¹⁰ is a divalent organic group (aliphatic group, alicyclic group, aromatic group) having 1 to 18 carbon atoms which may be branched, and alkylene having 2 to 6 carbon atoms which may be branched. A group is preferred. Examples of the divalent organic group which may have 1 to 18 carbon atoms and the alkylene group which may have 2 to 6 carbon atoms include the alkylene groups exemplified as R ³ in the general formula (2). Preferably, it can be mentioned.

  Specific examples of the compound represented by the general formula (4) include N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine, N- (1, 3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (methyldimethoxysilyl) -1-propanamine, N- (1, 3-dimethylbutylidene) -3- (methyldiethoxysilyl) -1-propanamine and the like.

  In the composition of the present invention, one kind of the above ketimine silane compound may be used, or two or more kinds thereof may be used in combination.

  Among these, N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine (manufactured by Chisso Corporation) in that the above functions of the composition can be exhibited in a balanced manner at a higher level. ), N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

  The film-forming resin d) used in the composition of the present invention 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.

  The epoxy resin (including the prepolymer) e) used in the composition of the present invention is a resin that does not contain the hydrolyzable substituent of the silyl group described in the silane compound c) in the molecule, By containing the resin, the jointability at a low temperature to the modified silicone sealant can be remarkably improved.

  The epoxy resin e) is not particularly limited, and for example, bisphenol A, bisphenol F, bisphenol S, hexahydrobisphenol A, tetramethylbisphenol A, pyrocatechol, resorcinol, cresol novolac, tetrabromobisphenol A, trihydroxybiphenyl, bis Glycidyl ether type obtained by the reaction of polyphenols such as resorcinol, bisphenol hexafluoroacetone, tetramethylbisphenol F, bixylenol and epichlorohydrin; glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, hexylene Aliphatic polyhydric alcohols such as glycol, polyethylene glycol, polypropylene glycol and epichlorohydrin Polyglycidyl ether type obtained by reaction; glycidyl ether ester type obtained by reaction of hydroxycarboxylic acid such as p-oxybenzoic acid and β-oxynaphthoic acid and epichlorohydrin; phthalic acid, methylphthalic acid, isophthalic acid, terephthalic acid, Polyglycidyl ester type derived from polycarboxylic acid such as tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, endomethylenehexahydrophthalic acid, trimellitic acid, polymerized fatty acid; aminophenol, aminoalkylphenol, etc. Glycidylaminoglycidyl ether type derived from glycidylaminoglycidyl ester type derived from aminobenzoic acid; aniline, toluidine, tribromoaniline, xylylenediamine Glycidylamine type derived from styrene, diaminocyclohexane, bisaminomethylcyclohexane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, etc .; Nurate and the like; monoepoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, alkylphenyl glycidyl ether, benzoic acid glycidyl ester, styrene oxide, and the like, and one or a mixture of two or more thereof can be used.

Among these, bisphenol A and bisphenol F type epoxy resins are preferable because they are easily available and have a good balance of properties (performance) of the cured product.
The epoxy resin e) preferably has an epoxy equivalent of 156 to 1000 in view of excellent adhesiveness of the composition, and more preferably 156 to 700.
The epoxy resin may be a commercially available product or may be produced. The production conditions are not particularly limited, and can be performed under conditions usually used.

In the composition of the present invention, in addition to the above components, an organic solvent f) can also be contained in order to improve the ease of preparation and the workability of the coating process.
The organic solvent is not particularly limited as long as it is inert to the above components and has an appropriate volatility.
Specific examples of the organic solvent include methyl ethyl ketone, dimethylacetamide, acetone, ethyl acetate, butyl acetate, cellosolve acetate, mineral spirit, toluene, xylene, n-hexane, isohexane, methylene chloride, tetrahydrofuran, ethyl ether, dioxane. Etc. Among these organic solvents, methyl ethyl ketone, ethyl acetate, butyl acetate, isohexane, and toluene are preferable.
These organic solvents are preferably used after sufficiently dried.
In the composition of the present invention, one kind of the above organic solvent may be used, or two or more kinds thereof may be used in combination.

