JP2001152080A - Primer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a primer composition excellent in weather resistance, heat resistance and waterproof property, and capable of being widely applied to various materials to be applied having extremely different surface form such as various metal sashes, etc., mortar, etc. SOLUTION: This primer composition is characterized by containing (A) an organic polymer having a saturated hydrocarbon as its skeleton and at least one reactive functional group, (B) an organic solvent, (C) at least one kind selected from a group consisting of a polyisocyanate compound and a reaction material or a mixture of the polyisocyanate compound with a silane coupling agent and (D) an epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a primer composition, and more particularly to a primer composition having excellent weather resistance, heat resistance, and water resistance and having extremely different surface morphologies such as mortar and various metal sashes. It relates to a primer composition which can also be applied to the body.

[0002]

2. Description of the Related Art Organic polymers such as polyisobutylene having a saturated hydrocarbon as a skeleton and having a reactive functional group can be used as sealing materials, coating agents, sealants, etc. due to their excellent weather resistance, heat resistance and water resistance. It is preferably used.

[0003] For example, Japanese Patent Application Laid-Open No. 10-324811 discloses that a coating agent having good initial curability can be obtained by using an epoxy resin in combination with the organic polymer.

Further, JP-A-10-204303 and JP-A-10-182992 disclose a saturated hydrocarbon polymer having a hydrolyzable silicon-containing group, a curing agent, and a silane coupling agent. A curable composition having the composition is disclosed.

Further, Japanese Patent Application Laid-Open No. 08-269343 discloses that a curable composition containing the above organic polymer is brought into contact with an isocyanate group-containing compound to remove moisture in the composition, and the composition has excellent storage stability. A curable composition is disclosed.

However, organic polymers such as polyisobutylene have problems in adhesiveness and the like because of their non-polarity.
It has been extremely difficult to select a primer that can adhere to various adherends.

[0007] For this reason, Japanese Patent Application Laid-Open No. 11-209702 discloses that the above organic polymer is dissolved in an organic solvent, a catalyst is added internally to form a binder, and an isocyanate group-containing silane coupling agent and an amino group-containing silane cup are added thereto. A primer composition to which a ring agent or the like is added has been proposed. However, for adherends having a very porous surface morphology such as mortar, there is a problem that a sufficient coating film cannot be formed and adhesiveness is insufficient. For adherends with a porous surface morphology
There has been a demand for a primer that can be widely applied to various metal sashes and the like.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a porous substrate such as a mortar having excellent weather resistance, heat resistance, and water resistance and having extremely different surface morphologies, as well as various metal sashes. An object of the present invention is to provide a primer composition which can be widely applied to a body.

[0009]

That is, the present invention provides:
(A) an organic polymer having a skeleton of a saturated hydrocarbon and having at least one reactive functional group (hereinafter referred to as a saturated hydrocarbon polymer (A)), (B) an organic solvent, and (C) a polyisocyanate compound And (D) an epoxy resin, which comprises at least one selected from the group consisting of a reaction product or a mixture of a polyisocyanate compound and a silane coupling agent, and a (D) epoxy resin.

The reactive functional group contained in the saturated hydrocarbon polymer (A) is preferably at least one selected from the group consisting of a hydrolyzable functional group and a hydroxyl group. The epoxy resin (D) is preferably at least one selected from the group consisting of a bisphenol A epoxy resin and a bisphenol F epoxy resin.

[0011] The present invention also provides a primer composition characterized in that the primer composition further contains a latent curing agent (E). The latent curing agent is preferably at least one selected from the group consisting of block amines, aminosilanes, silicone compounds represented by the following formula (1), and compounds represented by the following formula (2).

[0012]

Embedded image In the formula, m and n are positive integers.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The primer composition of the present invention uses (A) an organic polymer having a saturated hydrocarbon skeleton and having at least one reactive functional group (hereinafter referred to as a saturated hydrocarbon polymer (A)).

The saturated hydrocarbon polymer (A) is a polymer substantially containing no carbon-carbon unsaturated bond other than the aromatic ring. The above saturated hydrocarbon polymer (A) can be obtained by the following method. (1) A method in which an olefinic compound having 1 to 6 carbon atoms such as ethylene, propylene, 1-butene, and isobutylene is polymerized as a main monomer. (2) A method of homopolymerizing a diene-based compound such as butadiene, isoprene, or 1,3-cyclohexanediene, or copolymerizing the olefin compound with a diene-based compound and then hydrogenating the compound.

