JPS60186576A - Tackifier - Google Patents

Abstract

PURPOSE:A tackifier that contains a reaction product from an amine bearing specific alloxysilyl groups and an excess amount of a carbonyl compound, thus increasing adhesion, especially the adhesion to metal, when it is combined with a polyurethane resin. CONSTITUTION:The objective adhesive is composed of a reaction product from (A) an amine bearing at least one, per molecule, of an alkoxysilyl group of formula I (R<1>, R<2> are 1-4C alkyl; n is 0-2), preferably an aminoalkylalkoxysilane of formula II (R<3> is 1-4C divalent hydrocarbon; Z is H, 1-4C aminoalkyl; m is 0-2) such as N-(beta-aminoethyl)aminoethyltrimethoxysilane and (B) an excessive amount of a carbonyl compound, preferably a beta-dicarbonyl compound of formula III (R<4>, R<5> are 1-16C alkyl, 6-12C aryl, 1-4C alkoxy).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is directed to adhesive agents, more specifically to polyurethane resins. IL! Suddenly, the contact, the 6th sex is directed,
Special +'-'011'A K as metal (stainless steel,
Sufficient contact Tlt force to aluminum plates, galvanized steel plates, etc.).

This invention relates to an adhesion promoter that imparts adhesion.

Polyurethane resin has a wide range of physical and chemical properties, ranging from viscous liquids to rubber elastic bodies and even tough plastics, due to its flexible molecular design. It is an indispensable material for plastic molded objects, plastic foam molded objects, rubber processed products, paints, adhesives, sealants, etc. in the fields of industrial use, and has been actively used for a long time. Research and development has been carried out, and various polyurethane resin compositions have been put into practical use.

These polyurethane resins can be used as adhesives, sealants,
When used in paints, coating materials, etc., the composition is required to have excellent adhesion and adhesion to the body or object to be coated.

However, conventionally known polyurethane resin compositions generally do not have sufficient adhesion to inorganic bodies such as metal, glass, and concrete, and rocky bodies such as plastics, rubber, and surfaces coated with various paints. Since the surface of the adherend or the object to be coated is coated with a solvent solution such as a polyincyanate compound, silane Katzbrin 1 [1], titanate compound 11, etc., in advance,
After carrying out so-called adhesion promoting primer 91L processing, a method is adopted in which a polyurethane resin (acid) is applied and processed.

However, with this method, due to primer treatment, the contact cost is 7 yen.
There are disadvantages such as an increase in the labor involved in work, painting, etc., and an increase in production and processing costs.

On the other hand, the adhesive strength and adhesion of polyurethane resin compositions can be improved.
To increase the content of active in-i-7 groups, or to add silane coupling agents, etc.:i'-7
(A method of blending a doping agent has been proposed. However, such a method has problems such as low storage stability and foaming. There is also a limit to the adhesion to the above-mentioned adhesion agents, and the cost is also high. However, on the other hand, the active hydrogen of Ami 7 groups instantly reacts with the old incyanate groups in polyurethane to induce a crosslinking reaction, so it is extremely difficult to formulate them as the same composition. Trouble 1
There are 11. Furthermore, the use of epoxyalkoxysilanes and mercaptoalkoxysilanes has also been proposed, but the improvement in adhesion is often insufficient.

In view of these problems, the present inventors conducted intensive research to provide an excellent adhesion promoter, and as a result, they developed an amino compound having a specific alkoxysilyl group! The reaction product obtained by reacting with Fukisada's carbonyl compound and converting its primary and/or secondary amino groups into ketimine or enaminate with the carbonyl group effectively improves the R contact properties of polyurethane resin compositions. The present invention was completed based on the discovery of the following.

20% 44 Noya! That is, the present invention provides at least one formula in one molecule, , straight-chain or branched alkyl groups having 1 to 4 carbon atoms (e.g. methyl, ethyl, propyl, isopropyl,
butyl, imbutyl, 5ec-butyl], and 11 means 0, 1 or 2], and the reaction product of an amine compound having an alkoxysilyl group shown in the following formulas and an excess of the carbonyl compound of I-5. The present invention provides a characteristic adhesive agent.