Furthermore, the composition of the present invention may contain other additives as necessary.
For example, inorganic pigments such as lamp black, titanium white, bengara, titanium yellow, zinc white, red lead, cobalt blue, iron black, aluminum powder; neozabon black RE, neoblack RE, orasol black CN, urasol black Ba (Both manufactured by Ciba-Geigy) and organic pigments such as spiron blue 2BH (manufactured by Hodogaya Chemical Co., Ltd.).
In addition, the composition of the present invention absorbs ultraviolet rays such as Siasorb (Cyasorb UV24 Light Absorber, manufactured by American Cyanamid), Ubinur (Uvinul D-49, D-50, N-35, N-539, manufactured by General Aniline). Inclusion of an agent or the like is effective in improving the light resistance by shielding or absorbing ultraviolet rays and visible light, and inclusion of carbon black can provide weather resistance because it can shield or absorb ultraviolet rays and visible light.
Furthermore, the composition of the present invention may contain a catalyst such as a tertiary amine or an organotin compound, and further contains glass powder, clay, powdered silica gel, ultrafine powdered silicic acid, molecular sieves (which has a water absorbing ability). And a thickener, butylbenzyl phthalate, dioctyl phthalate, dibutyl phthalate, a plasticizer such as chlorinated paraffin, and a stabilizer such as diethyl malonate.

Next, the composition of the present invention will be described.
The composition of the present invention comprises: a) a polyisocyanate; b) a condensate of an alkoxysilane containing a trialkoxysilane having a structure represented by the general formula (1); and c) a general formula (2). At least one selected from the group consisting of an aminosilane compound having a structure represented by the formula, an aminosilane compound having a structure represented by the general formula (3), and a ketimine silane compound having a structure represented by the general formula (4). A primer composition containing a silane compound and d) a film-forming resin.

Here, the compounding quantity of each component with respect to 100 mass parts of component a) is as follows.
Component b) is preferably 1-50 parts by weight, more preferably 3-30 parts by weight. Within this range, it contributes to improvement in adhesion, particularly improvement in initial adhesion to a modified silicone sealant.
Component c) has an equivalent ratio (NH ₂ / NCO or NH / NCO) of amino groups (including amino groups generated by hydrolysis of ketimine groups) of the silane compound to all isocyanate groups in the composition of 0.05 to 0 .35 is preferable, 0.05 to 0.25 is more preferable, and 0.05 to 0.20 is particularly preferable. Within this range, the jointability (initial and water-resistant adhesiveness) to the modified silicone sealant is improved, and further contributes to the improvement of storage stability.
Component d) is preferably 5 to 50 parts by weight, more preferably 5 to 40 parts by weight, and particularly preferably 5 to 20 parts by weight. Within this range, it contributes to improvement in adhesion to various adherends such as an aluminum coated plate.

  The composition of the present invention contains the components a) to d) described above, and by blending them in a balanced manner within the above range, the composition is excellent in storage stability and adhesiveness to various adherends, and modified silicone-based sealing. It is excellent in jointability (initial and water-resistant adhesiveness) to the material, and can suppress the whitening phenomenon even when exposed to water for a long time or under severe conditions.

The composition of the present invention is a primer composition containing the above components a) to d) and e) an epoxy resin.
Here, 0.5-30 mass parts is preferable and, as for the compounding quantity of component e) with respect to 100 mass parts of component a), 0.5-20 mass parts is more preferable. Within this range, the jointability at low temperatures for the modified silicone sealant can be significantly improved.

  Since the composition further contains the component a) to d) and the component e), the composition has excellent storage stability, adhesiveness to various adherends, and impact on a modified silicone sealant. The splicing property (initial, water-resistant adhesiveness) and the effect of suppressing whitening phenomenon are not impaired, and furthermore, the splicing property at low temperature for the modified silicone sealant is excellent.

  That is, the composition of the present invention has storage stability, adhesion to various adherends, jointability to a modified silicone sealant, suppression of whitening phenomenon, and the like required by the above-described recent technological innovations. It is satisfactory and its usefulness is very high.

  As described above, even if an organic solvent is used, it does not affect the adhesion to various adherends, storage stability, and jointability. Therefore, in order to improve the ease of preparation of the composition and the workability of the coating process, it is preferable to further contain f) an organic solvent. The blending amount of the organic solvent is preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the total solid content in the composition.