Among these polymers, isobutylene-based polymers and hydrogenated polybutadiene-based polymers are preferred in that they can easily introduce a functional group into the terminal, control the molecular weight, and increase the number of terminal functional groups. It is preferably a polymer.

The isobutylene-based polymer may be formed of an isobutylene monomer, and another monomer having copolymerizability with isobutylene is preferably 50% (% by weight, hereinafter the same) or less in the isobutylene-based polymer. The content may be more preferably 30% or less, particularly preferably 10% or less.

Examples of such other monomer components include olefins having 4 to 12 carbon atoms, vinyl ethers,
Examples include aromatic vinyl compounds, vinyl silanes, allyl silanes, and the like.

Specific examples of such a copolymer include, for example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene and 4-methyl-
Olefins such as 1-pentene, hexene and vinylcyclohexane; styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-
Aromatic vinyl compounds such as pinene and indene; vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane,
Vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane,
Vinyl silanes such as 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane and tetravinylsilane; allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyl Allylsilanes such as trimethylsilane, diallyldichlorosilane, diallyldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylmethyldimethoxysilane; and the like.

When vinyl silanes or allyl silanes are used as monomers copolymerizable with these isobutylenes, the silicon content of the polymer increases, and the number of groups that can act as a silane coupling agent increases, resulting in a composition that can be obtained. The adhesiveness of the object is improved.

Further, in the hydrogenated polybutadiene-based polymer and other saturated hydrocarbon-based polymers, similarly to the case of the isobutylene-based polymer, in addition to the monomer as the main component,
Other monomers may be contained.

In the saturated hydrocarbon polymer used in the present invention, a monomer unit having a double bond remaining after polymerization, such as a polyene compound such as butadiene or isoprene, may be used as long as the object of the present invention is achieved. May be contained in a small amount, preferably 10% or less, more preferably 5% or less, particularly 1% or less.

Representative examples of the reactive functional group bonded to the saturated hydrocarbon polymer (A) include an isocyanate group, a hydroxyl group, or the following formula (3):

[0023]

Embedded image And a group in which a hydrolyzable group is bonded to a silanol group or silicon.

In the formula, R ¹ and R ² each represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,
An aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ Si
O- (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′s may be the same or different), and represents a triorganosiloxy group; R ¹
And when two or more R ² are present, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more are present, they may be the same or different. a is 0, 1, 2 or 3, b is 0, 1 or 2, but a + pb ≧ 1.

Further, the p number of the p-numbers represented by the following equation (4), which are shown in the above-mentioned equation (3),

Embedded image B need not be the same. p is 0 or 1
It is an integer of 19.

The hydrolyzable group in the general formula (3) is not particularly limited, and may be a conventionally known hydrolyzable group. Specific examples thereof include, for example, a hydrogen atom, a halogen atom, an alkoxy group and an acyloxy group. , A ketoxime group, an amino group, an amide group, an aminooxy group, a mercapto group, an alkenyloxy group and the like. Among these, an alkoxy group is particularly preferred because it has a mild hydrolytic property and is easy to handle.

This hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3 and (a +
pb) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different.

The number of silicon atoms forming the reactive silicon group may be one or two or more. In the case of silicon atoms linked by a siloxane bond or the like, 20
It is preferred that there be more than one. In particular, equation (5):

Embedded image (In the formula, R ² , X and a, b are the same as described above.)
Is preferred because the reactive silicon group represented by is easily available.

The reactive functional group is at least one, and preferably at least one, in one molecule of the saturated hydrocarbon polymer (A).
There are one to five. If the number of reactive functional groups contained in the molecule is less than one, the curability becomes insufficient and it becomes difficult to exhibit good rubber elasticity behavior.

The reactive functional group may be present at the terminal of the molecular chain of the saturated hydrocarbon polymer, may be present inside, or may be present at both ends. In particular, when a reactive functional group is present at the terminal, since the effective network chain amount of the saturated hydrocarbon polymer component contained in the finally formed cured product increases, the rubber has high strength and high elongation. It is preferable from the viewpoint that a cured product is easily obtained. These saturated hydrocarbon polymers (A) may be used alone,
More than one species may be used in combination.