The amine compound having at least one alkoxysilyl group in one molecule in the present invention includes those known in the art, preferably of the formula 1: [wherein 1 (1 and 2 are the same as above, 1 ( is a divalent hydrocarbon group having 1 to 4 carbon atoms (e.g. methylene, ethylene, propylene, butylene), l is a hydrogen atom or an aminoalkyl group having 1 to 4 carbon atoms (e.g. aminomethyl, aminoethyl, amino (propyl, aminobutyl), n] means 0.1 or 2].Specifically, N-[β-aminoethyl]aminomethyltrimethoxysilane, r-aminopropyltriethoxysilane, a-aminopropylmethyljethoxysilane, N-(β-aminoethyl)-t-aminopropyltri-1-toxinlane, N=(β-aminoethyl)
-γ-Aminopropylmethyldimethoxysilane and the like can be used.

Other examples of the amine compound include an excess of aminoalkylalkoxysilane compound (1) and the following (wherein R'', k2, R3 and m are the same as above, and G is glycidoxy or epoxy Examples include compounds obtained by heating and reacting epoxyalkylalkoxysilane compounds with cyclohexyl groups under stirring.

This reaction is performed on aminoalkylalcoquinsolane compounds (
(2) It is desirable to use 1 mol of the epoxyalkylalkoxysilane compound (H) and 0.9 mol or less, preferably 0.1 to 0.6 mol. Examples of the epoxyalkylalkoxysilane compound (11) include f-glycidoxypropyldimethylethoxysilane, l-glycidoxypropylditylethoxysilane, l-glycidoxypropylditylethoxysilane, l-glycidoxypropyldimethylethoxysilane, β-(3,4 −
-r-poxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, and the like.

1-, ,,L! In amine compounds such as, the hydrogen bonded to the elementary atom is active, so if the compound is blended as is, it will quickly react with the active isocyanio groups in the polyurethane resin fi111 and form urea bonds. In order to form, crosslink, and fi'Jj, in the present invention, this is reacted with a carbonyl compound in advance, and the primary and/or secondary amino group in the amine compound and the carbonyl group are dehydrated and condensed. They are reacted and combined to form a compound having so-called enamine groups and ketimine groups, in which the amino groups are blocked with water-free 1. Since the reaction product returns to the amine compound and carbonyl compound even if it is hydrolyzed by moisture and steam in the air, it is necessary to store the product under sufficient moisture protection before use and after blending.

Carbonyl compounds used for the purpose mentioned above include known ones, such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylace)aldehyde, glyoxal,
Aldehydes such as benzaldehyde, cyclopentanone, trimethylcyclopentanone, cyclohexanone,
Cyclic ketones such as trimethylcyclohexanone, aliphatic ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diimpropyl ketone, dibutyl ketone, diisophthyl ketone, etc. 1, and the formula: %Formula%([1) (wherein II and 1 (5 are the same or different)
7. Alkyl groups each having 1 to 16 carbon atoms (e.g., methyl, ethyl, propyl, butyl, heptyl, hexyl,
octyl, nonyl, decyl, undecyl, hexadecyl, etc.), an aryl group having 6 to 12 carbon atoms (for example, phenyl, tolyl, hexyl, naphthyl, etc.), or an alkoxy group having 1 to 4 carbon atoms (for example, methoxy, ethoxy, propoxy, methoxy, etc.)], such as acetylacetone, methyl acetoacetate, ethyl acetoacetate, 71-
Examples include dimethyl nonate, diethyl malonate, methylethyl malonate, and dibenzoylmethane. Among these, β-dicarbonyl compounds (Ill) having an active methylene group are particularly preferred.

The reaction between the above amine compound and carbonyl compound is carried out under the same conditions -F as for the usual dehydration condensation reaction between an amine and an aldehyde or ketone, for example, 1j! It is carried out in the presence of (water?'i1) or while removing water L'! under heating reflux.More specifically, a carbonyl compound ( Ta!
In the case of β-dicarbonyl compound (In), one of the two keto groups is reacted) in a suitable solvent such as toluene, xylene, benzene, etc., with molecular sieve;
A water-absorbing agent such as magnesium phosphate is added to the silkworms and allowed to react under heating for 7 minutes.

