JPH03239761A - Primer composition - Google Patents

Abstract

PURPOSE:To prepare a primer compsn. improved in the compatibility and adhesion to an adhesive by using, as the main component, a compd. which is prepd. by adding a specific compd. and then introducing an acrylic copolymer chain to a hydrogenated polybutadiene glycol. CONSTITUTION:A primer compsn. contg., as the main component, a reaction product obtd. by adding a vinylated and hydroxylated compd. or a mercaptized and hydroxylated compd. to the terminal hydroxyl groups of a hydrogenated polybutadiene glycol through isocyanate groups of a polyisocyanate compd. and then copolymerizing vinyl or mercapto groups of the resulting adduct with at least one copolymerizable monomer selected from the group consisting of acrylic acid, an acrylic ester, methacrylic acid, a methacrylic ester, and a compd. having a copolymerizable unsaturated bond in the presence of a hydroxylated copolymerizable monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is useful as a primer composition, more specifically as an adhesive primer for polyolefin materials, and comprises a hydrogenated polybutadiene glycol with a specific compound added thereto. , relates to moisture-curable or two-part curable primer compositions.

Prior Art and Problems to be Solved by the Invention Hydrogenated polybutadiene glycol has been attracting attention as a new adhesive material for polyolefin materials, which are being put into practical use as automobile interior materials, especially from the viewpoint of weight reduction. Due to its low polarity, it has poor compatibility with other components, and when used as a primer component, it has poor adhesion to adhesives.

Means for Solving the Problems The present inventors conducted intensive research to take advantage of the use of such hydrogenated polybutadiene glycol as an adhesive material, and found that a specific compound was added to the terminal end of hydrogenated polybutadiene glycol. They discovered that if they were introduced and further modified by introducing an acrylic copolymer chain, the polarity would be increased, the compatibility would be improved, and the adhesion to adhesives would be improved, and this led to the completion of the present invention. Ta.

That is, the present invention adds a compound having a vinyl group and a hydroxyl group in the molecule or a compound having a mercapto group and a hydroxyl group in the molecule to the terminal hydroxyl group of hydrogenated polybutadiene glycol via the isocyanate group of a polyisocyanate compound. Then, a copolymer selected from the group of acrylic acid acrylate, methacrylic acid, methacrylate ester, and a compound having a copolymerizable unsaturated bond is added to the vinyl group or mercapto group in the presence of a hydroxyl group-containing copolymerizable monomer. The present invention provides a primer composition characterized by containing as a component a reaction product copolymerized with at least one polymerizable monomer.

The hydrogenated polybutane ene glycol used in the present invention is a telechelic polymer containing a hydroxyl group at the end of the molecule, and may have a hydrogenation rate of 20% or more, preferably 90% or more.

Examples of compounds having a vinyl group and a hydroxyl group in the molecule used in the present invention include 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, and 4-hydroxypropyl acrylate. a hexyl acrylate,
5-hydroxycyclooctyl acrylate, 5-hydroxycyclooctyl methacrylate, 2-hydroxo-
3-phenyloxypropyl acrylate, 3-chloro(
Examples include 7-2-hydroxypropyl methacrylate, glycerol monomethacrylate, and compounds having a mercapto group and a hydroxyl group in the molecule include 2-mercaptoethanol, 3-mercaptopropanol,
-Mercaptopropatol, 2-hydroxypropanethiol, etc. (hereinafter, these compounds are referred to as bridge compounds).

In the present invention, the addition and introduction of the bridge compound to the terminal of hydrogenated polybutadiene glycol can be carried out via the isocyanate group (NGO) of the polyisocyanate compound, and specifically, it is carried out by the following method.

■Excess amount of polyisocyanate compound (NGO10H equivalent ratio -1
After urethane prepolymerization at 0 to 1.5/l, the remaining NGO was treated with a bridge compound (NGOloH or SH
Equivalence ratio = 1/1.0-1゜5)
(hereinafter referred to as method ①), or ② a bridge compound and an excess amount of a polyisocyanate compound (NG Olo H or SH equivalent ratio = 1.0 to 1.
5/I), the terminal hydroxyl group (NCOlo) of hydrogenated polybutadiene glycol (
Equivalence ratio = 1/1.0-1.5)
(hereinafter referred to as method ■).