The number average molecular weight of the saturated hydrocarbon polymer (A), particularly the isobutylene polymer or the hydrogenated polybutadiene polymer, is preferably about 500 to 100,000, particularly preferably 1,000 to 30. Those having a liquidity or fluidity of about 2,000 are preferred from the viewpoint of easy handling. Further, regarding the molecular weight distribution (M _w / M _n ), M _{w in} terms of lower viscosity at the same molecular weight.
The smaller / _Mn , the better.

The above manufacturing method is disclosed in
It is disclosed in detail in, for example, Japanese Patent Publication No. 1360, and these descriptions can be referred to. As the saturated hydrocarbon polymer (A), commercially available products can be used, and examples thereof include EPION (103S) manufactured by Kanegabuchi Chemical Industry Co., Ltd. and NEO manufactured by Asahi Kasei Corporation.

(B) Organic Solvent The primer composition of the present invention is preferably used as a solution or dispersion by dissolving or dispersing the above-mentioned saturated hydrocarbon polymer (A) and each of the following components in a solvent. .

The organic solvent (B) used in the present invention is an organic solvent in which the above-mentioned saturated hydrocarbon polymer (A) is easily soluble, and is inert to the saturated hydrocarbon polymer (A). Is not particularly limited as long as it has a proper volatility.

Specifically, aromatic hydrocarbons such as benzene, xylene and toluene, aliphatic hydrocarbons such as n-hexane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, methyl acetate, ethyl acetate and butyl acetate Such as esters, diethyl ether, tetrahydrofuran, ethers such as dioxane, dichloromethane,
Examples include halogenated hydrocarbons such as chloroform and 1,2-dichloroethane, and phenols such as phenol and p-cresol. These may be used alone or in combination of two or more.

Among them, toluene or ethyl acetate which has a moderate volatility and is excellent in solubility of various compounds,
Alternatively, it is preferable to use a mixed solution of toluene and ethyl acetate. By using such a solvent, the composition of the present invention can penetrate deep into a porous adherend such as mortar.

(C) Polyisocyanate compound and / or reaction product or mixture of polyisocyanate compound and silane coupling agent The primer composition of the present invention contains a polyisocyanate compound or a polyisocyanate compound and a silane coupling agent. By containing a reactant or a mixture, or both, the adhesion of the saturated hydrocarbon-based polymer (A) to the adherend, which has been problematic due to its non-polarity, is improved, It can be applied to a mortar or the like having a surface morphology.

As the polyisocyanate compound, tolylene diisocyanate, phenylene diisocyanate,
Xylene diisocyanate, diphenylmethane diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, polyisocyanates such as triphenylmethane triisocyanate, or addition reaction products of these polyisocyanates, for example, trimethylolpropane and Adducts using glycols and the like, modified isocyanurates thereof, modified carbodiimides, modified allohanates, modified burettes, and the like can be given. Among these, isocyanurate-bonded TDI having an isocyanurate ring, isocyanurate-bonded HDI, isocyanurate-bonded TPDI, and the like are extremely high in polarity and have strong adhesiveness, so that they are used for porous adherends such as mortar. It is effective for. In particular, a polyfunctional isocyanurate compound having an isocyanurate ring is preferable, and specifically, Desmodur IL manufactured by Sumitomo Bayer Urethane Co., Ltd.
Death Module HL (trade name) and the like. These may be used alone or in combination of two or more.

The reaction product or mixture of the polyisocyanate compound and the silane coupling agent is a reaction product or mixture of at least one selected from the above-described polyisocyanate compounds and at least one selected from the silane coupling agents described below. It is.

As the silane coupling agent, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ
-Mercaptopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane,
N-phenyl-γ-aminopropyltrimethoxysilane and the like can be mentioned.

As the reaction product or mixture of the polyisocyanate compound and the silane coupling agent used in the present invention, particularly, the reaction product or mixture of γ-mercaptopropyltrimethoxysilane and the above-mentioned polyisocyanate compound, Excellent effect of improving the adhesion to a wet surface, and a reaction product or a mixture of N-phenyl-γ-aminopropyltrimethoxysilane and the above-described polyisocyanate compound is a urethane-based baking paint or an acrylic electrodeposition plate. It is preferably used because the adhesiveness to the resin is improved. These may be used alone or in combination of two or more.

The silane coupling agent is used in an amount of 1 to 160 parts by weight based on 100 parts by weight of the isocyanate compound.
Preferably, the reaction product is obtained by blending 10 to 80 parts by weight. It is preferable if it is within this range since a reaction product can be easily obtained without gelation.