The production method of the composition of the present invention is not particularly limited. For example, depending on the components a) to d), the performance of the desired composition, etc., the epoxy resin e), the organic solvent f), and further if necessary. It can be obtained by mixing carbon black, other additives, and the like, kneading thoroughly at room temperature or under heating (for example, 40 ° C.) using a mixing device such as a ball mill, and uniformly dispersing.
Thus, the primer composition of the present invention can be prepared by simply blending the components a) to d) and the like, and has an advantage that it is easy to produce.

  The composition of the present invention can be applied to an adherend using a commonly applied application method such as a brush coating method, a spray coating method, a wire bar method, a blade method, a roll coating method, or a dipping method.

The composition of the present invention can be suitably used for various architectural and various automotive sealing materials. Specifically, the composition of the present invention exhibits good adhesion to porous members such as mortar and stone, acrylic electrodeposition paint, etc. as well as glass and aluminum as adherends, Good adhesion to various sealing materials such as silicone, silicone and polyurethane. Moreover, if it is a combination of these adherends and a sealing material, it has excellent adhesiveness in any combination.
Furthermore, it is excellent in the joining property of the modified silicone-based and silicone-based sealing materials, and can be suitably used for repairing the joining surface of the pre-coated silicone-based sealing material.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Examples 1 to 25 and Comparative Examples 1 to 14>
Each component shown in Table 1 below was mixed in the formulation (parts by mass) shown in Table 1 and sufficiently kneaded at room temperature using a ball mill to prepare a primer composition.
For component c), the equivalent ratio of amino groups to all isocyanate groups in the composition (NH ₂ / NCO or NH / NCO) is shown as “NH ₂ / NCO” in Table 1 for convenience. In Comparative Examples 9 and 10, the equivalent ratio (SH / NCO) of mercapto groups to all isocyanate groups in the composition was shown.

For each composition obtained, storage stability, adhesion to mortar, adhesion to aluminum coating, storage adhesion to aluminum coating, jointability to modified silicone sealant, and whitening state after hot water aging are as follows. It was evaluated by.
The results are shown in Table 2.

<Storage stability>
The viscosity immediately after the preparation of each composition obtained and the viscosity after curing at 60 ° C. for 2 weeks in an airtight container were measured with an E-type viscometer, and the viscosity immediately after preparation of the viscosity after curing at 60 ° C. for 2 weeks. The rate of increase (times) with respect to was calculated and storage stability was evaluated.
When the rate of increase is 1.5 times or less, “◯” is given, when it is more than 1.5 times and less than 2.0 times, “△”, and when it is 2.0 times or more, “x”. did.

<Adhesiveness to mortar>
Each composition obtained was applied to the surface of a mortar and allowed to stand for 30 minutes under conditions of 23 ° C. and 50% relative humidity (RH), and then a modified silicone sealant (manufactured by Yokohama Rubber Co., Ltd.) was applied to the coated surface of the composition. “Super One”) was pressure-bonded to a thickness of 3 mm to obtain a test piece.
After curing under the following conditions using this test piece, the modified silicone sealant is cut with a knife, the cut part is peeled off by hand (pick by hand), and the peeled state is observed (hand by knife cutting). The state of the adhesion interface between the adherend and the composition was evaluated by performing a peeling test.

(1) Initial adhesion Curing for 3 days in an environment with a temperature of 23 ° C and a relative humidity of 50% (2) Water-resistant adhesion After curing for 3 days in an environment with a temperature of 23 ° C and a relative humidity of 50%, soaked in warm water at 50 ° C for 7 days

  The evaluation was “◎” when the cohesive failure of the sealing material was 95% or more, “◯” when the sealing material was 70% or more and less than 95%, and “50” or less when the sealing material was 50% or more and less than 70%. "△" and those which were less than 50% were taken as "x".

<Adhesion to aluminum coated plate>
Each composition obtained was applied to the surface of an aluminum coated plate and allowed to stand for 30 minutes under conditions of 23 ° C. and 50% relative humidity (RH), and then a modified silicone sealant (manufactured by Yokohama Rubber Co., Ltd.) was applied to the coated surface of the composition. “Super One”) was pressure-bonded to a thickness of 3 mm to obtain a test piece.
After curing under the following conditions using this test piece, the modified silicone sealant is cut with a knife, the cut part is peeled off by hand (pick by hand), and the peeled state is observed (hand by knife cutting). The state of the adhesion interface between the adherend and the composition was evaluated by performing a peeling test.

