JPH0623372B2 - Resin bonding composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin-adhesive composition, and more specifically, a resin-adhesive composition with improved adhesiveness used when at least one of the adherends is a resin. Regarding

[Problems to be Solved by Prior Art and Invention]

Non-solvent type or non-solution type adhesive is selected and used as the adhesive when the synthetic resin or its foam is used as the adherend because the adhesive surface of the adherend is easily corroded by solvent etc. . As such an adhesive for resins, an adhesive composition comprising a polymer such as hydroxyl group-containing liquid polybutadiene and a compound such as diphenylmethane diisocyanate, and a composition obtained by adding a bituminous substance such as asphalt to the composition have been proposed.

Although this adhesive can avoid erosion and destruction of the resin to be adhered, it cannot be said to be sufficiently satisfactory in practical use because of its low 180 ° peel strength.

[Means for solving problems]

An object of the present invention is to provide a resin bonding composition that solves such problems.

That is, the present invention relates to a resin bonding composition comprising a hydroxyl group-containing liquid diene polymer, a polyisocyanate compound, a bituminous substance, an inorganic filler and a polyol compound.

The hydroxyl group-containing liquid diene polymer has a number average molecular weight of 300 to 25 having a hydroxyl group in the molecule, preferably at the molecular end.
000, preferably 500 to 10,000, is a liquid diene polymer. These liquid diene polymers are C4-12 diene polymers, diene copolymers, and further copolymers of these diene monomers and C2-22 α-olefin addition polymerizable monomers. There is. The hydroxyl group content is 0.1-10 meq / g, preferably 0.3-5.
It is 0 meq / g. Specifically, butadiene homopolymer,
Isoprene homopolymer, butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-
Examples thereof include octadecyl acrylate copolymer. These liquid diene polymers can be produced, for example, by reacting a conjugated diene monomer in a liquid reaction medium in the presence of hydrogen peroxide with heating.

In addition, the polyisocyanate compound is an organic compound having two or more isocyanate groups in one molecule, and is suitable for the active hydrogen-containing functional group of the hydroxyl group-containing liquid diene polymer and the polyol compound added as necessary. It has a reactive isocyanate group. Examples of the polyisocyanate compound include ordinary aromatic, aliphatic and alicyclic compounds, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI), liquid modified diphenylmethane diisocyanate and polymethylene polyisocyanate. Phenyl isocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5
-Diisocyanate, isopropylbenzene-2,4-
There are diisocyanate, polypropylene glycol and tolylene diisocyanate addition reaction products, especially M
DI, liquid modified diphenylmethane diisocyanate, tolylene diisocyanate and the like are preferable.

The mixing ratio of the hydroxyl group-containing liquid diene polymer and the polyisocyanate compound is not particularly limited, but usually the molar ratio of the hydroxyl group (OH) of the hydroxyl group-containing liquid diene polymer and the isocyanate group (NCO) of the polyisocyanate compound. Is NCO / OH = 0.2 to 10.0, preferably 0.
It is 5 to 6.0. If the blending ratio of both is out of this range, it becomes difficult to cure, which is not preferable.

Next, the bituminous substance is not particularly limited, and examples thereof include petroleum asphalt such as straight asphalt, blown asphalt, semi-blown asphalt, propane (solvent) deasphalted asphalt, petroleum pitch, coal tar, and coal pitch. The bituminous substance is 10 to 100 with respect to 100 parts by weight of the hydroxyl group-containing liquid diene polymer.
It is used in a proportion of 0 parts by weight.

Further, as the inorganic filler, mica, graphite, leucite, calcium carbonate, slate powder or the like can be used. The inorganic filler is used in an amount of 1 to 1000 parts by weight, preferably 5 to 700 parts by weight, based on 100 parts by weight of the hydroxyl group-containing liquid diene polymer.

Next, various kinds of polyol compounds can be used, and any of primary polyol, secondary polyol and tertiary polyol may be used. Specifically, for example, 1,2-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 2,5-hexanediol, 2,4-hexanediol, 2-ethyl-1,3
-Hexanediol, cyclohexanediol, glycerin, N, N'-bis-2-hydroxypropylaniline, N, N'-bishydroxyisopropyl-2-methylpiperazine, propylene oxide adduct of bisphenol A, and the like. A low molecular weight polyol containing a hydroxyl group bonded to a primary carbon can be mentioned.

Further, as the polyol, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or the like which does not have a hydroxyl group bonded to secondary carbon may be used. . A diol is usually used as the polyol used in the present invention, but triol or tetraol may be used, and the molecular weight thereof is in the range of 50 to 500.