The adhesion agent according to the present invention may be a reaction product of an amine compound having an amino group blocked with a carbonyl compound or a combination of two or more of them. By blending this into a normal polyurethane resin composition, desired adhesiveness can be imparted.The blending weight is usually 0.05 to 5.0% (heavy equipment
, hereinafter the same), preferably in the range of 01 to 1.0%. If it is less than 0.05%, the desired adhesion property will not be achieved.
On the other hand, if more than 50% of the silyl ether water, 9471j, is combined with e-self, the alcohol produced by the silyl ether water, 9471j, will react with the inanate. It's a hindrance! Once i (A7,.

In addition, the polyurethane resin composition described in "-" is, for example, a random or block copolymer obtained by ring-opening bonding of propylene oxide and ethylene oxide in the presence of an elementary compound of polymexyl alkylene ether polyol (low molecular weight F layer active). Polyoxyethylene-propylene polyol, polyoxybutramethylene glycol nat by ItM ring base of tetrahylonolane), polyester polyol (polyol obtained by reacting polybasic acid and polyhydric alcohol, ε- Lu caprolactone
ll m bonded polyol, etc.), hydroxyl group-containing polybutadiene polyol, acrylic polyol, castor tone, Su7 body, Tollura. React with polyols such as cotton and excess; 11 polyisocyanate compounds (aliphatic polyisocyanates, FJJ+, alicyclic polyisocyanates, aromatic polyisocyanates, etc.) The main component is a urethane prepolymer obtained from
Examples include those to which catalysts, anti-aging agents, pigments, etc. are added.

By blending the adhesive of the present invention with the above-mentioned structure into a polyurethane resin composition, the adhesion to metal adherends such as stainless steel, aluminum plates, and zinc-treated temporary surfaces is improved, and It is recognized that the amine compound whose amino group is blocked is dissociated from moisture after application of the composition, and the block is removed when the composition is applied, reacts with the insea ester, develops a crosslinking effect, and contributes to the improvement of physical properties. .

The present invention will now be described in more detail with reference to Examples. In Examples and Test Examples, ``part'' means 屯; ketto means foam: taste.

Example 1 Reaction tank +C purged with dry nitrogen gas, 150 parts of dehydrated toluene, 22.2 parts of N-(β-aminoethyl)-r-aminopropyltrimethochine silane, and 15 parts of molecular sheep as a water absorbing agent. JJD, 20 r3'13 t-acetylacetone was gradually added under stirring at room temperature, and after 7 hours of addition, it was left in the room for another 4 hours. Stir the mixture to react. After the reaction is complete, suck the water absorbing agent, add adhesive ft 9- agent toluene,
122%).

Example; 2 22.1 parts of γ-aminopropyl 1-ethoxysilane and γ-glycidoxypropyltrimethoxysilane 7C)3
part (molar ratio, 1:0.3) of dehydrated toluene 150i1i
1≦1 month] The reaction is then heated under stirring at 50'C for several hours to obtain a mixture containing aminoalkoxysilane having unreacted amino groups and imino groups.

To a solution of 179.13 parts of the above mixture in toluene, 1sss of molecular sieves was added at night, 26 parts of 1 methyl acetoacetate was added dropwise in room 1A1j under vigorous stirring, and the mixture was stirred at room temperature for 6 hours. and react to obtain an adhesion promoter solution.

Examples: 3 to 9 Using each component in the number of copies shown in Table 1 in the same manner as in Example 1, incubate 18 and 71. Obtain adhesive (t'7 agent solution).

Test Example + Iij The effect of adhesion on polyurethane resin & Il acid was tested using the adhesion agent (-14) of Examples 1 to 9.

(1) Preparation of urethane prepolymer polyoxyalkylene ether diol (molecule i, 7'
(: , 2600, i ('6 Product name San-X PL-2
100, manufactured by Seiseikasei TL Gyo Co., Ltd.) 56 parts, polyester polyol (polypropylene glycol adipate ester, trade name T Decanyu Ace F-67, manufactured by Asahi Denka Kogyo Co., Ltd.) 50 Fr1 (and diphenylmethane-
8100 parts of 4,4'-diisocyanate was substituted with dry nitrogen residue to allow addition of 1000 parts of 4,4'-diisocyanate. , reacted for 4 hours, and immediately became active isocyanate.
Group content: 14%, viscosity: 10. +100 CI) S urethane prepolymer? 1 noru.

