JPH1017845A - Adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive compsn. excellent in stability even through it contains a bituminous substance, wet heat resistance, and peeling strength. SOLUTION: This compsn. essentially contains a bituminous substance, an org. polyisocyanate compd., and a polyol compd. which contains at least 10wt.% ether units represented by the formula: -(CR1 R2 -R3 R4 -O) (wherein R1 to R4 are each H or a hydrocarbon group provided the total number of carbon atoms contained in R1 to R4 is 2 or higher).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition having excellent stability, heat and moisture resistance and peel strength, and more particularly, to an adhesive composition having improved adhesiveness used when at least one of the adherends is a resin. It relates to a composition.

[0002]

2. Description of the Related Art A non-solvent type or non-solution type adhesive is selected as an adhesive when a synthetic resin or its foam is used as an adherend because the adherend surface of the adherend is easily eroded by a solvent or the like. ,It is used.

As an adhesive for such a resin, there has been proposed an adhesive composition comprising a polymer such as liquid hydroxyl-containing polybutadiene and a compound such as diphenylmethane diisocyanate, and a composition obtained by adding a bituminous substance such as asphalt to the composition. Although these adhesives can prevent erosion and destruction of the resin as an adherend, they cannot be said to be sufficiently satisfactory in practical use because of their low 180 ° peel strength.

[0004] Further, an adhesive composition comprising a compound such as polyoxypropylene glycol and diphenylmethane diisocyanate and a composition obtained by adding a bituminous substance such as asphalt to the composition have been proposed, but the phase of asphalt and other components have been proposed. It has drawbacks such as poor solubility and inability to obtain sufficient adhesive strength.

[0005]

That is, an object of the present invention is to provide an adhesive composition having excellent stability with bituminous substances, excellent heat and moisture resistance, and excellent peel strength.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve these difficulties, and as a result, have completed the adhesive composition of the present invention.

That is, the present invention provides a bonding composition obtained from a bituminous substance, a polyol compound and an organic polyisocyanate compound, which comprises a polyol containing at least 10% by weight of an ether unit represented by the formula 1 as a polyol compound. Preferably, the polyol containing at least 10% by weight of the ether unit represented by Chemical Formula 1 has an unsaturated double bond content of 0.1 meq / g or less and a hydroxyl group content of 0.2
To 10 meq / g, and an inorganic filler.

[0008]

## STR2 ## _{- (CR 1 R 2 -R 3} R 4 -O) - Formula 1 (wherein, R ₁ to R ₄ are each hydrogen or hydrocarbon, R ₁
The total number of carbon atoms contained in the to R ₄ is 2 or more)

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The bituminous substance used in the present invention is not particularly limited, but is generally used such as straight asphalt, blown asphalt, semi-blown asphalt, propane (solvent) deasphalted asphalt and the like. Single or mixture of petroleum asphalt, petroleum pitch, coal tar, coal pitch and the like can be used.

The polyol compound used in the present invention is:
It is essential that the ether unit represented by the formula 1 be contained in an amount of 10% by weight or more, preferably 10 to 100% by weight. If necessary, another polyol capable of reacting with the organic polyisocyanate compound in an amount of preferably less than 90% by weight of all the polyol compounds may be used in combination. If the ether unit represented by the formula 1 is less than 10% by weight, stability, adhesiveness,
Moisture and heat resistance is inferior.

[0011]

## STR3 ## _{- (CR 1 R 2 -R 3} R 4 -O) - Formula 1 (wherein, R ₁ to R ₄ are each hydrogen or hydrocarbon, R ₁
The total number of carbon atoms contained in the to R ₄ is 2 or more)

The ether unit of the formula 1 is obtained by an alkylene oxide, and specific examples thereof include 1,2-butylene oxide, 2,3-butylene oxide, isobutylenoxide, styrene oxide, and a compound having 5 or more carbon atoms. There are 1,2-epoxyalkane and the like, preferably 1,2-butylene oxide. These compounds can be used alone or in combination of two or more. Polyols containing ether units of formula 1 may contain less than 90% of oxypropylene and / or oxyethylene and / or teoxytetramethylene ether units.

The ether unit represented by the formula 1 of the present invention is represented by 1
The polyol compound containing 0% by weight or more preferably has an unsaturated double bond content of 0.1 meq / g or less, more preferably 0.0meq / g or less.
7meq / g or less, the hydroxyl content is preferably 0.2 to 10meq / g
And more preferably 0.1 to 3 meq / g.

The polyol compound having an ether unit of the formula 1 of the present invention is a polyhydric alcohol having 2 or more hydroxyl groups in one molecule as an initiator, for example, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 3-methyl-1,5-pentanediol, 1,5-pentanediol, 1,6-hexa Methylene glycol, bishydroxyethoxybenzene, p-xylene glycol, neopentyl glycol, glycerin, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, sorbitol, sucrose, methylglucoside and the like, or an amine compound such as ethylenediamine , Urea, hex Diamine, diethylenetriamine, monoethanolamine, diethanolamine, triethanolamine, obtained by ring-opening adding an alkylene oxide.

