JPH02169681A - Steam resistant adhesive method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for bonding a plastic material and a polyurethane resin with excellent steam resistance.

[Conventional technology]

Bonding polyurethane resin to plastic materials has been done for a long time, and is a plastic material with similar polarity to polyurethane resin.

For example, it normally adheres relatively strongly to vinyl chloride resin, acrylonitrile-styrene copolymer resin, etc. On the other hand, plastic materials such as polyolefin resins with low polarity or polyamide resins with high crystallinity do not adhere strongly, but the adhesive force under normal conditions can be improved by applying surface oxidation treatment before adhering. but,
In any of the above cases, if exposed to hot water or steam, it will peel off in a short period of time, and its uses are inherently limited and cumbersome. for example.

Materials applied in the food industry and medicine are required to withstand extreme steam treatment.

Steam-resistant adhesion has been attempted for food conveyance belts, artificial organs, etc. by bonding plastic materials and polyurethane resin! ! Next. However, since these peel off during steam sterilization or their adhesive strength is significantly reduced, other non-convenient sterilization treatments (ethylene oxide aeration, gas/11s irradiation,
Currently, we have no choice but to rely on alcohol cleaning.

[Means to solve the problem]

The present invention eliminates these conventional drawbacks, and provides a plastic material with a surface oxidation treatment.
The primer used in this case is (1) polycaprolact/diol poly (hexamethylene adipate) diol poly (hexamethylene adipate) diol as a long chain diol with a molecular weight of 1,500 to 4,000.
(hexamethylene carbonate) diol alone, a mixture of two or more, or a copolymer thereof (2) alicyclic diisocyanate (3) polyurethane urea solution prepared by reacting organic diamine in an organic solvent It is. Further, a primer prepared by blending an organic polyinsyanate into this polyurethaneurea solution may also be used.

The plastic material of the present invention can be used as a tube, plate, or sheet.

Thermoplastic resin 9 molded into a film or other shape, such as polystyrene resin, polyester resin, polyamide resin, polyolefin resin.

Polyurethane resin, polyurea resin, poly(meth)acrylate resin, polyacrylonitrile resin.

These include cellulose resins and copolymers thereof. 2. Good thermosetting resins that are molded into the above shape, such as phenol resins, urea resins, epoxy resins, and unsaturated polyester resins.

These include polyurethane resins, polyurea resins, and copolymers thereof. Further, the hybrid resin 2 made of a thermoimageable resin/thermosetting resin molded into the above shape, for example, a hybrid resin made of polyvinyl chloride/polyurethane, a hybrid resin made of polyoxymethylene/polyurethane, etc. The above tree is filled with filler.

Reinforcements, plasticizers, liquid extenders, flame retardants 1 colorants.

A7 may contain stabilizers and other compounding agents.

The polyurethane resin of the present invention is a thermoplastic resin obtained by the reaction of an active hydrogen compound and an organic polyisocyanate. IIJ curable resin.

Included are poly9 urethane resin and polyurethane urea resin. These resins contain isocyanurate structures, allophanate bonds, and biraleft bonds.

An amide bond, an acylurea bond, and other compounding agents may be included. polyurethane resin.

It can be used in the method of the invention either as a polymer or as a liquid curable formulation.

The polycaprolact/diol of the present invention has a molecular weight of 1.500 to 4,000 as a long chain diol.

Glycols 1 to ε-turnip clactone, e.g.
It is obtained by ring-opening polymerization using glycol, diethylene glycol, neobe/tyl glycol, cyclohexane dimetatool, bis(hydroxyethoxy7)benzene, or the like as an initiator by a known method. Poly (hexamethylene adipate) diol (P HA ) is 1.6
- It is obtained by polycondensing hexanediol and adipic acid by a known method. Also, poly (hexamethylene carbonate) diol (PHC) ii, 1
．． It is obtained by polycondensing 6-hexanediol with ethylene carbonate, diethyl carbonate, diphenyl carbonate, etc. by a known method. these are,
It may be used alone or as a mixture of two or more or a copolymer thereof.

Hereinafter, the above-mentioned long chain diol will be referred to as the long chain diol of the present invention. What is the molecular weight of the long chain diol of the present invention?

The number average is 1.500 to fD in ooo, and if it is outside this range, the adhesiveness is poor and is not preferred.

The number average molecular weight of a diol is calculated using the formula below based on its hydrocarbon value.

1 sailor group song That is, the hydroxyl value of the long chain diol of the present invention is 9.

