JPS60118782A - Heat-resistant adhesive composition - Google Patents

Abstract

PURPOSE:The titled composition, consisting of a liquid diene based polymer containing active hydrogen groups, a specific polyisocyanate compound and a bituminous substance, capable of exhibiting improved tackiness and adhesive property, and suitable for adhesive tapes, etc. CONSTITUTION:A composition obtained by incorporating (A) a liquid diene based polymer containing active hydrogen groups, e.g. polybutadiene homopolymer, with (B) a polyisocyanate compound having >2, preferably >=2.7 isocyanate groups, e.g. tolylene polyisocyanate, and (C) a bituminous substance, preferably straight asphalt. The amounts of the components are preferably as follows; 0.35-0.85 equivalent, based on the active hydrogen groups in the component (A) and 50-500pts.wt., based on 100pts.wt. component (A), component (C).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-resistant adhesive composition, and more particularly to an adhesive composition that has good tack and adhesive properties and can be used even at high temperatures of 200''C or higher.

Various proposals have been made regarding adhesive compositions, and liquid reactive adhesive compositions containing active hydrogen group-containing liquid diene polymers and polyisocyanate compounds as main components are already known. For example, there are products in which bituminous substances are blended with these main components (Japanese Patent Application Laid-open Nos. 57-182!172 and 57-209977), and these exhibit excellent tackiness at normal usage temperatures, but 20
When used at a high temperature of 0° C. or higher, there is a drawback that the adhesiveness decreases.

Therefore, the present inventors further investigated adhesive compositions that can overcome these drawbacks and maintain good adhesive properties even at relatively high temperatures. It was discovered that the desired composition could be obtained, and the present invention was completed based on this finding.

Specifically, 1 the present invention is directed to a liquid diene polymer containing active hydrogen groups (hereinafter referred to as component (A)), a polyisocyanate compound having more than 2 incyanate groups (hereinafter referred to as component (B)
) ingredients. ) and a blue substance (hereinafter referred to as component (0)).

The active hydrogen group-containing liquid diene polymer which is component (A) of the composition of the present invention refers to a liquid diene polymer having an active hydrogen group such as a hydroxyl group, carboxyl group, amino group, imino group, or mercapto group at the molecular end. These liquid diene polymers are not particularly limited, and for example, those having an average molecular weight of 300 to 200
00, preferably 500 to 10,000 carbon atoms 4 to 12
There are diene polymers, copolymers thereof, and copolymers of these diene monomers and α-olefinic addition polymerizable monomers having 2 to 22 carbon atoms. In addition, liquid diene-based M modified by grafting a polymerizable monomer or adding an unsaturated carboxylic acid such as maleic anhydride or a derivative thereof to these liquid diene-based polymers [also includes combinations] It is something. in particular,
Examples include polyptadiene/homopolymer, polyisoprene homopolymer, polychloroprene homopolymer, butadiene-styrene copolymer, butadiene-imprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-octadecyl acrylate copolymer, etc. be able to. Among these, a polymer having a viscosity of 2000 poise or less, more preferably 500 poise or less, and a fine structure containing 50% or more of 1,4 bonds is used.

Next, component (B) in the present invention is a liquid diene polymer containing active hydrogen groups, which is component (A), in which the number of reactive isocyanate groups with respect to functional groups is more than 2, preferably 2.7 or more. It is a polyinsyanate compound that has two properties. In the present invention, by using such a specific polyisocyanate compound, an adhesive composition with improved heat resistance can be obtained.

In addition to the polyincyanate compounds described above, component (B) may also be a compound in the form of a prepolymer having more than two incyanate groups at the terminals obtained by reacting a polyol and a polyisocyanate in advance. (
Specific examples of component E) include the usual aromatic, aliphatic, and alicyclic compounds, such as tolylene polyisocyanate, hexamethylene polyisocyanate, diphenylmethane polyisocyanate, liquid modified diphenylmethane polyisocyanate, and polymethylene polyisocyanate. and liphenyl isocyanate, xylene polyisocyanate, and cyclohexyl polyisocyanate.

Cyclohexane phenylene polyisocyanate.

Examples include naphthalene polyisocyanate, isopropylbenzene polyisocyanate, and polypropylene glycol and tolylene polyisocyanate reaction products.

These organic polyisocyanate compounds act as a curing or crosslinking component of the active hydrogen group-containing liquid diene polymer of component (A), and in the adhesive composition of the present invention, the amount of this organic polyisocyanate compound is There is no particular restriction, and the isocyanation (isocyanation) is about 0.15 to 0.95, preferably 0.5 to the active hydroxyl group of component (A).
The prize is determined to be approximately 5 to 0.85. If the amount is too small, the effect of improving heat resistance will be insufficient, and if it is too large, the adhesive force will decrease, making it impractical.

As the bituminous substance which is the component (0) of the present invention, there is no particular restriction and known substances can be used, such as slate asphalt, semi-brown asphalt, blown asphalt, tar, or mixtures thereof, preferably. Straight asphalt or slate asphalt and other asphalts that do not require much IVLi temperature for processing are used.