Examples of the polyisocyanate compound used here include aliphatic polyisonoanates such as hexamethylene diisocyanate, 2.2.4-trimethylhexamethylene diisocyanate, and lysine methyl ester diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, hydrogenated Alicyclic polyisocyanates such as tolylene diisocyanate, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthylene diisocyanate, xylylene diisocyanate, triphenylmethane triisocyanate, tris(4-phenyl isocyanate) thiophosphate, Aromatic polyisocyanates such as a trimethylolpropane adduct of diisocyanate can be mentioned.

In the present invention, the hydroxyl group-containing copolymerizable monomer to be copolymerized with the vinyl group or mercapto group of the bridge compound added to the hydrogenated polybutadiene glycol is
A compound having a vinyl group and a hydroxyl group in the molecule, such as the above-mentioned 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxobutyl acrylate, 2-hydroxyethyl methacrylate, hydroquinpropyl methacrylate, hydroxybutyl methacrylate, 4-hydroxy Examples include synchronohexyl acrylate, 5-hydroxycyclooctyl acrylate, 5-hydroxycyclooctyl methacrylate, 2-hydroquine-3-phenyl oxinbrobyl acrylate, 3-chloro-2-hydroquinepropyl methacrylate, and glycerol monomethacrylate. , in the presence of at least one of these, acrylic acid, acrylic ester (e.g. methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, 2-ethoxoethyl acrylate, glycidyl acrylate, acrylic acid) acid tetrahydrofurfuryl,
1.4-butanediolne acrylate, 1.6-hexanediol diacrylate, pentaerythritol triacrylate, etc.), methacrylic acid, methacrylic acid esters (e.g. methyl methacrylate, edyl methacrylate, butyl methacrylate, isobutyl methacrylate, methacrylate) t-butyl acid, 2-ethylhexyl methacrylate, octyl methacrylate, isodecyl methacrylate,
Lauryl methacrylate, uryl methacrylate, tridecyl methacrylate, cetyl methacrylate
Stearyl, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoedyl methacrylate, t-butylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc.), and acrylamide , acrylonitrile, acrolein, vinyl acetate, styrene, N-methylolacrylamide, vinylpyrimene, maleic anhydride, vinylpyrrolidone, butadiene, and the like. The seeds are subjected to copolymerization.

The above copolymerization can be carried out by a conventional method.

For example, hydrogenated polybutadiene glycol to which a bridge compound has been added (hereinafter referred to as addition-introduced hydrogenated polybutadiene glycol) is mixed with a solvent (toluene, benzene, 1,
1.1-Trichloroethane, etc.), and then a radical-generating polymerization initiator (benzoyl peroxide, azobisisobutyronitrile, cumene hydroperoxide, L-
butyl hydroperoxide, potassium persulfate, ammonium persulfate, etc.) and the copolymerizable monomer in the presence of the hydroxyl group-containing copolymerizable monomer,
60～! Copolymerization is carried out for 1 hour or more, preferably 2 to 4 hours while heating at 00°C under reflux. In this copolymerization reaction, the ratio of addition-introduced hydrogenated polybutadiene glycol and copolymerizable monomers (hydroxyl group-containing copolymerizable monomer and other copolymerizable monomers) is 100 parts of addition-introduced hydrogenated polybutadiene glycol. (parts by weight, the same applies hereafter) to 1 to 100 parts, preferably 5 to 30 parts, of the copolymerizable monomer. If the amount of the copolymerizable monomer is less than 1 part, no improvement in compatibility will be observed, and if it exceeds 100 parts, good adhesion to polyolefin materials will tend not to be obtained.

The hydroxyl group-containing copolymerizable monomer is used in combination with the copolymerizable monomer so that the molecule of the copolymerized reaction product has 2 to 10 hydroxyl groups.

