JPH075869B2 - Adhesive imparting agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an adhesion promoter.

[Prior Art] Conventionally, as an adhesion-imparting agent, there is one which comprises a reaction product of (1) a primary aminoalkylalkoxysilane and (2) an epoxy compound (for example, JP-A-59-24771).

[Problems to be solved by the invention]

However, in this case, the antifouling property is insufficient for various metals, ceramics and plastics.

[Means for solving problems]

The present inventors have arrived at the present invention as a result of extensive studies for the purpose of obtaining an adhesion-imparting agent having excellent antifouling properties.

That is, the present invention has the general formula [Wherein R is an alkyl group or aryl group having 1 to 4 carbon atoms, X is an alkoxy group, an alkenoxy group or OC ₂ H ₄ O
CH ₃ ), A and A'are divalent hydrocarbon groups having 1 to 4 carbon atoms, R '
Is a monovalent hydrocarbon group, and m and n are 0, 1 or 2. ] An adhesion-imparting agent comprising a reaction product of a compound (a) having a hydrolyzable silicon group and an epoxy compound (b).

In the general formula (1), examples of the alkyl group having 1 to 4 carbon atoms for R include a methyl group, an ethyl group, a propyl group and a butyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Of R, a methyl group and a phenyl group are preferable. Examples of the alkoxy group for X include an alkoxy group having usually 1 to 8 carbon atoms (for example, a methoxy group and an ethoxy group). Examples of the alkenoxy group include a propenoxy group. Of X, a methoxy group and a propenoxy group are preferred.

Examples of the divalent hydrocarbon group having 1 to 4 carbon atoms of A and A'include a linear or branched alkylene group (ethylene group, propylene group, trimethylene group, etc.).

The monovalent hydrocarbon group of _R'is an alkyl group (C _1-12
An alkyl group such as an ethyl group and a hexyl group), an aryl group (a phenyl group, a naphthyl group, etc.), an arylalkyl group (a benzyl group, a phenethyl group, etc.), an alkylaryl group (an aryl group having a C _1-12 alkyl group),
Examples thereof include a tolyl group and a nonylphenyl group), a vinylarylalkyl group (such as a vinylbenzyl group), a cycloalkyl group (such as a cyclohexyl group), and an allyl group.

In the general formula (1), when R'is a hydrogen atom, the stain resistance is poor.

Specific examples of the compound represented by the general formula (1) include N-
Alkylaminosilanes (including N-alkylaminosilanes and NN-alkylaminoalkyl substitutes thereof).
The same description is used below. ) [N-ethyl-γ-aminopropyltrimethoxysilane, N-ethyl-γ-aminopropylmethyldimethoxysilane, N-β- (Nethylaminoethyl) -γ-aminopropyltrimethoxysilane, etc.], N-aryl Aminosilane [N-phenyl-
γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethylmethoxysilane, etc.], N-arylalkylaminosilane [N-benzyl-γ-aminopropyltrimethoxysilane, N-β-
(N-phenethylaminoethyl) -γ-aminopropyltrimethoxysilane, etc.], N-alkylarylaminosilane [N-tolyl-γ-aminopropyltriethoxysilane, N-β- (N-tolylaminoethyl)- γ-
Aminopropyltrimethoxysilane, etc.], N-vinylarylalkylaminosilane [N-vinylbenzyl-
γ-aminopropyltrimethoxysilane, N-β- (N
-Vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, etc.], N-cycloalkylaminosilane [N-cyclohexyl-γ-aminopropyltrimethoxysilane, N-β- (N-cyclohexylaminoethyl) -γ-amino Propyltrimethoxysilane, etc.], N-allylaminosilane [N-allyl-γ-aminopropyltrimethoxysilane, N-β- (N-allylaminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (N -Allylaminoethyl) -γ-aminopropyltripropenoxysilane, N-β- (N-allylaminoethyl) γ-aminopropyltriethoxymethoxysilane, etc.] and the like. The compound represented by the general formula (1) may be used alone or in combination of two or more.