This polyol compound is used together with the above-mentioned inorganic filler, and the amount thereof is 1 to 1000 parts by weight, preferably 3 to 200 parts by weight, per 100 parts by weight of the hydroxyl group-containing liquid diene polymer. .

The resin bonding composition of the present invention can be obtained by blending the above-mentioned components, but other additives can be appropriately added if necessary. For example, a polyamine compound can be added as a reinforcing agent, and the polyamine compound is not particularly limited, and may be any of diamine, triamine, and tetraamine. Furthermore, any of primary polyamine, secondary polyamine, and tertiary polyamine can be used. Examples of the polyamine compound include aliphatic amines such as hexamethylenediamine; 3,3′-dimethyl 4,
Alicyclic amines such as 4'-diaminodicyclohexylmethane; aromatic amines such as 4,4'-diaminodiphenyl:
Examples thereof include tetramine such as 2,4,6-tri (dimethylaminomethyl) phenol.

Furthermore, a plasticizer such as dioctyl phthalate may be added as a viscosity modifier, a softener such as an aroma-based, naphthene-based or paraffin-based oil may be added, and an alkylphenol resin, terpene resin, Tackifying resins such as terpene phenolic resins, xylene formaldehyde resins, rosins, hydrogenated rosins, coumarone resins, aliphatic and aromatic petroleum resins can also be added. Further, a curing accelerator such as dibutyltin dilaurate, stannous octoate, or polyethylenediamine may be added. Further, an antiaging agent may be added for improving weather resistance, and a silicone compound or the like may be added as an antifoaming agent.

The resin bonding composition of the present invention can be obtained by blending and kneading the above-mentioned respective raw materials. As a general production method, raw materials other than the polyisocyanate compound are first blended and kneaded. The kneading conditions at this time may be determined in consideration of the types of raw materials, the mixing ratio, etc., but are usually 10 to 120 ° C., preferably 50 to 100 ° C. for 5 to 360 minutes, preferably 60 to 180 minutes. . Then, a polyisocyanate compound is added to this composition, and the mixture is stirred at room temperature for 1 to 2 minutes to obtain the resin bonding composition of the present invention.

At least one of the adherends of the adhesive composition of the present invention is a resin, and is targeted for various resins. For example, polyvinyl chloride resin (hard, soft); polyolefin resin such as polyethylene and polypropylene; polystyrene resin; polycarbonate resin; acrylonitrile-butadiene-
Styrene copolymers (ABS resins); polybutylene terephthalate resins; resins such as acrylic resins and foams thereof.

The other adherend is not particularly limited, and paper, cloth, wood, metal, mortar, concrete and the like can be used in addition to the above resins.

The adhesive composition of the present invention is liquid at the uncured stage,
After being adhered to the adherend by a suitable means, it is cured. The conditions for curing this composition differ depending on the type of each component, the amount used, etc., but are usually 0-2.
At a temperature of 00 ° C., preferably 15 to 150 ° C. for 5 minutes
It may be heated for 168 hours, preferably 30 minutes to 96 hours.

〔The invention's effect〕

The adhesive composition of the present invention exhibits extremely good adhesiveness when at least one of the adherends is a resin, and particularly 180
The markedly improved peel strength and tensile shear bond strength.

〔Example〕

 Next, the present invention will be described in detail with reference to Examples.

Comparative Examples 1 to 5 Hydroxyl group-containing liquid diene polymer (hereinafter abbreviated as A component) and an inorganic filler (hereinafter abbreviated as D component) were mixed in predetermined amounts, and then heated to 120 ° C. bitumen. Add a predetermined amount of substance (hereinafter abbreviated as C component) and
And mixed for 30 minutes with stirring. Next, each predetermined amount of a polyisocyanate compound (hereinafter abbreviated as B component) and dibutyltin dilaurate (curing accelerator) was added to this mixture, and the mixture was stirred and mixed with a paint mill roll at room temperature for 3 minutes.

The adhesive thus obtained is applied to a degreased adherend (shown), and then a cotton canvas (JIS L
A normal cotton canvas 1209) specified in 3102 was laminated and adhered to obtain a test piece. This test piece was cured under conditions of 20 ° C. for 2 hours and 70 ° C. for 15 hours, and then JIS K6 was used.
The 180 ° peel strength was measured according to 854. The results are shown in Table 1.