The above polymerization initiator is usually used in an amount of 0.2 to i parts per 100 parts of addition-introduced hydrogenated polybutadiene glycol. Although the properties are improved, the viscosity of the solution may increase and gelation may occur. Furthermore, a chain transfer agent (such as a mercaptan compound) may be added as necessary.

Through such copolymerization, a reaction product of hydrogenated polybutadiene glycol into which an acrylic copolymer chain containing a hydroxyl group has been introduced (hereinafter referred to as copolymerized modified hydrogenated polybutadiene glycol) is obtained.

The primer composition according to the present invention is prepared by diluting and dissolving the copolymerized modified hydrogenated polybutadiene glycol (3 to 20% weight%), reaction catalysts (dibutyltin silaurylate, triethylamine, lead octylate, etc.), stabilizers [4-methoxyphenol, 2.6-
Sheet-t-butyl-4-methylphenol, 2,2-methylene-bis (4-methyl-6(-methylphenol), nickel dibutylnodiocarbamate, etc.), polyol components (acrylic polyol, polyether polyol,
It is composed of a system containing appropriate amounts of polyester polyol, himan oil derivatives, etc.), epoxy resin, etc.

The primer composition of the present invention having such a structure can form a film by volatilization of the solvent, and is useful for promoting adhesion of moisture-curable urethane adhesives and the like.

Further, the moisture-curable primer composition according to the present invention has a hydroxyl group of the copolymerized modified hydrogenated polybutadiene glycol,
The component is an isocyanate group-containing urethane prepolymer obtained by reacting an excess amount of a polyisocyanate compound. In such a reaction, the polyisocyanate compound may be selected from polyisocyanate compounds used for addition and introduction of a bridge compound to the terminal of the hydrogenated polybutadiene glycol, NGO10 for the hydroxyl group of glycol
Blended in an excess amount so that the H equivalent ratio is 2 to 10/1,
Incubate at ~110°C for 1-48 hours. If necessary, the above-mentioned solvent, reaction catalyst, stabilizer, etc. can also be blended in appropriate amounts with the isocyanate group-containing urethane prepolymer.

Furthermore, the two-component primer composition according to the present invention comprises the copolymerized modified hydrogenated polybutadiene glycol and a polyisocyanate compound, and these two components are prepared before use and then applied as a primer. As the polyisocyanate compound, the polyisocyanate compound used to add and introduce the bridge compound to the terminal of the hydrogenated polybutadiene glycol is used, and is cured by reacting with the hydroxyl group of the copolymerized modified hydrogenated polybutadiene glycol. Forms a film.

These primer compositions of the present invention may be applied to the adhesive surface of an adherend according to a conventional primer coating method, and then a bonding operation may be carried out using a conventional adhesive. Applicable adherends include the intended target polyolefin material (P
(P, EPDM, modified PP, modified PE, PP composite, etc.)
In addition, various materials such as synthetic resin films or sheets, synthetic resin leather, glass materials, ceramic materials, and concrete materials can be mentioned. Further, as adhesives that can be used in combination with the primer composition of the present invention, any adhesive (or sealant) such as urethane resin, acrylic resin, epoxy resin, cyano resin, CR rubber, silicone resin, modified silicone resin, etc. can be used. You can choose. It can also be used as a paint primer.

The primer composition of the present invention has the following properties in terms of plasticizer resistance, chemical resistance, heat resistance, and water resistance. ; shows remarkable significance.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Examples 1 to 6 (1) Production of addition-introduced hydrogenated polybutadiene glycol: Method ■ 100 parts of hydrogenated polybutadiene glycol (manufactured by Mitsubishi Chemical Industries, Ltd., Polyteal H, hydrogenation rate 100%) and M
After reacting DI (2 tl) in 400 parts of toluene at 80°C for 8 hours, 7 parts of 2-mercaptoethanol was added thereto, and the reaction was carried out at 80'C for 4 hours to form a hydrogenated polyamide containing mercapto groups. Obtain butadiene glycol lysate.