The epoxy compound (b) usually has a molecular weight of 44 to 16,00.
0, epoxy compounds having an epoxy equivalent of 44 to 4,000 can be mentioned.

Specific examples include the following.

(1) Alkylene oxide (ethylene oxide,
(Propylene oxide, butylene oxide, etc.) (2) Epichlorohydrin (3) Bisphenol epoxide (SHELL Co., Ltd.)
(Epikote 828, Epikote 1001 etc.) (4) phenol epoxides (novolak type phenolic resin epoxides, phenyl glycidyl ether, etc.) (5) alcohol epoxides (monool, polyol epoxides, such as butyl glycidyl ether) (6) ) Polyoxyalkylene epoxides (glycidyl ether of polyoxyethylene polyol, glycidyl ether of polyoxypropylene polyol, etc.) (7) Epoxy epoxides (glycidyl ether of adipic acid polyester, polycarplactone, etc.) (8) Diene compound Epoxide (Po from Idemitsu Co., Ltd.
Glycidyl ethers such as lyBD (polybutadiene glycol) etc. (9) Polysiloxane epoxides (polymethylsiloxane epoxide etc.) (10) Acrylic epoxides (glycidyl methacrylate methacrylic acid, acrylic oligomer or polymer epoxide etc.) (11) General formula [Wherein R ₁ is an alkyl group or aryl group having 1 to 4 carbon atoms, X ₁ is an alkoxy group, an alkenoxy group or OC ₂ H ₄ O
CH ₃ ), A ₁ and A ₂ are divalent hydrocarbon groups having 1 to 4 carbon atoms, E is a glycidoxy or epoxycyclohexyl group, and 1 is 0
Or an integer of 1 to 20, p is 0, 1 or 2. ] A compound represented by, for example, (a) Glycidoxy-based alkoxysilane (γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxydimethylethoxysilane, γ-glycidoxypropyl (Triethoxysilane, glycidoxydiethyleneoxypropyltrimethoxysilane, etc.) (b) Glycidoxy-based alkenoxysilane (γ-glycidoxypropylmethyldiisopropenoxysilane, γ
-Glycidoxypropyltriisopropenoxysilane, etc.), (c) Non-glycidoxy-based alkoxysilane (β- (3,
4 Epoxycyclohexylethyltrimethoxysilane, etc.) (d) Non-glycidoxy type alkenoxysilane (β-
Compounds such as (3,4 epoxy cyclohexylethylmethyldiisopropenoxysilane).

The epoxy compound (b) may be used alone or in combination of two or more.

Of (b), preferably (1), (3), (4),
The compounds described in the groups (5), (6), (10) and (11), and more preferably the compounds described in the groups (4), (5), (6) and (11).

The equivalent ratio of the silane compound (a) and the epoxy compound (b) is usually 1.0: 0.01 to 5.0, preferably 1.0: 0.1 to 3.0. When (b) is within this range, the antifouling property is excellent.

The reaction products of (a) and (b) are obtained, for example, by charging a sufficiently dried four-necked flask with a predetermined amount of the silane compound (a) and heating it in an oil bath to raise the temperature to 70 ° C. ) Is added dropwise and the mixture is reacted at the same temperature for about 5 hours.

The imparting agent of the present invention includes various inorganic substances (iron, tin, galvanized iron, tin,
It is applicable to substrates such as aluminum, glass, roof tiles, slate, tiles, enamel, etc. and organic substances (wood, paper, cellophane, plastics, organic paints, etc.).

The imparting agent of the present invention is a sealant (modified silicone sealant, silicone sealant, urethane sealant, etc.)
And paints (modified silicone paints, silicone paints, etc.) and the like. Further, the imparting agent of the present invention alone or, if necessary, a solvent, a resin (petroleum resin, a ketone resin, a urethane resin, etc.) and a polymer having a functional group capable of reacting with the imparting agent of the present invention (such as an NCO group-terminated prepolymer) ) Or the like can be used as a primer after being mixed or reacted.