Comparative Examples 6 to 9 Comparative Examples 1 to 5 were performed in the same manner as Comparative Examples 1 to 5 except that a polyol compound (hereinafter abbreviated as E component) was used instead of the D component. The results are shown in Table 2.

Examples 1 to 7 Comparative Examples 1 to 5 were performed in the same manner as Comparative Examples 1 to 5 except that the D component and the E component were used instead of the D component. The results are shown in Table 3.

Comparative Examples 10 to 17 Comparative Examples 1 to 5 were performed in the same manner as Comparative Examples 1 to 5 except that the C component and the D component were omitted. The results are shown in Table 4.

Comparative Examples 18 to 20 After mixing respective predetermined amounts of the components A and D, a predetermined amount of the component C heated to 120 ° C was added, and the mixture was stirred and mixed at 50 ° C for 30 minutes. Next, the respective predetermined amounts of the component B and dibutyltin dilaurate (curing accelerator) were added to this mixture, and the mixture was stirred and mixed with a paint mill roll at room temperature for 3 minutes.

The adhesive thus obtained was applied between two degreased adherends (shown) (width of adhesive layer: 25 mm, length: 12 m).
m, thickness 0.5 mm) The test piece. This test piece at 20 ° C
After curing for 2 hours at 70 ° C. for 15 hours, the tensile shear adhesive strength was measured according to JIS K6850. The results are shown in Table 5.

Comparative Examples 21 to 22 Comparative Examples 18 to 20 were performed in the same manner as Comparative Rows 18 to 20 except that the E component was used instead of the D component.
The results are shown in Table 5.

Examples 8 to 12 Comparative Examples 18 to 20 were performed in the same manner as Comparative Examples 18 to 20 except that the D component and the E component were used instead of the D component. The results are shown in Table 6.

Comparative Examples 23 to 27 Comparative Examples 18 to 20 were performed in the same manner as Comparative Examples 18 to 20 except that the C component and the D component were omitted. The results are shown in Table 7.

Comparative Example 28 Comparative Examples 18 to 20 were performed in the same manner as Comparative Example 18 except that the D component was omitted. The results are shown in Table 7.

In addition, each component in Tables 1-7 is as follows.

Component A: Hydroxyl group-containing liquid polybutadiene (Idemitsu Petrochemical
"R-45HT", number average molecular weight 2800,
Hydroxyl content 0.79 meq / g) B component: Liquid modified diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., “Millonate MT
L ”, isocyanate group content 29.0% by weight) C component (1): 60/80 straight asphalt (manufactured by Idemitsu Kosan Co., Ltd.) C component (2): 10/20 blown asphalt (Sankyo Yuka Kogyo Co., Ltd. ) D component (1): precipitated calcium carbonate (calcium shiraishi)
Ltd., "Hakuenka CCR") D component (2): aluminum hydroxide (Showa Denko KK,
"Higilite H-42M") E component (1): N, N-bis (hydroxypropyl) aniline (Chemical Upjohn Co., Ltd., "Isonol C-10"
0 ") E component (2): propylene oxide adduct of bisphenol A (" BAP-3 "manufactured by Nippon Emulsifier Co., Ltd.) Adherent Rigid PVC: Rigid polyvinyl chloride (Sun Arrow Chemical Co., Ltd.)
Soft PVC: Soft polyvinyl chloride (Sun Arrow Chemical Co., Ltd.)
PS: Polystyrene (manufactured by Idemitsu Petrochemical Co., Ltd.) PC: Polycarbonate (manufactured by Idemitsu Petrochemical Co., Ltd.) ABS: Acrylonitrile-butadiene-styrene copolymer (manufactured by Mitsubishi Rayon Co., Ltd.) PBT: Poly Butylene terephthalate (Mitsubishi Rayon
Acrylic resin: Polymethylmethacrylate (Mitsubishi Rayon Co., Ltd.) Expanded PS: Expanded polystyrene (Nippon Styrene Paper)
(Made by)

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-57-209977 (JP, A) JP-A-51-30839 (JP, A) JP-A-57-182372 (JP, A) JP-A-60- 219279 (JP, A) JP 61-255971 (JP, A) JP 60-118782 (JP, A)

Claims (2)

[Claims] 1. A resin bonding composition comprising a hydroxyl group-containing liquid diene polymer, a polyisocyanate compound, a bituminous substance, an inorganic filler and a polyol compound. 2. The composition according to claim 1, wherein the hydroxyl group-containing liquid diene polymer has a hydroxyl group content of 0.1 to 10 meq / g.