Onnasenbo TDI (14 parts) and 2-hydroxyethyl methacrylate
After reacting 110 parts at 80°C for 8 hours, 40 parts of toluene
0 parts and hydrogenated polybutadiene glycol (Polychye AyH
) IQON is added, dissolved, and reacted at 8°C for 8 hours to obtain a solution of hydrogenated polybutadiene glycol having a vinyl group end added thereto.

(2) Preparation of primer composition: Example 1.2 (Primer composition containing copolymerizable modified hydrogenated polybutanoene glycol) Addition-introduction hydrogenation obtained by method (1) or (1) above Add 8 parts of methyl methacrylate, 1 part of 2-hydroquinethyl methacrylate, 1 part of maleic anhydride, and 0 parts of azobisisobutyronitrile to 1+oo parts of polybutanoene glycol solution, and make 80 parts of polybutanoene glycol solution.
After reacting for 4 h at °C, 4-methquinphenol 0
．． 2 parts were added to obtain a hydroxyl group-containing copolymerized modified hydrogenated polybutadiene glycol solution, which was used as the primer composition of Example 1.2.

Example 3.4 (Moisture-curable primer composition) To 100 parts of the hydroxyl group-containing copolymerized modified hydrogenated polybutanoene glycol solution of Example 1.2 above, MDI (2 parts) and toluene (1 part) were added.
00 parts and 001 parts of dibutyltin silaurylate were added and stirred and mixed at 50°C for 24 hours to obtain an NCO group-containing urethane prepolymer solution, which was combined with the moisture-curable primer composition of Example 3.4. do.

Example 5.6 (Two-night primer composition) Example 1 above
．． A component obtained by adding 100 parts of toluene to 100 parts of the hydroxyl group-containing copolymerized modified hydrogenated polybucnoene glycol solution d of No. 2;
The two-legged primer composition of Example 5.6 is prepared in which two components consisting of triphenylmethane triisonoanate and a 20% solution of methylene chloride are mixed in a ratio of 100:3 as the polyisocyanate compound.

(3) Adhesion test: PP board (manufactured by Mitsui Petrochemical Industries, Ltd., IP-407)
The primer compositions of Examples 1 to 6 were coated with 309/butt 2 and dried at room temperature for 15 minutes. -053) on one side of the PP board (manufactured by Sunstar Giken Co., Ltd., Penguin Semen L-#903), and after drying at room temperature for 5 minutes, overlap the PP board and the chloride pinyrunte, 5 parts g
After compaction with a roller, initial peel strength, normal peel strength and heat creep resistance are measured. The results are shown in Table 1 below.

Comparative Example 1.2 Adhesion test conducted in the same manner as in Example using the addition-introduced hydrogenated polybutadiene glycol solution obtained by method (1) or (1) as the primer composition of Comparative Example 1.2. The results are shown in Table 1.

Table 1 ■) After 20°C x 24 hours ■) After 20°C x 24 hours in an 80°C atmosphere, 1009/
Apply a load of 25mm in a 90” corner direction and measure the peeling length after 24 hours.

Claims (1)

[Claims] 1. To the terminal hydroxyl group of hydrogenated polybutadiene glycol, via the isocyanate group of a polyisocyanate compound,
A compound having a vinyl group and a hydroxyl group in the molecule or a compound having a mercapto group and a hydroxyl group in the molecule is added into the molecule, and then acrylic acid or acrylic acid is added to the vinyl group or mercapto group in the presence of a hydroxyl group-containing copolymerizable monomer. A primer composition comprising as a component a reaction product copolymerized with at least one copolymerizable monomer selected from the group of esters, methacrylic acid, methacrylic esters, and compounds having copolymerizable unsaturated bonds. thing. 2. A moisture-curable primer composition comprising an isocyanate group-containing urethane prepolymer obtained by reacting the hydroxyl groups of the copolymerized reaction product according to claim 1 with an excess amount of a polyisocyanate compound. 3. A two-component primer composition comprising the copolymerized reaction product according to claim 1 and a polyisocyanate compound.