(D) Epoxy Resin The primer composition of the present invention contains the epoxy resin (D), and thereby contains a saturated hydrocarbon polymer (A), a polyisocyanate compound or a polyisocyanate compound and a silane coupling agent. With the reactant or mixture (C). Such compatibility makes the primer suitable as a primer in terms of adhesion and storage stability.

Examples of the epoxy resin (D) include glycidyl ether type epoxy resins such as bisphenol A type, bisphenol F type, hydrogenated bisphenol A type and phenol novolak type; and glycidyl such as glycidyl ester of hexahydrophthalic acid and glycidyl methacrylate copolymer. Ester-type epoxy resin; glycidylamine-type epoxy resin such as tetraglycidyldiaminodiphenylmethane; 3,4-epoxycyclohexylmethyl-3,4
-Cyclic oxirane types such as epoxycyclohexanecarboxylate.

Among these, it is preferable to use a bisphenol A type epoxy resin or a bisphenol F type epoxy resin in view of the above-mentioned compatibility, chemical resistance, adhesion, heat resistance, corrosion resistance, economy and the like. In particular, it is more preferable to use a bisphenol A type epoxy resin which has both the tough properties of a bisphenol A structure and the flexibility of an ether bond and has excellent adhesion.

The amount of each component described above is such that 50 parts of the organic solvent (B) is added to 10 parts by weight of the saturated hydrocarbon polymer (A).
1 to 20 parts by weight of a polyisocyanate compound, a reaction product or a mixture of a polyisocyanate compound and a silane coupling agent, or both (C),
The amount of the epoxy resin (D) in the range of 1 to 15 parts by weight is appropriate. Within this range, the composition is compatible,
It can be dispersed uniformly. Further, the concentration is appropriate, and a sufficient coating film can be formed on a porous adherend.

In order to enhance the curability of the primer composition of the present invention, it is effective to include a latent curing agent (E). This is because the cured product of the composition has good warm water resistance.

As the latent curing agent (E), a block that does not react with the epoxy resin in the absence of moisture or has extremely low reactivity, but can react by hydrolysis in the presence of moisture. It is particularly effective to use amines, aminosilanes, silicone compounds represented by the following formula (1), and compounds represented by the following formula (2). These may be used alone or in combination of two or more.

[0049]

Embedded image In the formula, m and n are positive integers.

Examples of the block amine that forms a primary or secondary amino group in the presence of moisture include aldimine compounds, ketimine compounds, enamine compounds, and oxazolidine compounds.

More specifically, condensation of a compound having active hydrogen such as at least one primary or secondary amino group or hydroxyl group (hereinafter referred to as compound (A)) with an aldehyde or ketone And compounds having two or more ketimines or oxazolidines in the molecule obtained by reacting an organic polyisocyanate compound with ketimine alcohol or oxazolidine alcohol, which is also the above condensate. Among these, ketimine compounds or oxazolidine compounds having relatively mild reactivity are preferably used. This is because the composition sufficiently penetrates deep into the adherend before being cured.

Representative examples of the compound (A) include a compound having a primary amino group and a hydroxyl group, a compound having a secondary amino group and a hydroxyl group, and a compound having a primary amino group and a hydroxyl group. Compound having primary amino group, compound having primary amino group, secondary amino group, and hydroxyl group, compound having two primary amino groups, compound having two secondary amino groups And a compound having a secondary amino group and two hydroxyl groups.

The ketimine compound can be obtained by reacting a polyamine with a ketone. For example, methyl isobutyl ketone (MIBK), methyl ethyl ketone (ME
It can be obtained by reacting a ketone such as K) and methyl isopropyl ketone with a polyamine such as ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and N-aminoethylpiperazine.

Among them, ketimine compounds synthesized from a ketone having a substituent at the α-position and having a large steric hindrance, and a polyamine having a methylene group at the α-position and having a small steric hindrance are particularly preferred for the composition of the present invention. Such ketimines have a bulky substituent near the double bond of the ketimine group, which protects the ketimine nitrogen, greatly reducing its basicity and consequently storage stability. Can be prevented, and at the same time, the curability becomes good.