The catalyst used for the ring-opening addition includes BF
₃ · Et may be a basic catalyst such as an alkali metal hydroxide in ₂ acidic catalysts O and the like.

Other polyol compounds which can react with the organic polyisocyanate compound which can be used in combination with the polyol compound containing an ether unit of the formula 1 of the present invention include propylene oxide, ethylene oxide and the like added to the above-mentioned initiators. Polyether polyol obtained, polycarboxylic acid, polycarboxylic anhydride, polyester polyol obtained by dehydration condensation of carboxylic acid half ester and low molecular weight polyol, polylactone polyol obtained by polymerizing caprolactone, polymerization of tetrahydrofuran And the like. Further, polyhydric alcohols such as the above-mentioned initiators can also be used in combination.

As the polyisocyanate compound used in the present invention, all known organic polyisocyanates can be used. For example, 2,4-toluene diisocyanate, 2,6-
Toluene diisocyanate, 2,4 / 2,6 isomer ratio 65/35
(Weight ratio) toluene diisocyanate, 2,4 / 2,6 isomer ratio 80/20 (weight ratio) toluene diisocyanate,
4 'diphenylmethane diisocyanate, liquid modified diphenylmethane diisocyanate, meta-xylylene diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl polyisocyanate, crude toluene diisocyanate, Crude diphenylmethane diisocyanate, and alone or a mixture of isocyanate-terminated prepolymer obtained by previously reacting the above polyols and polyisocyanate, preferably, 4,4 ′ diphenylmethane diisocyanate, liquid modified diphenylmethane diisocyanate, toluene diisocyanate, isocyanate End step Polymer, and the like.

The mixing ratio of the polyol compound and the polyisocyanate compound used in the present invention is not particularly limited.
The molar ratio of the hydroxyl group (OH) of the polyol compound to the isocyanate group of the polyisocyanate compound is preferably N
CO / OH = 0.2 to 10.0, more preferably 0.5 to 6.0. If the mixing ratio of the two is out of this range, it is difficult to cure.

The mixing ratio of the polyol compound and the bituminous substance used in the present invention is preferably 5 to 1000 parts by weight, more preferably 10 to 300 parts by weight, based on 100 parts by weight of the polyol compound.

The inorganic filler used in the present invention includes:
For example, calcium carbonate, silica sand powder, clay, adob, ball clay, bauxite clay, bentonite, binding clay, bleached clay, terracotta clay, flow resistant clay, burley clay, kaolin clay, red clay, loam, loess, mica clay , Glass powder, asbestos, mica, gypsum, talc, graphite, hillstone, slate powder and the like, and mixtures thereof can be used.

The mixing ratio of the polyol compound and the inorganic filler used in the present invention is preferably 1 to 1000 parts by weight, more preferably 5 to 600 parts by weight, based on 100 parts by weight of the polyol compound.

The adhesive composition of the present invention can be obtained by blending the above-mentioned components, and other additives can be added as needed. 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 tetramine. Further, any of primary polyamine, secondary polyamine, and tertiary polyamine can be used. Examples of the polyamine compound include aliphatic amines such as hexamethylenediamine, alicyclic amines such as 3,3-dimethyl-4,4-diaminocyclohexylmethane, aromatic amines such as 4,4-diaminodiphenyl, and 2,4, Examples thereof include tetramine such as 6-tri (dimethylaminomethyl) phenol.

Further, a plasticizer such as dioctyl phthalate may be added as a viscosity modifier, or an aroma type, a naphthene type,
Alkylphenol resin, terpene resin, terpene phenol resin, xylene formaldehyde resin, rosin, hydrogenated rosin, coumarone resin, aliphatic and aromatic petroleum resins, etc. Can be added.

Further, a curing accelerator such as dibutyltin dilaurate, stannous octoate, or polyethylenediamine may be added. Further, an antioxidant can be added to improve weather resistance, and a silicon compound can be added as an antifoaming agent.

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

The adherend to which the adhesive composition of the present invention is applied is preferably at least one resin, and may be various resins. For example, polyvinyl chloride resin (hard / soft);
Polyolefin resins such as polyethylene and polypropylene; polystyrene resins; polycarbonate resins; acrylonitrile-butadiene-styrene copolymer (ABS resin); polybutylene terephthalate resins; acrylic resins;

The other adherend is not particularly limited, and examples thereof include paper, cloth, wood, metal, mortar, concrete, and the like in addition to the above resins.

The adhesive composition of the present invention is in a liquid state at an uncured stage, and after being adhered to the adherend by an appropriate means, is cured. Although the conditions for curing this composition vary depending on the type of each component, the amount used, etc.,
Usually, at a temperature of 0 to 200 ° C, preferably 15 to 150 ° C for 5 minutes to 170 hours, more preferably 30 minutes to 1 hour.
What is necessary is just to heat for 00 hours.

[0029]

Next, the present invention will be described with reference to Examples, but it should not be construed that the invention is limited thereto. In the text, "parts" and "%" are based on weight.

