JPH0641580B2 - Resin bonding composition - Google Patents

Description

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

[Problems to be Solved by the Related Art and Invention] As an adhesive used when a synthetic resin or a foam thereof is used as an adherend, since the adherend adherend surface is easily eroded by a solvent or the like, Choice of solvent or non-solution type adhesive,
It is used. As such an adhesive for resins, an adhesive composition comprising a polymer such as a hydroxyl group-containing liquid polybutadiene and a compound such as diphenylmethane diisocyanate, or a composition obtained by adding a bituminous substance such as asphalt or an inorganic filler to the composition. Etc. have been proposed.

Although this adhesive can avoid erosion and breakage of the resin to be adhered, it tends to foam during the curing reaction due to the water content of the composition, causing a decrease in adhesive strength.

[Means for solving problems]

An object of the present invention is to solve the above problems and to provide a resin bonding composition having improved initial adhesive strength.

The present inventors have conducted extensive studies based on the above object, and by adding a hygroscopic agent as one component of the composition,
It has been found that the adhesive strength, especially the initial adhesive strength, is significantly improved. The present invention has been completed based on these findings. That is, the present invention provides a resin bonding composition comprising a hydroxyl group-containing liquid diene polymer, a polyisocyanate compound, a hygroscopic agent, an inorganic filler and / or a polyol compound.

The hydroxyl group-containing liquid diene polymer used in the present invention has a number average molecular weight of 300 to 25,000, preferably 500 to 100, which has a hydroxyl group in the molecule, preferably at the terminal of the molecular chain.
00 is a liquid diene polymer. These liquid diene-based polymers include diene polymers and diene copolymers having 4 to 12 carbon atoms, and further these diene monomers and 2 to 2 carbon atoms.
There are copolymers with the α-olefinic addition polymerizable monomer of 2 and the like. The hydroxyl group content is 0.1 to 10 meq / g, preferably 0.3 to 5.0 meq / g. Specifically, butadiene homopolymer, isoprene homopolymer, butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-
Examples thereof include 2-ethyl-hexyl acrylate copolymer and butadiene-n-octadecyl acrylate copolymer. These liquid diene polymers are
For example, it can be produced by reacting a conjugated diene monomer in a liquid reaction medium in the presence of hydrogen peroxide with heating.

Further, the polyisocyanate compound is an organic compound having two or more isocyanate groups in one molecule, and the hydroxyl group-containing liquid diene-based polymer and an active hydrogen-containing functional group of a polyol compound added as necessary. Having a reactive isocyanate group with respect to. 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, polymethylene polyphenyl isocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexanephenylene diisocyanate, naphthalene-1,5
-Diisocyanate, isopropylbenzene-2,4-diisocyanate, polypropylene glycol and tolylene diisocyanate addition reaction product, etc.
I, 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 is usually the isocyanate group (NCO) of the polyisocyanate compound with respect to the hydroxyl group (OH) of the hydroxyl group-containing liquid diene polymer.
The molar ratio of NCO / OH, that is, NCO / OH is 0.2 to 25.0, preferably 0.5 to 15.0. When the molar ratio is outside the above range, the composition obtained is difficult to cure, which is not preferable.

In the present invention, it is necessary to use a hygroscopic agent as one component of the composition. By adding this hygroscopic agent,
The adhesive strength of the resulting composition is significantly increased. here,
Although various kinds of hygroscopic agents can be used, usually, inorganic hygroscopic agents such as zeolite, anhydrous or hemihydrate gypsum, silica gel, calcium oxide, calcium chloride are preferably used. The inorganic hygroscopic agent itself may be in the form of powder, granules or the like. Zeolite is preferable as the inorganic hygroscopic agent, and various zeolites are available. Either natural zeolite or synthetic zeolite may be used, but synthetic zeolite is particularly preferable. This synthetic zeolite is usually crystalline aluminosilicate, but other zeolites such as crystalline borosilicate and crystalline boroaluminosilicate can also be used. Examples of crystalline aluminosilicate zeolite include A type zeolite,
L-type zeolite, X-type zeolite, Y-type zeolite, etc., and ultra-stable Y-type (USY-type) zeolite,
ZSM type zeolite and the like are also included, and silica /
Alumina (molar ratio) is 0.1 to 500, preferably 0.2 to 4
0, particularly preferably 0.4 to 35. Here, since zeolite has more active sites that absorb moisture due to its crystal structure than other moisture absorbents, it has a large moisture absorption capacity and can selectively and completely absorb water or moisture. In addition, the composition has good storage stability, and there is no trouble such as precipitation even after long-term storage.