The ketone having a substituent at the α-position is a ketone having a substituent at the α-position counted from the carbonyl group, and includes methyl t-butyl ketone, diisopropyl ketone,
Specific examples thereof include propiophenone, benzophenone, etc. in addition to methyl isopropyl ketone and the like. Among these, a compound represented by the following formula (6) is particularly preferable, and specifically, methyl isopropyl ketone, methyl t -Butyl ketone. This is because a blend of ketimine and an epoxy resin synthesized using these is excellent in balance between storage stability and curability.

[0056]

Embedded image R ³ : any one selected from the group consisting of alkyl groups having 1 to 6 carbon atoms R ⁴ : methyl group or ethyl group R ⁵ : hydrogen atom, methyl group or ethyl group

As the polyamine having at least two amino groups having methylene at the α-position in the molecule, a compound represented by the following formula (7) is preferable.

[0058]

Embedded image R ⁶ : organic group (including a group having O, S, N) q: an integer of 2 or more

Specifically, ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, N-aminoethylpiperazine, 1,2- Diaminopropane, iminobispropylamine, methyliminobispropylamine,
Jeffamine EDR148 manufactured by Sun Techno Chemical Co.
Diamine having a polyether skeleton represented by, 1,3-bisaminomethylcyclohexane, 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3,
3,5-trimethyl-cyclohexylamine, a diamine having a norbornane skeleton represented by NBDA manufactured by Mitsui Chemicals, Inc .; meta-xylylenediamine; a polyamide amine having an amino group at a molecular terminal of polyamide;

The ketimine compound used in the present invention is reacted with the above ketone and polyamine in the absence of a solvent or in the presence of a solvent such as benzene, toluene, or xylene by heating to reflux and removing elimination water by azeotropic distillation. Obtained by:

Among the thus obtained ketimine compounds, ketimine compounds derived from a diamine having a norbornane skeleton represented by NBDA are particularly preferred because of their excellent storage stability.

The oxazolidine compound used in the present invention is represented by the following formula (8).

[0063]

Embedded image

In the formula, R ⁷ is an alkyl group such as a methyl group or an ethyl group, a polyether group or the like. R ⁸ and R
⁹ is an aliphatic hydrocarbon group having 1 to 6 carbon atoms, 6 to 8 carbon atoms
Is an aromatic hydrocarbon group. In particular, methyl, ethyl, propyl, isobutyl, isopentyl, or

[0065]

Embedded image

These are preferred from the viewpoint of obtaining raw materials. Also, R
It is preferably an alicyclic hydrocarbon group having 6 to 8 carbon atoms in which ⁸ and R ⁹ are bonded. R ¹⁰ represents a hydrogen atom or a methyl group. When R ¹⁰ is other than a hydrogen atom or a methyl group,
There is a problem in obtaining raw materials.

Specific examples include N-methyl-2-isopropyl-2,5-dimethyl-1,3-oxazolidine,
N-ethyl-2-isopropyl-2,5-dimethyl-
1,3-oxazolidine, N- represented by the above formula (9)
Methyl-2-isobutyl-2-methyl-1,3-oxazolidine, N-ethyl-2- represented by the following formula (10)
Methyl-2- (3-methylbutyl) -1,3-oxazolidine and the like. Among them, the compound of the formula (9), the compound of the formula (10) and the like are preferable in terms of curability.

[0068]

Embedded image

Examples of the silane used as the latent curing agent (E) in the present invention include ketimine silane (S340; Chisso Corporation), oxazolidine silane and the like.
Oxazolidinesilane is, for example, 2-phenyl-3-
Obtained as a reaction product of oxazolidine ethanol and isocyanate silane. In the present invention, a silicone compound represented by the above formula (1) or a compound represented by the above formula (2) is used as the latent curing agent (E).

The compounding amount of the latent curing agent used in the present invention is an equivalent ratio of the active hydrogen after hydrolysis of the latent curing agent to the epoxy group in the epoxy resin (active hydrogen / active hydrogen /
(Epoxy group) is preferably in a ratio of 0.1 to 1.2, and more preferably in a range of 0.2 to 0.8. If the equivalent ratio is less than 0.2, the curability is deteriorated, and if the equivalent ratio is 1.2 or more, the adhesiveness is rather lowered.

The primer composition of the present invention may contain a curing catalyst in addition to the above components as long as the object of the present invention is not impaired. Examples of the curing catalyst include titanates such as tetrabutyl titanate and tetrapropyl titanate; organic tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; lead octylate Butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine,
Xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,8-diazabicyclo (5.4.0)
Amine compounds such as undecene-7 (DBU) or salts thereof with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines with epoxy compounds; γ -Aminopropyltrimethoxysilane, N- (β-aminoethyl)
Known silanol composite catalysts such as silane coupling agents having an amino group such as aminopropylmethyldimethoxysilane and the like can be mentioned. These catalysts may be used alone or in combination of two or more.