(1) Low temperature adhesion Curing for 7 days in an environment of 5 ° C and 50% relative humidity (2) Initial adhesion Curing for 3 days in an environment of 23 ° C and 50% relative humidity (3) Water-resistant adhesive temperature 23 ° C, Immerse in warm water at 50 ° C for 7 days after curing for 3 days in an environment with a relative humidity of 50%

  The evaluation was “◎” when the cohesive failure of the sealing material was 95% or more, “◯” when the sealing material was 70% or more and less than 95%, and “50” or less when the sealing material was 50% or more and less than 70%. "△" and those which were less than 50% were taken as "x".

<Storage adhesion to aluminum coated plate>
The obtained composition was put in a sealed container and stored at 60 ° C. for 2 weeks, and then the state of the adhesion interface between the adherend and the composition was evaluated by the same conditions and methods as in the above <Adhesion to aluminum coated plate>.

<Punchability for modified silicone sealant>
As the modified silicone sealant as an adherend, “Super One” manufactured by Yokohama Rubber Co., Ltd. was cured for 7 days at room temperature (23 ° C.) and 7 days at high temperature (50 ° C.).
Each of the above compositions was applied to the surface of the cured sealing material so that the adhesion area was 10 mm × 50 mm, and left for 30 minutes at 23 ° C. and 50% relative humidity (RH), and then A modified silicone-based sealing material (“Super One” manufactured by Yokohama Rubber Co., Ltd.) was placed on and bonded to a thickness of 3 mm to obtain a test piece.
After curing under the following conditions using this test piece, the adhesive interface is cut with a knife, the cut part is peeled off by hand (pick by hand) and the peeled state is observed (hand peeling test by knife cut) ) To evaluate the destruction state.

(1) Low temperature adhesion Curing for 7 days in an environment of 5 ° C and 50% relative humidity (2) Initial adhesion Curing for 3 days in an environment of 23 ° C and 50% relative humidity (3) Water-resistant adhesive temperature 23 ° C, Immerse in warm water at 50 ° C for 7 days after curing for 3 days in an environment with 50% relative humidity

(1) Evaluation of low-temperature adhesiveness was “◎” when the cohesive failure of the sealing material was 70% or more, “◯” when it was 50% or more and less than 70%, and less than 50%. "X" was used.
(2) Initial adhesion and (3) Water-resistant adhesion were evaluated as “◎” when the cohesive failure of the sealing material was 95% or more, and “◯” when it was 70% or more and less than 95%. In addition, the case where it was 50% or more and less than 70% was designated as “Δ”, and the case where it was less than 50% was designated as “X”.

<Whitening state after hot water aging>
The obtained composition was applied to the surface of an aluminum coated plate, cured for 3 days in an environment of 23 ° C. and relative humidity of 50 RH, and then immersed in warm water at 50 ° C. for 7 days. “◎” indicates that the entire surface of the coated plate is visible, “○” indicates that the entire surface of the coated aluminum plate is whitened, but “○” indicates that the entire surface of the coated aluminum plate is transparent, and “△” indicates that the surface of the coated aluminum plate is partially invisible. The case where the entire surface of the aluminum coated plate was not visible was designated as “x”.

Each component and catalyst used in the composition of the present invention are shown below.
Polyisocyanate 1; TDI / HDI isocyanurate, Desmodur HL (Isocyanate group content 10.5% by mass, manufactured by Sumitomo Bayer Urethane Co., Ltd.)
Polyisocyanate 2; HDI isocyanurate, D170N (isocyanate group content 21.0% by mass, manufactured by Mitsui Takeda Chemical Co., Ltd.)
Polyisocyanate 3; IPDI isocyanurate, VESTANAT T1890 / 100 (isocyanate group content 15.7% by mass, manufactured by Degussa Huls)
Polyisocyanate 4: HDI-TMP adduct, Takenate D160N (isocyanate group content 12.8% by mass, manufactured by Mitsui Takeda Chemical Co., Ltd.)