The blending amount of these bituminous substances is determined depending on the use and performance of the composition of the present invention, but is usually 30 to 10 parts by weight per 100 parts by weight of the active hydrogen group-containing diene polymer.
It is determined in the range of 00 heavy forged parts, more preferably 50 to 500 heavy forged parts. If the amount is too small, the adhesive force and adhesive force will not be sufficient, and if the amount is too large, the adhesive force and adhesive force will decrease, and the heat resistance will also decrease, which is not preferable.

The composition of the present invention basically consists of the above (A) and (E).
, (0), but various additives can be added as necessary. For example, glycerin, diglycerin, trimethylolpropane,
6 moles of ethylene oxide adduct of 1,4-butanediol, ethylene glycol, and bisphenol A + ”, N
-bis(2-hydroxypropyl)aniline, etc. can be added. Still, di-n-butyltin dilaurate, stannath octoate, triethylenediamine, diethylenediamine,
Urethane catalysts such as triethylamine, naphthenic acid metal salts, octylic acid metal salts, etc. can be used. Furthermore, process oil, phthalate esters, phosphate esters, etc. can be added as plasticizers, calcium carbonate, barium sulfate, carbon black, etc. can be added as fillers, and petroleum resins, terpene resins, etc. can be added as tackifiers.

Various methods can be applied to prepare the heat-resistant adhesive composition of the present invention from the above-mentioned raw material components, such as a method in which predetermined edges of the raw material components are blended and kneaded under heating.

Since the composition of the present invention uses a special polyisocyanate compound as a raw material, it has excellent heat resistance in addition to good viscosity and adhesive properties.

Therefore, the composition of the present invention has a temperature of 200°C or more.
; It can be used effectively even at 1 μl or less without deteriorating the tackiness and adhesion.

Therefore, the adhesive composition of the present invention can be used for various adhesive tapes, anticorrosion tapes, sealants, waterproofing 4A', 1AJj
It can be used in various fields as a vibration material, vibration damping material, etc.

Next, the present invention will be explained in detail with reference to examples.

Examples 1 to 3 and Comparative Example 1 Liquid polybutadiene, polyisocyanate compound, M blue substance and urethane catalyst (di-n-butylstin dilaurate) according to the formulation fit shown in Table 1.
An adhesive composition was prepared by thoroughly mixing and stirring o and o 5 Sl- at 150°C. This composition was applied onto an i'llll paper pattern to produce adhesive paper. Composition preparation conditions and adhesive paper evaluation #! The results are shown in Table 1.

・1...Polybutadiene having a hydroxyl group at the end (Output...Polymethylene polyphenylisocyanate (manufactured by Nippon Polyurethane, Millionate Mto 200, NCoC)
O group content: 30% by weight, average number of isocyanate groups: 2.6
) ・4... Polymethylene polyphenylisocyanate (same structural formula as Kushi 3) (Made by Nippon Polyurethane 1
Milli, t-nate MIB-500, NOO-containing rat 30.
0% by weight, average isocyanate group @2.7)・S...
Made of polymethylene polyphenylisocyanate (same structural formula as φ3) (Japan Polyurethane Needle), Millionate MR-400. NOO content 30.0 mold open%, average incyanate group v! i2.9)-6...4.4'-
Diphenylmethane diisocyanate (manufactured by Nippon Polyurethane, Millionate MT.

NOO content @3s, 6mNk%, average number of functional groups 2.0)
- Ding: Measured using an inclined ball tack measuring machine (manufactured by Dejima Seisakusho ■). Measurement temperature 20'C, tilt angle 40
°, evaluated using a numerical value from 0 to 52 (the higher the value, the better the adhesion) ・8... Attach adhesive paper to a steel plate with a thickness of 2 mm, stand vertically at the test temperature, and measure the highest temperature without slippage. did.

Patent applicant: Idemitsu Petrochemical Co., Ltd. Procedural amendment (voluntary) December 26, 1982 Mr. Kazuo Wakasugi, Commissioner of the Patent Office 1. Display of incident Patent application No. 58-225454 2 Name of Hatsuho Heat-resistant adhesive composition (5) Person making the amendment Relationship to the incident: Patent applicant Idemitsu Petrochemical Co., Ltd. 4. Agent 〒104 5. Subject of correction & Contents of correction (1) Amend the claims as shown in the attached sheet.

(2) [2,7J on page 4, line 11 of the specification] [2,
Correct it to 5J.

(And more) Claims fl+ A heat-resistant adhesive composition comprising a liquid diene polymer containing active hydrogen groups, a polyisocyanate compound having more than 2 isocyanate groups, and a bituminous material. (2) A heat-resistant adhesive composition having more than 2 isocyanate groups. Claim 1, wherein the polyisocyanate compound is a polyisocyanate compound having 2.5 or more incyanate groups.
Compositions described in section ・

Claims (2)

[Claims] (1) A heat-resistant adhesive composition comprising a liquid diene polymer containing active hydrogen groups, a polyisocyanate compound having more than two incyanate groups, and a bituminous substance. (2) The composition according to claim 1, wherein the polyisocyanate compound having more than 2 isocyanate groups is a polyisocyanate compound having 2.7 or more isocyanate groups.