75-14 Il! It is surrounded by

The alicyclic diisocyanate of the present invention is, for example, 9.

dicyclohexylmethane-4,4'-diisocyanate)
(H-*M D I L dicyclohexylmethane-2
゜4'-diincyanate), 1,4-cyclohexane diinocyanate (CHDI)t 1,3-cyclohexane diinocyanate, inphorone diinocyanate (IPDI), 1-methyl-2,4-diisocyanatocyclohexane, l-methyl -2,6-diisocyanatocyclohexane, II 4-bis(incyanatomethyl)cyclohexane, 1,3-bis(incyanatomethyl)cyclohexane natodicyclohexylmethane, etc. These may be used alone or in combination of two or more. It is a mixture. Among these.

Industrially easily available H, MDI, CHDI, I
Particularly preferred are PDI and the like.

The organic diamines of the present invention include aromatic diamines, alicyclic diamines, aliphatic diamines, and aromatic substituted aliphatic diamines, such as 4,4'-diaminodiphenylmethane (MDA), 2,4-diaminotoluene (2 ,4-T
DA), diethyldiaminotoluene, 4.4'-diaminodicyclohexylmethane (HnMDA), 2.4'-
Diaminodicyclohexylmethane, 1,4-cyclohexanediamine.

1.3-cyclohexanediamine, inphoronediamine (IPDA) 1-methyl-2,4-diaminocyclohexane, l-methyl-2,6-diaminocyclohexane,
1#4-bis(aminomethyl)cyclohexane, 1.3
-bis(aminomethyl)cyclohexane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane,
piperazine.

N,N'-his(aminomethyl)bibe>diy(BAM
P), ethylenediamine, N,N'-di-tert-butylethylenediamine 7,l,6-hexanediamine (H
DA), 1,8-octanediamine, and 1,4-bis(aminomethyl)benzene.

The polyurethaneurea solution of the present invention comprises the above & chain diol,
Alicyclic diisocyanate and organic diamine, respectively, a
, b, c mol.

b eHere child 0.95~1.02 =0.3~1.
are in 5
It is preferable for adhesiveness to be large.

As organic solvents, tetrahydrofuran, methyl ethyl ketone, dioxane, stationary ethyl, etc. are mainly used during the polymerization process.

Dimethylformamide, dimethylacetamide, N
-Methylpyrrolidone, toluene, dichloroethane, inbrobanol, etc. can also be used.

The polyurethaneurea solution can be produced by various known methods. For example, 50 to
A method of reacting at 90°C to synthesize an isocyanate group-terminated prepolymer, extending the chain with an organic diamine, and diluting it with an organic solvent as necessary. For example, a method in which the Maki group diincyanate is added dropwise while stirring is used. The solid content of the polyurethaneurea solution when used as a brimer is:
5 to 50 inches, viscosity is Zo.

It is preferable that the temperature is about 10.000 cps/25°C.

The polyisocyanates that can be incorporated into the polyurethaneurea solution are organic polyisocyanates and inorganic-organic polyyn/anates such as silylborysonanate. Organic polyisocyanates are 9 e.g. toluef diisocyanate (TDI), diphenylmeth/diisocyanate) (
MDI).

Naphthalene diiso7anate, the above-mentioned alicyclic diisocyanate), 1.6-hetosane diisocyanate) (HDI),
Xylylene/diisocyanate, etc.

and carbodiimide-modified polyisocyanates and biuret-modified polyisocyanates derived therefrom,
Urethane/modified polyisocyanate, incyanurate modified polyisocyanate.

Cretidione-modified polyinsyanate, etc., are added in an amount of 5 to 3% based on the solid content of the polyurethane urea solution.
The adhesion process, in which approximately 0% by weight is used, begins with surface treatment of the plastic material. The surface oxidation treatment can be carried out by a wet method by immersion in a chromic acid mixture or an aqueous hydrogen peroxide solution, or a dry method by immersion in a plasma that introduces ozone or oxygen gas. Processing efficiency is great.

Dry methods are particularly preferred. A primer is applied to the surface of the plastic material at a solid content of 2 to 100 l/♂ to adhere the polyurethane resin.

In the case of cast-type polyurethane resin, the primer-treated plastic material is wetted with uncured resin and cured to bond.