The primer composition of the present invention may contain, in addition to the above components, a rust preventive, a plasticizer, a filler, a thickener, an antioxidant, an inorganic pigment, and the like, as long as the object of the present invention is not impaired.
Components such as an organic pigment, an ultraviolet absorber, and a water absorbing agent may be blended.

Examples of the rust preventive include various rust preventive pigments, zinc phosphate, tannic acid derivatives, phosphates, basic sulfonates and the like. Examples of the plasticizer include phthalic acid ester, adipic acid ester, sebacic acid ester and tricresyl phosphate. Examples of the filler include glass powder, clay, powdered silica gel, ultrafine silica powder, and molecular sieves.

The method for producing the primer composition of the present invention comprises:
Although not particularly limited, for example, a saturated hydrocarbon polymer (A), an organic solvent (B), a polyisocyanate compound, a reaction product of a polyisocyanate compound and a silane coupling agent, a mixture, or Both (C), the epoxy resin (D), and other additives are appropriately added, kneaded sufficiently using an apparatus such as a ball mill, and uniformly dispersed to obtain a composition.

As described above, the primer composition of the present invention comprises an organic polymer having a saturated hydrocarbon skeleton excellent in weather resistance, heat resistance and water resistance, and a polyisocyanate compound and / or The combined use of a reaction product or a mixture of a polyisocyanate compound and a silane coupling agent can be realized by blending an epoxy resin.

That is, compatibility is generated by blending the epoxy resin, and a uniform composition is obtained. In addition, the composition of the present invention is paint-like, and has excellent deep-penetration and adhesiveness on a wet surface. Therefore, not only various metal sashes having a smooth surface, but also a porous adherend such as mortar. Also show good adhesion. Furthermore, by blending a latent curing agent into the composition, the curability tends to be improved and the cured product to have good warm water resistance.

Therefore, the composition of the present invention having such properties can be suitably used as a primer for bonding an adherend having various surface morphologies and a sealing material. As the sealing material, in addition to those using a saturated hydrocarbon-based polymer as a main component, for example, those using an inorganic polymer such as silicone, modified silicone-based, polysulfide-based, polyurethane-based, and acrylic urethane-based are also suitable. .

[0078]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. (Examples 1 to 6) A saturated hydrocarbon polymer (A), a mixed solution of toluene and ethyl acetate as a solvent, a polyisocyanate compound, a reactant or a mixture of a polyisocyanate compound and a silane coupling agent (hereinafter, a reactant) ), An epoxy resin, a ketimine silane and a oxazolidine as a latent curing agent in a composition shown in Table 1 or 2, and uniformly kneaded to obtain a primer composition.

Comparative Example 1 A saturated hydrocarbon polymer (A), a mixed solution of n-hexane and xylene as a solvent, aminosilane as a silane coupling agent, and a tin catalyst as a curing catalyst were blended in the composition shown in Table 2. Then, the mixture was uniformly kneaded to obtain a primer composition. (Comparative Example 2) A primer composition was obtained in the same manner as in Example except that the epoxy resin and the latent curing agent were not blended.

<Adhesion Test> The primer compositions obtained in Examples and Comparative Examples were applied to a baked fluorine-coated plate and mortar, and after curing, a sealing material having a composition shown in Table 1 was applied to a thickness of 6 mm. And the adhesion was evaluated under the following conditions.

[0081]

Initial Adhesion After leaving for 10 days at 20 ° C. and 55% RH, it was peeled off by hand. Hot Water Adhesion After leaving for 10 days under the conditions of 20 ° C. and 55% RH, it was left in water of 40 ° C. for 7 days, and then peeled off by hand. The test method was based on the simple test method described in the Sealant Handbook (edited by the Japan Sealant Manufacturers Association). The criteria for the determination are as follows. ：: CF: breaking of sealing material △: TCF: thin layer peeling ×: AF: interfacial peeling: means mixed. Table 2 shows the results.

[0083]

[Table 1]

[0084]

[Table 2]

In the table, (initial): initial adhesiveness (hot water resistance): hot water resistant adhesiveness.