In the present invention, anhydrous or semi-aqueous gypsum can be used as the inorganic hygroscopic agent in addition to the above zeolite, and these gypsums may be natural gypsum or chemical gypsum. Examples of chemical gypsum include synthetic gypsum, recycled gypsum, and byproduct gypsum. Further, the silica gel may be either natural silica gel or synthetic silica gel. The inorganic hygroscopic agent having a particle size of 0.01 to 1000 μ is suitably used for work.

In the composition of the present invention, the hygroscopic agent is used in an amount of 5 to 50 parts by weight, preferably 15 to 35 parts by weight, based on 100 parts by weight of the hydroxyl group-containing liquid diene polymer. Here, if the amount of the hygroscopic agent is less than 5 parts by weight, sufficient dehydration and foaming prevention effects cannot be obtained, and the adhesive strength of the composition is lowered, which is not preferable. On the other hand, even if the blending amount of the hygroscopic agent exceeds 50 parts by weight, the hygroscopic effect is not increased, and rather the physical properties of the obtained composition may be deteriorated.

Further, in the composition of the present invention, either one or both of the inorganic filler and the polyol compound are used together with the hydroxyl group-containing liquid diene polymer, the polyisocyanate compound and the hygroscopic agent, but as the inorganic filler, Mica, graphite, silica, talc, clay, leucite, calcium carbonate, slate powder, feldspar, silicic acid, and white luster can be used. The inorganic filler is 1 to 1 with respect to 100 parts by weight of the hydroxyl group-containing liquid diene polymer.
000 parts by weight, preferably 5 to 700 parts by weight.

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, bisphenol A
And a low molecular weight polyol containing a hydroxyl group bonded to at least one secondary carbon, such as the propylene oxide adduct.

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 can be used. . In the present invention, a diol is usually used as the polyol, but triol or tetraol may be used,
Its molecular weight is in the range of 50-500.

This polyol compound is used in place of or together with the above-mentioned inorganic filler, and the amount thereof is 1 to 1000 parts by weight, preferably 3 to 100 parts by weight based on 100 parts by weight of the hydroxyl group-containing liquid diene polymer. 200 parts by weight is suitable. Further, two or more kinds of the inorganic filler and the polyol compound may be mixed and used.

The resin bonding composition of the present invention can be obtained by blending each of the above components, but other additives can be appropriately added if necessary. For example, a polyamine compound can be added as a strengthening agent. In this case, the polyamine compound to be added is not particularly limited as the polyamine compound 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-4,4'-
Alicyclic amines such as diaminodicyclohexylmethane; 4,
Aromatic amines such as 4'-diaminophenyl; tetramine such as 2,4,6-tri (dimethylaminomethyl) phenol and the like.

When these polyamine compounds are added, the addition amount is not limited, but is usually 1 to 1000 parts by weight, preferably 3 to 200 parts by weight, relative to 100 parts by weight of the hydroxyl group-containing liquid diene polymer.

If desired, bituminous substances such as petroleum asphalt such as straight asphalt, blown asphalt, semi-blown asphalt, propane (solvent) deasphalting asphalt, petroleum pitch, coal tar, and coal pitch can be added. In this case, the bituminous substance is 10 to 1000 relative to 100 parts by weight of the hydroxyl group-containing liquid diene polymer.
Used at a ratio of parts by weight.

In addition, a plasticizer such as dioctyl phthalate may be added as a viscosity modifier, a softener such as an aroma, naphthene or paraffin oil may be added, and an alkylphenol resin or terpene resin may be used to adjust the adhesive strength and the adhesive strength. Adhesive resins such as terpene phenol resin, xylene formaldehyde resin, rosin, hydrogenated rosin, coumarone resin, aliphatic and aromatic petroleum resins can also be added. Further, a curing accelerator such as dibutyl tin laurate, stannous octoate, or polyethylene diamine may be added. Furthermore, an anti-aging agent may be added to improve weather resistance, and a silicon 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 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 various resins are targeted. For example, polyvinyl chloride resin (PVC resin) (hard, soft); polyolefin resin such as polyethylene and polypropylene; polystyrene resin; polycarbonate resin: acrylonitrile-butadiene-styrene copolymer (ABS resin); acrylonitrile-ethylene-styrene copolymer Coalescence (AES
Resin); polybutylene terephthalate resin (PBT resin); resins such as acrylic resin and foams thereof, and these resins are used as glass fiber, carbon fiber,
There are also reinforced plastics reinforced with asbestos.