In the case of thermoplastic polyurethane resin, the polyurethane resin is treated with a primer, brought into contact with the optical plastic material, and then heated under pressure to its melting point, or the polyurethane resin is melted and flowed and calendered to adhere. Steam-resistant bonding is possible with the above bonding method, but the mechanism is not clear. Possible causes include optimizing the polarity and strengthening the surface of the plastic material, stabilizing the adhesion between the primer and the surface of the plastic material under high humidity and heat, and stabilizing the adhesion between the primer and the surface of the polyurethane material, but it is not clear.

The adhesion method of the present invention is 1. Lamination of food conveyance belts.

It can be applied to artificial organ hollow fiber tube plate adhesion and electronic device implant sealing, and is useful for assembling highly reliable products, making it extremely useful industrially.

〔Example〕

Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. 1+Example Middle and Chi represent parts by weight.

Examples 1 to 6 and Comparative Examples 1 to 6 Production of polyurethaneurea solution A Fraxel CI)-220 (polycaprolactone diol, manufactured by Daicel Chemical Industries, hydroxyl value 56.1) 1.00
0 parts, IPDI 144.5 parts, tetrahydrofuran 1
145 parts and 2 parts of tin octylate were charged into a flask.

Stirring [Reaction was carried out at 760°C for 3 hours. Next, IPDA25
．． A solution consisting of 5 parts of toluene, 806 parts of toluene, and 806 parts of ethyl acetate A was divided into 3 parts, and 6 parts were reacted with vigorous stirring at °C for 30 minutes to obtain a viscous polyurethaneurea solution At-9. Solid content 30.5%, viscosity 12.500
cps/25°C.

Manufacture of polyurethaneurea solution B PHA (hydroxyl value 56.1) 1,000 parts, Desmody” W (Hu MDI, manufactured by 4 Bay)
210 parts, 1.210 parts of tetrahydrofuran and Octi #l! i! Pour 2 parts of tin into a flask, stir and heat to 60°C.
The mixture was allowed to react for 3 hours. Next, a solution consisting of 36 parts of IC2,4-TDA, 1,080 parts of toluene, and 1.080 parts of ethyl acetate was heated for 3 minutes and reacted with vigorous stirring at 60°C for 30 minutes to form a viscous polyurethane. Solution B was obtained.

Solids content 27.1%, viscosity 7.900 cps/25
℃ at nine.

Production of polyurethaneurea solution C Desmofen 2020E (PHC, manufactured by Bayer).

Hydroxyl value 56.1) 1.000 parts, C) IDI 166
parts, 1,166 parts of tetrahydrofuran and oct/l
2 parts of tin/l'12 was charged into a flask, stirred, and reacted at 60° C. for 3 hours. NextKkiI-MDA 105
parts, 1.136 parts of toluene and 1,136 parts of ethyl acetate.
The solution consisting of 3 parts was divided into 3 parts and each part was reacted at 60°C for 30 minutes with vigorous stirring to obtain a viscous polyurethane solution C.9. Solid content 27.3%, viscosity fiF 9.910 cp
s/ at 25℃-)Next.

Preparation of polyurethaneurea solutions D to 1. Polyurethaneurea solutions D to 2 were prepared in the same manner as A to C above. These are summarized in Table 1.

Margin Steam Resistance Adhesion Test A polystyrene plate of 25 mm width x 150 mm length x 2 tap thickness was previously surface-treated, and a KW1 cloth of 5 to 8 μm thickness (after drying) of brimer was applied to one side of the 25 mm edge of the plate.

Ply beak - Treat the round surfaces to face each other, create a gap of 1 mm, and seal the 'I11 side and bottom part with silicone rubber.
・Polyurethane for casting from the top 4! I fat (DN-495
4/DC-4964 manufactured by Nippon Polyurethane Industries).
Let it harden at 65℃ for 3 hours. Glue this lap to nine pieces (adhesion area 25 x 25 mrn' 1 at 25℃5
After leaving it for 24 hours at 0° R, H, put it in an autoclave, introduce steam, and reduce the internal pressure t-2, 1/- (temperature [12
0°C) and maintain this pressure for 30 minutes. After steam treatment, it was left for 24 hours at 25°C and 50mm R,H, and then subjected to a tensile tester to measure the shear adhesive strength. Table 2 shows the test results when the crosshead speed was 20 mm/6.
The adhesion method of the example has superior sdam resistance compared to the comparative example.

Notes on Shishi 1. Praxel CI)-220300 parts and PHA70
A copolymerized diol prepared by transesterifying 0 parts (molecular weight 2,000) with 220'C, Ql gas for 4 hours. Water P11 monovalent group 5.7. .