Silane condensate 1; methyltrimethoxysilane / dimethyldimethoxysilane cocondensate (X-40-9246, alkoxy group content 12% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.)
Silane condensate 2; methyltrimethoxysilane / dimethyldimethoxysilane cocondensate (X-40-9250, alkoxy group content 25% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.)
Silane condensate 3; dimethyldimethoxysilane / phenyltrimethoxysilane cocondensate (X-40-9227, alkoxy group content 15% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.)
Silane condensate 4; phenyltrimethoxysilane condensate (KR-217, alkoxy group content 25 mass%, manufactured by Shin-Etsu Chemical Co., Ltd.)
Silane condensate 5: dimethyldimethoxysilane / phenyltrimethoxysilane cocondensate (X-40-9247, alkoxy group content 16% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.)
Silane compound 1; γ-glycidoxypropyltrimethoxysilane (A-187, manufactured by Nihon Unicar)
Silane compound 2; methyltrimethoxysilane (KBM13, manufactured by Shin-Etsu Chemical Co., Ltd.)
Silane condensate 6; tetramethoxysilane condensate (MS-51, weight average molecular weight 600, manufactured by Mitsubishi Chemical Corporation)

Ketimine silane compound 1; N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine (S340, manufactured by Chisso Corporation)
Ketimine silane compound 2; N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine (KBM-9103, manufactured by Shin-Etsu Chemical Co., Ltd.)
Aminosilane compound 1; N, N-bis [(3-trimethoxysilyl) propyl] amine (A1170, manufactured by Nihon Unicar Co., Ltd.)
Aminosilane compound 2; γ-aminopropyltrimethoxysilane (A1110, manufactured by Nippon Unicar Co., Ltd.)
Mercaptosilane compound; mercaptopropyltrimethoxysilane (A189, manufactured by Nihon Unicar)

Hydrogenated terpene resin; Clearon M105 (manufactured by Yasuhara Chemical Co., Ltd.)
Thermoplastic urethane resin; Pandex T5205 (Dainippon Ink Chemical Co., Ltd.)

Epoxy resin; bisphenol A type epoxy resin (YD-128, epoxy equivalent 186, manufactured by Tohto Kasei Co., Ltd.)
Toluene, ethyl acetate, butyl acetate, stannous octylate; Kanto Chemical Co., Ltd. isohexane; Maruzen Petrochemical Co., Ltd.

Claims (6)

a) a polyisocyanate;
b) a condensate of alkoxysilane containing trialkoxysilane having a structure represented by the following general formula (1);
c) From an aminosilane compound having a structure represented by the following general formula (2), an aminosilane compound having a structure represented by the following general formula (3), and a ketimine silane compound having a structure represented by the following general formula (4) One or more silane compounds selected from the group consisting of:
d) A primer composition containing a film-forming resin.

(In the formula, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, and R ² is an optionally branched alkyl group having 1 to 8 carbon atoms.)

(Wherein R ³ is an alkylene group having 1 to 12 carbon atoms which may be branched, and R ⁴ and R ⁵ are each an alkyl group optionally having 1 to 8 carbon atoms which may be the same or different. R ⁶ is an optionally branched alkylene group having 1 to 12 carbon atoms, R ⁷ is a hydrogen atom, an optionally branched alkyl group having 1 to 8 carbon atoms, or 7 to 7 carbon atoms. 18 is an aralkyl group which may be branched or an aryl group having 6 to 18 carbon atoms, and R ⁸ and R ⁹ are each a monovalent organic group which may be branched having 1 to 12 carbon atoms. However, they may be different, R ¹⁰ is a divalent organic group having 1 to 18 carbon atoms which may be branched, and n is an integer of 0 to 2.)   The primer composition according to claim 1, wherein the a) polyisocyanate is a polyisocyanate having an isocyanurate ring.   The primer composition according to claim 2, wherein the polyisocyanate having an isocyanurate ring is an aliphatic or alicyclic polyisocyanate.   Furthermore, e) The primer composition in any one of Claims 1-3 containing an epoxy resin.   The equivalent ratio of amino groups (including amino groups generated by hydrolysis) of the silane compound c) to all isocyanate groups in the composition is 0.05 to 0.35. The primer composition described. The primer composition according to any one of claims 1 to 5, wherein the condensate of alkoxysilane is a condensate of alkoxysilane containing 20 mol% or more of trialkoxysilane having a structure represented by the following general formula (1). object.

(In the formula, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, and R ² is an optionally branched alkyl group having 1 to 8 carbon atoms.)