(11) Production of polyurethane resin composition
+rC The obtained urethane prepolymer 5o part i was preliminarily 0.
Add 30 parts of calcium carbonate dried to a moisture content of 0.5% or less, 10 parts of clay, 1.0 part of adhesive solution of each thick example, and 711 parts of xylene, Stir and mix to prepare polyurethane resin χ11 composition 'd:' 7:
do.

(il) Adhesion and storage stability test The urethane resin composition obtained in the above (11) was
25 mm, length 10 (1 m, thickness 3. Apply evenly to the plywood: 1609/nf), knead, and paste a stainless steel plate of the same shape (1'l 0.2 mm). The sample was left in a warm and humid room at 2°C/65% Rl-1 for curing.

180'il secondary strength (initial adhesive strength) of the obtained cured product
The water-resistant adhesive strength (cured product was placed in water at 40'C for 1 month) was measured, and the results are shown in Table 2. In addition, storage stability was evaluated by leaving the polyurethane 1 fat composition at 40' and checking the number of days until solidification.The results are also shown in Table 2.

As a comparative example, a polyurethane resin composition was produced in the same manner except that no adhesion promoter was used, and its initial adhesive strength and water resistance rj/jnj are also listed in Section 2k.

Table 2 Also, the adhesive chair of the present invention]! j, agent is polyurethane tree 1
In addition to iN, modified silicones (e.g., reaction products obtained by silylating the terminals of polyalkylene needle polyols), silicone resins (e.g., silyl,
14 bonds are classified as the upper class, and the terminal reacts with a hydroxyl group to form acetic acid-removed type,
It has also been recognized that it is effective as a physical property improver for epoxy resins, etc.

Example 10 Modified silicone Pvl S P-20A (manufactured by Recording Chemical Industry Co., Ltd.) 45 parts, ]) OPIO part, ash acid carne 1
45 parts of cum, 3.5 parts of titanium oxide, browning f4 of Example 2
A sealing material ti11 composition made of exfoliated silicone is prepared by mixing and stirring 1.0 part of agent 1j and 0.5 part of catalyst.

Next, a Type 11 tensile test sample was prepared using the above sealing hole composition and using an aluminum plate as an adherend.

Adhesive strength after curing for 2 weeks at 20°C is 3.5.2g
The cohesive failure was /tJ, and the adhesion was good.

Note that the adhesive agent of the present invention is added to JI
In a dumbbell physical property test based on the SK 63011 scent, the tensile strength was 11/(g/cyl), the elongation at break was 870%, and the physical properties were also improved.

Claims (1)

[Claims] 1. At least one formula, R1 -S i -(0R2) -n in one molecule [wherein kl and lζ2 are the same or different and each is an alkyl group having 1 to 4 carbon atoms] , and n means 0.1 or 2] An adhesion promoter comprising a reaction product of an amine compound having an alkoxysilyl group represented by the following formula and a carbonyl compound of excessive stabilization. 2. The amine compound having an alkoxysilyl group is
Formula, [In the formula, 1 (1 and 2 are the same or different, so that it is an alkyl group with 1 to 4 carbon atoms, 1 (1 is a radical number of 1 to 4)
4 divalent hydrocarbon groups, Z is a hydrogen fragment J"- or an aminoalkyl group having 1 to 4 carbon atoms, and m means 0.1 or 2. 3. An amine compound having an alkoxysilyl group has the formula: [In the formula, 1 (and 2 are the same or different and are each an alkyl group having 1 to 4 carbon atoms, 1 ( 3 is a double hydrocarbon group having 1 to 4 carbon atoms, Z is a hydrogen fragment J1 or a carbon number 1 to 4
4 aminoalkyl groups, and m means 0, l or 2] and [wherein R, R, R and 1n are the same as above; An anti-LL having an amino group or an imino group in the reverse layer with a less than modern epoxyalkylalkoxyrane represented by
4. The carbonyl compound has the formula: % formula % [wherein ■ (and 1 ( are the same or different and each has an ash number of 1 to 16). an alkyl group having 6 to 12 ash atoms, or an alkoxy group having 1 to 4 carbon atoms. .