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,
This is adhered to the adherend by an appropriate means such as coating or spraying and then cured. The conditions for curing this composition differ depending on the type of each component, the amount used, etc., but are usually 0 to 200 ° C., preferably 50 to 15 ° C.
The treatment may be performed at a temperature of 0 ° C. for 5 minutes to 168 hours, preferably 10 minutes to 72 hours.

Further, the thickness of coating or spraying the composition of the present invention,
There is no particular limitation, but usually about 0.05 to 10 mm is sufficient.

〔The invention's effect〕

The adhesive composition of the present invention as described above has improved adhesiveness because there is no foaming during the curing reaction. That is, according to the present invention, the tensile shear adhesive strength, especially the initial adhesive strength is remarkably improved.

Moreover, the adhesive composition of the present invention does not cause erosion of the adherend resin or material destruction.

Therefore, the adhesive composition of the present invention is particularly useful as a resin adhesive containing at least one of the adherends as a resin.

〔Example〕

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

Examples 1, 2 Hydroxyl group-containing liquid diene polymer (hereinafter abbreviated as A component), moisture absorbent (hereinafter abbreviated as C component), polyol compound (hereinafter abbreviated as D component), inorganic Predetermined amounts of the filler (hereinafter abbreviated as component E) and dibutyltin laurate (curing accelerator) shown in Table 1 were sampled in a container and mixed with stirring at 80 ° C. for 30 minutes. Next, a polyisocyanate compound (hereinafter abbreviated as component B) and dibutyltin laurate (curing accelerator) are added to this mixture.
Was added and the mixture was stirred at room temperature for 1 minute to obtain a liquid composition.

The tensile shear adhesive strength of the adhesive composed of this composition was measured by the following method.

Tensile shear adhesive strength Various resins shown in Table 1 were used for both adherends, and the adhesive obtained as described above was applied to the surface of one adherend by 0.5 m.
It was applied in a thickness of m, and the other adherend was laminated and adhered. After stacking and depositing, leave it for 15 minutes at room temperature and after leaving it for 24 hours JIS
The tensile shear adhesive strength was measured at a pulling speed of 5 mm / min. According to K-6850. The results are shown in Table 1.

Comparative Examples 1 and 2 The same procedure as in Examples 1 and 2 was repeated except that the hygroscopic agent (component C) was omitted from Examples 1 and 2. First result
Shown in the table. In addition, each component in Table 1 is as follows.

Component A: Liquid polybutadiene containing terminal hydroxyl group (“R-45HT” manufactured by Idemitsu Petrochemical Co., Ltd., number average molecular weight 280)
0, hydroxyl content 0.82 meq / g) B component: liquid modified diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., “Millionate MT
L ", isocyanate group content 28.9% by weight) C component: synthetic zeolite (manufactured by Bayer," Synthetic zeolite 4A ") D component (1): N, N-bis (hydroxypropyl) aniline (chemical conversion up Ltd., "C-100", hydroxyl group content 9.64meq / g) D component (2): propylene oxide adduct of bisphenol A (Nippon Emulsifier Ltd., "BAP-3", hydroxyl group content 5.04meq) / g) E component: Precipitable calcium carbonate (manufactured by Shiraishi Industry Co., Ltd.,
"Shiragure CCR") Adherend PC resin: Polycarbonate (made by Idemitsu Petrochemical Co., Ltd.,
ABS resin: acrylonitrile-butadiene-styrene copolymer (manufactured by Mitsubishi Rayon Co., Ltd.) PBT resin: polybutylene terephthalate (manufactured by Mitsubishi Rayon Co., Ltd.) PVC resin: hard polyvinyl chloride (manufactured by Sun Arrow Chemical Co., Ltd.) Acrylic resin: Polymethylmethacrylate (manufactured by Mitsubishi Rayon Co., Ltd.) AES resin: Acrylonitrile-ethylene-styrene copolymer (manufactured by Hitachi Chemical Co., Ltd.) FRP: Glass fiber reinforced resin of the acrylic resin

Claims (3)

[Claims] 1. A liquid diene polymer having a hydroxyl group, a polyisocyanate compound, a hygroscopic agent and an inorganic filler and / or
Alternatively, a resin bonding composition comprising a polyol compound. 2. A hydroxyl group-containing liquid diene polymer having a hydroxyl group content of 0.1 to 10 meq / g.
The composition according to the item. 3. The composition according to claim 1, wherein the hygroscopic agent is zeolite.