<Each component in Table 1> Saturated hydrocarbon-based polymer: EPION505S (manufactured by Kanebuchi Chemical Industry Co., Ltd.) (PIB oligomer) Process oil: PAO5004 (manufactured by Idemitsu Petrochemical Co., Ltd.) Surface-treated calcium carbonate: Searets 200 ( Heavy calcium carbonate: Super S (manufactured by Maruo Calcium) Epoxy resin: bisphenol A type epoxy resin; Epicoat 828 (manufactured by Yuka Shell Epoxy) Thixotropic agent: Dispalon ^# 305 (manufactured by Kusumoto Kasei) Anti-aging agent: Tinuvin 327 (manufactured by Ciba Geigy) Titanium oxide: R-820 (manufactured by Ishihara Sangyo) Laurylamine: Farmin 20D (manufactured by Kao Corporation) Tin catalyst 1: Neostan U-28 (manufactured by Nitto Kasei)

<Each component in Table 2> Saturated hydrocarbon polymer (A): EPION103S (manufactured by Kaneka Chemical Co., Ltd.) Polyisocyanate compound 1: Desmodur HL (manufactured by Sumitomo Bayer Urethane Co.) Polyisocyanate compound 2: Takenate D110N
Reactant 1: Reactant or mixture obtained by blending 3.5 parts by weight of KBM803 (manufactured by Shin-Etsu Chemical Co., Ltd.) with 11.5 parts by weight of polyisocyanate compound 1 Reactant 2 : Reactant or mixture obtained by mixing 3.5 parts by weight of Y9669 (manufactured by Nippon Unicar Co., Ltd.) with 11.5 parts by weight of polyisocyanate compound 1 Reactant 3: 10.6 parts by weight of polyisocyanate compound 2 A reaction product or a mixture obtained by blending 4.4 parts by weight of Y9665 (manufactured by Nippon Unicar) with respect to the parts Aminosilane: aminosilane A1120 (manufactured by Nippon Unicar) Tin catalyst 2: Neostan U-303 (manufactured by Nitto Kasei) Epoxy resin: bisphenol A type epoxy resin; Epicoat 828 (manufactured by Yuka Shell Epoxy) Ketimine silane: S-340 (manufactured by Chisso) Sazorijin: MS-PLUS (ANGUS Co., Ltd.)

As is evident from Table 2, it was found that the compositions of Examples were improved in adhesiveness to mortar as compared with the conventional primer composition (Comparative Example 1). The effect of blending the epoxy resin is clear from comparison with Comparative Example 2. It was also found that the addition of the latent curing agent improved the hot water resistance.

[0089]

The composition of the present invention comprises an organic polymer having a saturated hydrocarbon skeleton having excellent weather resistance, heat resistance and water resistance;
The combined use of a polyisocyanate compound and / or a reaction product or mixture of a polyisocyanate and a silane coupling agent effective for imparting adhesiveness was realized by blending an epoxy resin. The composition thus obtained can form a sufficient coating film even on a porous mortar or the like, and exhibits good adhesiveness. Therefore, the composition of the present invention is suitable as a primer composition that can be widely applied to adherends having extremely different surface morphologies, from various metal sashes to mortars and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 175/04 C09D 175/04

Claims (5)

[Claims] 1. An organic polymer (A) having a saturated hydrocarbon skeleton and having at least one reactive functional group (hereinafter referred to as a saturated hydrocarbon polymer (A)); and (B) an organic solvent. A primer composition comprising: (C) at least one selected from the group consisting of a polyisocyanate compound and a reaction product or mixture of a polyisocyanate compound and a silane coupling agent; and (D) an epoxy resin. . 2. The primer composition according to claim 1, wherein the reactive functional group of the saturated hydrocarbon polymer (A) is at least one selected from the group consisting of a hydrolyzable functional group and a hydroxyl group. object. 3. The primer composition according to claim 1, wherein the epoxy resin (D) is at least one selected from the group consisting of a bisphenol A epoxy resin and a bisphenol F epoxy resin. object. 4. The primer composition according to claim 1, wherein the primer composition further comprises a latent curing agent (E). 5. The latent curing agent (E) is at least one selected from the group consisting of a block amine, an aminosilane, a silicone compound represented by the following formula (1), and a compound represented by the following formula (2). The primer composition according to claim 4, wherein the primer composition is one kind. Embedded image In the formula, m and n are positive integers.