*2. Mixed diol of Zuck*le CD-22030ON and fx Moyxn 2Q 20g 700 parts. Hydroxyl value 56.
1゜rice 3. Poly (Nato2medelenadivate) Geo-
Le.

Manufactured by Nippon Polyurethane Industries. Hydroxyl value 56.1° or less Margin Table 2 Notes 1. Put a piece of plastic into an ozone generation chamber,
It was treated for 10 minutes at an ozone concentration of 30 t/d.

Coming 2.1! *Compared to a plastic piece placed in a plasma generation chamber that introduces elementary gas and treated for 10 minutes.

Next 3. The surface of the plastic piece was wiped with gauze and air-dried.

Rice 4. The plastic piece was placed in a plasma generation chamber into which argon gas was introduced and treated for one portion.

Margin below Example 7 The plastic material is polycarbonate.

Otherwise, the steam adhesion resistance was tested in the same manner as in Example 1, and the adhesive strength was 24.3, showing a good value of 9/-.

Example 8 The plastic material was soft vinyl chloride, and the other conditions were the same as in Example 2, and the steam resistance adhesion was tested, and the adhesive strength was 13.8, showing a good value of #/-.

Just in case.

Example 9 A polynisder fiber woven fabric (fabric thickness: Inm) was subjected to ozone oxidation treatment and then impregnated with K in a 15% solid content diluted polyurethane urea solution (diluted with tetrahydrofurano).

It was dried at 70°C for 30 minutes. Primer adhesion amount is 32
It was t/at. On top of this, Paraprene 22S (thermoplastic polyurethane, manufactured by Nippon Polyurethane Industries) 1k160
7. Melt by heating to ℃ and pour the next thing down. The fibers were rolled with a calendar roll, and a 2 mm thick thermoplastic polyurethane was laminated on the fibers. The laminate piece was placed in an autoclave and treated with 120°C steam for 30 minutes. The ones that were not primed peeled off.

Book 114 N4 piece was firmly adhered.

Example 10 Coronate L (polyol/TDI adduct polyisocyanate solution, l
A steam adhesion test was conducted in the same manner as in Example 1 except that a mixture of 5 parts and 8 parts (manufactured by Nippon Polyurethane Industries) was used as a primer, and a good value of 29.7 and 9/- was obtained for the adhesion strength.

Comparative Example 7 Using a 21% solution of Baraprene 228 in tetrahydrofuran (viscosity 5.300 cps/25°C) as a primer, a steam resistance adhesion test was conducted in the same manner as in Example 1, and the adhesive strength was 1.3 kg/cl11. Next you get a bad value.

Comparative Example 8 Poly (oxytetramethylene) diol (hydrogen value 5
6.1) 1,000 parts, 144.5 parts of IPDI, 1,145 parts of tetrahydrofuran, and 2 parts of diptyltin dilaurate were charged into a flask, stirred, and reacted at 60° C. for 3 hours. Next, each solution was divided into three parts in solution 1 consisting of 25.4 parts of KIPDA, 916 parts of toluene, and 916 parts of ethyl acetate.
The reaction was carried out at 60°C for 30 minutes with vigorous stirring to obtain a viscous polyurethaneurea solution. The solid content was 28.2%, and the viscosity was 9.800 cps/25°C.

A steam-resistant adhesion test was conducted in the same manner as in Example 1 except that 100 parts of the above solution was mixed with Coronate EH (I (DI polyisocyanurate polyinsyanate solution 1 was not included). ] The method of the present invention enables steam-resistant adhesion between plastic materials and polyurethane resin, which not only provides stable adhesion under high humidity and heat conditions, but also allows steam heating to be applied to sterilization in food and medical applications.Product safety and reliability Sexuality improves dramatically.

Claims (2)

[Claims] (1) In a method in which a primer is applied to a plastic material subjected to surface oxidation treatment and bonded to a polyurethane resin, the primer is (a) a long-chain diol with a molecular weight of 1,500 to 4,000; hexamethylene adipate) diol poly(hexamethylene carbonate) diol, either alone;
Alternatively, a steam-resistant adhesive method comprising a polyurethaneurea solution prepared by reacting a mixture of two or more types or a copolymer thereof (b) alicyclic diisocyanate (c) organic diamine in an organic solvent. (2) The method according to claim (1), wherein the primer is a mixture of the polyurethaneurea solution and an organic polyisocyanate.