Examples 1 to 5 After mixing predetermined amounts of a polyol compound (hereinafter abbreviated as component A) and an inorganic filler (hereinafter abbreviated as component D), the mixture was heated to 120 ° C. and the bitumen substance (hereinafter abbreviated as component A). , C component) and stirred and mixed at 60 ° C for 20 minutes. The mixture of A, C, and D was left at room temperature for 5 hours to confirm the stability of the mixture. Next, predetermined amounts of a polyisocyanate compound (hereinafter, abbreviated as a component B) and dibutyltin dilaurate were added to the mixture, and the mixture was stirred at room temperature for 3 minutes.

After the adhesive thus obtained was applied on a degreased adherend, the same adherend was overlaid and adhered to obtain a test piece. The test piece was cured at 20 ° C. for 2 hours and at 70 ° C. for 10 hours, and the 180 ° peel strength was measured according to JIS K6854.

A test piece cured in the same manner was heated at 70 ° C.
X 2% for 2 weeks in a humid atmosphere under the condition of 95% RH,
It was taken out and the 180 ° peel strength was measured to determine the retention.
The results are shown in Table 1.

[0033]

[Table 1] DBTDL: dibutyltin laurate

Comparative Examples 1 to 4 The same procedures as in Examples 1 to 5 were carried out according to the mixing ratios shown in Table 2. The results are shown in Table 2.

The components in Tables 1 and 2 are as follows. Component A (1): Poly (oxy-1,2-butylene) glycol [oxy-1,2-butylene unit content 100 having an unsaturated double bond content of 0.021 meq / g and a hydroxyl group content of 1.0 meq / g.
%]

A component (2): unsaturated double bond content 0.0
Poly (oxypropylene) (oxy-1,2-butylene) triol [oxy-1,5 meq / g, hydroxyl group content 0.6 meq / g
2-butylene unit content 80%]

Component A (3): unsaturated double bond content 0.2
Poly (oxy-1,2-) with 0 meq / g and hydroxyl group content of 0.67 meq / g
Butylene) glycol [oxy-1,2-butylene unit content 100%]

Component A (4): unsaturated double bond content 0.0
Poly (oxypropylene) triol with 15meq / g and hydroxyl group content of 1.0meq / g [oxy-1,2-butylene unit content
0%]

Component A (5): unsaturated double bond content 0.0
Poly (oxy-1,4-) with 23meq / g and hydroxyl group content of 2.0meq / g
Butylene) glycol [oxy-1,2-butylene unit content 0%]

Component B: liquid modified diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., "Mi
llonate MTL ", isocyanate group content 29.0% by weight)

C component: blown asphalt (manufactured by Sankyo Yuka Kogyo Co., Ltd.) D component: calcium carbonate (Shiroishi Calcium Co., Ltd.)
Made)

[0042]

[Table 2]

[0043]

The adhesive composition of the present invention exhibits extremely good adhesiveness when the adherend is a resin, and is excellent in wet heat resistance and stability.

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[Procedure amendment]

[Submission date] July 15, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

## STR1 ## _{- (CR 1 R 2 - C} R 3 R 4 -O) - in Formula 1 (wherein, R ₁ to R ₄ are each hydrogen or hydrocarbon, R ₁
The total number of carbon atoms contained in the to R ₄ is 2 or more)

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction contents]

That is, the present invention provides a bonding composition obtained from a bituminous substance, a polyol compound and an organic polyisocyanate compound, which comprises a polyol containing at least 10% by weight of an ether unit represented by the formula 1 as a polyol compound. Preferably, the polyol containing at least 10% by weight of the ether unit represented by the formula 1 has an unsaturated double bond content of 0.1 meq / g or less and a hydroxyl group content of 0.2
To 10 meq / g, and an inorganic filler.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction contents]

[0008]

## STR2 ## _{- (CR 1 R 2 - C} R 3 R 4 -O) - in Formula 1 (wherein, R ₁ to R ₄ are each hydrogen or hydrocarbon, R ₁
The total number of carbon atoms contained in the to R ₄ is 2 or more)

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction contents]

[0011]

## STR3 ## _{- (CR 1 R 2 - C} R 3 R 4 -O) - in Formula 1 (wherein, R ₁ to R ₄ are each hydrogen or hydrocarbon, R ₁
The total number of carbon atoms contained in the to R ₄ is 2 or more)

Claims (3)

[Claims] 1. An adhesive composition obtained from a bituminous substance, a polyol compound and an organic polyisocyanate compound, wherein a polyol compound containing 10% by weight or more of an ether unit represented by the formula 1 is used as a polyol compound as an essential component. An adhesive composition, comprising: ## STR1 ## _{- (CR 1 R 2 -R 3} R 4 -O) - Formula 1 (wherein, R ₁ to R ₄ are each hydrogen or hydrocarbon, R ₁
The total number of carbon atoms contained in the to R ₄ is 2 or more) 2. The polyol compound containing 10% by weight or more of the ether unit represented by the chemical formula 1 has an unsaturated double bond content.
The adhesive composition according to claim 1, wherein the composition is a polyol compound having a hydroxyl group content of 0.1 meq / g or less and a hydroxyl group content of 0.2 to 10 meq / g. 3. The adhesive composition according to claim 1, further comprising an inorganic filler.