Examples of sealants include silicone sealants and urethane sealants described in “Sealant” (Adolfuss Damcis, published by Reinhold). Further, as a modified silicone sealant, Japanese Patent Laid-Open No. 59-
Polyether polymer having a hydrolyzable silicon functional group at the end described in JP-A-24771, for example, an isocyanate-terminated polyether urethane prepolymer, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-mercaptopropyl. As a reaction product with trimethoxysilane, or as a silyl ether group at the end _{(CH 3 O) 3 -Si-} CH 2 -CH 2 -CH 2 -O-, The main component is an oxypropylene polymer having, and if necessary, a usual filler, a plasticizer, a solvent, a catalyst, a deterioration inhibitor, a pigment and the like are added.

Further, as a urethane sealant, a polyurethane resin composition described in JP-A-60-186576, such as a polyoxyalkylene ether polyol (of a random or block copolymer obtained by ring-opening polymerization of propylene oxide and ethylene oxide in the presence of a low molecular weight active hydrogen compound). Polyoxyethylene-propylene polyol, polyoxytetramethylene glycol by ring-opening polymerization of tetrahydrofuran, etc., polyester polyol (polyol obtained by reacting polybasic acid with polyhydric alcohol, polyol obtained by ring-opening polymerization of ε-caprolactone with polyhydric alcohol, etc.) ),
Hydroxyl group-containing polybutadiene polyol, acrylic polyol, castor oil derivative, tall oil derivative, and other polyols react with excess polyisocyanate compound (aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, etc.) The urethane prepolymer obtained as a main component may be added with a usual filler, plasticizer, solvent, catalyst, deterioration inhibitor, pigment, etc., if necessary.

The amount of the imparting agent of the present invention is usually 0.01 to the additive.
It is 10.0%, preferably 0.05 to 5.0%.

As a compounding and application method, an ordinary method, for example, an additive (sealant such as modified silicone sealant, silicone sealant, urethane sealant and modified silicone-based paint, silicone-based paint, paint such as urethane paint) is kneaded to form a cartridge. After the filling, a method of caulking using a cartridge gun or the like and a method of applying the kneaded product with a spatula, a spray or the like can be mentioned.

The imparting agent of the present invention usually exhibits a satisfactory adhesive effect at a temperature of -30 ° C to + 150 ° C and a humidity of 5 to 100% and causes cohesive failure of the base material or the additive.

[Examples] The present invention will be further described with reference to Examples below, but the present invention is not limited thereto. The following parts indicate parts by weight.
The abbreviations used in the examples have the following meanings.

(Silane compound) VAMS: N-β- (N-vinylbenzylaminoethyl) -γ-
Aminopropyltrimethoxysilane AAMS: N-β- (N-allylaminoethyl) -γ-aminopropyltrimethoxysilane PAMS: N-phenyl-γ-aminopropyltrimethylmethoxysilane AES: γ-aminopropyltriethoxysilane (epoxy Compound) BGE: Butyl glycidyl ether GMS: γ-glycidoxypropyltrimethoxysilane PPGE-400: Polyoxypropylene diglycidyl ether (epoxy equivalent = 400) PPGE-2000: Polyoxypropylene diglycidyl ether (epoxy equivalent = 2,000) PSE-2000: Polyorganopolysiloxane epoxide (epoxy equivalent = 2,000) GPS: γ-glycidoxypropylmethyldiisopropenoxysilane (additive) MS-1: One-component modified silicone sealant U-1: One-component Type urethane sealant S-1: One-component silicone sealant implemented Examples 1 to 8 and Comparative Example 1 The imparting agent of the present invention (Example 1) was prepared by the following production method in accordance with (a), (b) and their compounding ratios (weight ratios) shown in Table 1.
~ 8) and a comparative product (Comparative Example 1) were obtained.

(Manufacturing method) A reaction vessel replaced with dry nitrogen gas is charged with a specified amount of the component (a) and a specified amount of the component (b), and the reaction system temperature is 50 ° C to 50 ° C.
Reaction was carried out at 150 ° C for about 3 to 20 hours to obtain the imparting agent of the present invention.

Use Examples 1 to 12 The additive of the present invention and a comparative product were blended with the additive as shown in Table 2 to evaluate antifouling property and adhesiveness.

(Staining property evaluation method) Each base material was hit with a sealant in a bead shape with a width of 10 mm and a thickness of 5 mm, and cured for 5 days under a curing condition of 20 ° C and 65% RH.
A cycle test was carried out in which the substrate was immersed in warm water at ℃ for 7 days, and then left in a gear oven at 90 ℃ for 7 days, and the discoloration of the sealant-bonded surface of the substrate and its periphery and the discoloration of the sealant itself were observed.

(Adhesiveness Evaluation Method) After curing under the above curing conditions, 90% peeling was performed while applying a razor blade to the adhesive interface to check the adhesiveness. Also,
At the same time, water-resistant adhesion (immersion condition: left in warm water at 50 ° C. for 7 days) was measured by the same method to check the adhesion.

The results are shown in Table-3.

As another test, storage stability (extrudability) tests were conducted for Use Examples 8 and 11, and the results are shown in Table 4 (Test method) 1/3 cartridges were filled with the composition of Test Example and the temperature conditions were changed. Four
After accelerated storage at 0 ° C. for a storage period of 30 days, the extrudability specified in JIS-A-5758 was evaluated.

[Effects of the Invention] Since the imparting agent of the present invention has no bleed-out or migration, it has excellent stain resistance and does not discolor the base material and the additive.

In addition, it has excellent adhesiveness and is durable (water resistant,
Excellent weather resistance, outdoor dynamic tackiness resistance, etc.) and durability (heat resistance, weather resistance, water resistance, outdoor dynamic tackiness resistance, etc.).

The composition of the present invention exhibits a synergistic effect by reacting (a) and (b), for example, the stain resistance is better than that of (a) alone, and the durability such as water resistance and weather resistance is improved. The adhesiveness is also superior to that of (a) and (b) alone.

From the above effect, the imparting agent of the present invention is a sealant such as a silicone sealant, a modified silicone sealant, a urethane sealant, and a modified urethane sealant,
It is useful as an adhesion promoter for applications such as paints, cast elastomers, and adhesives.

Claims (4)

[Claims] 1. A general formula [Wherein R is an alkyl group or aryl group having 1 to 4 carbon atoms, X is an alkoxy group, an alkenoxy group or OC ₂ H ₄ O
CH ₃ ), A and A'are divalent hydrocarbon groups having 1 to 4 carbon atoms, R '
Is a monovalent hydrocarbon group, and m and n are 0, 1 or 2. ] An adhesion-imparting agent comprising a reaction product of a compound (a) having a hydrolyzable silicon group represented by the above and an epoxy compound (b). 2. (b) has a molecular weight of 44 to 16,000 and an epoxy equivalent.
The imparting agent according to claim 1, which is an epoxy compound having 44 to 4,000. 3. The imparting agent according to claim 1 or 2, wherein (b) is polyoxyalkylene epoxide. 4. (b) is a general formula [Wherein R ₁ is an alkyl group or aryl group having 1 to 4 carbon atoms, X ₁ is an alkoxy group, an alkenoxy group or OC ₂ H ₄ O
CH ₃ ), A ₁ and A ₂ are divalent hydrocarbon groups having 1 to 4 carbon atoms, E is a glycidoxy or epoxycyclohexyl group, and 1 is 0
Or an integer of 1 to 20, p is 0, 1 or 2. ] The imparting agent of Claim 1 or 2 which is a compound shown by these.