JPH01278517A - Adhesive composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition suitable for adhesion and coating of rubber goods, synthetic resin goods, etc., and capable of forming a coating film excellent in hardwearing properties and adhesion to adherends by mixing a specified polyurethane with a halogenating agent and a silicone oil respectively in specified amounts. CONSTITUTION:(A) 100pts.wt. polyurethane consisting of a polyol (e.g., polypropylene glycol), triethanolamine and a polyisocyanate (e.g., 2,4-tolylene diisocyanate) in 1:0.05-2.0mol ratio of the polyol: triethanol amine and 1:1.5-7mol ratio of hydroxyl group (OH) : isocyanate group (NCO), (B) 0.002-20 pts.wt. halogenating agent (e.g., N-bromosuccinimide) and (C) >=10pts.wt. silicone oil are blended to provide the objective composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an adhesive composition suitable for adhering or painting rubber products, synthetic resin products, etc.

[Prior art] Conventionally, natural rubber (NR), styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), isobutylene-isoprene copolymer rubber (IIR), chloroprene rubber (CR), acrylonitrile-butadiene copolymer Surfaces of synthetic rubber such as rubber (NBR), isoprene rubber (IR), ethylene-propylene-shikonine copolymer rubber (EPDM), ethylene-propylene copolymer rubber (EPT), cotton, rayon, ABS resin, PS, etc. The painting is
Resin paints such as nylon, epoxy, acrylic, and acrylic-ethylene copolymer, or rubber paints such as BR, CR, and SBR are used.

In addition, methods for imparting wear resistance to automobile weather strips include applying a urethane paint containing chloroprene rubber to the surface to provide a chloroprene rubber film, or providing a silicone coating layer. be.

[Problem to be solved by the invention] 2. Conventional resin-based paints and rubber-based paints have problems such as poor adhesion to adherends and poor abrasion resistance of the resulting paint films. Ta. Further, the method of providing a coating of black 1-prene rubber on the Weathers 1 to lip or providing a silicon coating layer still has the problem of poor abrasion resistance.

An object of the present invention is to solve the above-mentioned problems and to provide an adhesive composition whose resulting film has excellent abrasion resistance and good adhesion to adherends.

[Means for Solving the Problem] In order to solve the above problems, the present invention comprises a polyol, triethanolamine and polyisocyanate,
The molar ratio of polyol:l/liethanol 7min is i:o
, os~2.0, and the molar ratio of hydroxyl group (-08): isocyanate group (-NGO) is 1:1.5 to 7, and a halogenating agent of 0°002 per 100 parts by weight of the same polyurethane. 20 parts by weight of silicone oil, 10 parts by weight or more of silicone oil, and a solvent.

[Detailed Description of Means] First, the polyurethane used in the present invention will be described.

As the polyol, polypropylene glycol (P
I) C) A compound obtained by adding propylene oxide to l-lyethylene glycol (FC) glycerin, a compound obtained by adding propylene oxide to saccharide sugar, and the like. The polypropylene glycol preferably has a number average molecular weight of 800 to 6,000.

The amine is 1-jetanolamine, and monoethanolamine and jetanolamine are unsuitable because they cause a crosslinking reaction and cause the polyurethane to gel.

Polyisocyanate is a compound having a plurality of isocyanate groups, such as 2.4-1 to lylene diisocyanate, 65/35 (2,4-tolylene diisocyanate and 2,6-1-lylene diisocyanate). Proportion of diisocyano-I-1, 8)
0/20+-relene diisocyanate-1., 4.4'-phenylmethane diisocyanone-1., dianine diisocyanate-1., tridene diisocyanate, hexamethylene diisocyanate-1., metagi silane diisocyanate,],]5-naphthalene diisocyanate-I, hydrogenated 4,4'-diphenylmethane diisocyanate-1, hydrogenated xylene diisocyanate, hydrogenated 2,4-h lylene diisocyanate, water Added 65/351-lylene diisocyanate, hydrogenated 80/20) lylene diisocyanate,
Isophorone diisocyanate, 4. 4', 4
″-1-rephenylmethane triisocyanate, 1 to 1
Js(p-isocyanatophenyl)thiophosphate-1
・etc. are used.

The molar ratio of the polyol to triethanolamine is 1:
It is 0.05 to 2.0. If this ratio is less than 0.05 or more than 2.0, the adhesive strength will be greatly reduced.

The molar ratio of hydroxyl group (-0H) in the polyol to isocyanate group (-NGO) in the polyisocyanate is 1.5 to 7, and the isocyanate group is blended in excess of the hydroxyl group.

If this ratio is less than 1.5 or more than 7, the adhesive strength will decrease, and there may be cases where no adhesion occurs.

Synthesis of polyurethane is performed by mixing the polyol, triethanolamine, and polyisocyanate, and reacting the mixture at 80° C. for 3 hours in a nitrogen gas atmosphere.

At this time, a solvent may be used if desired. The same solvents include n-hexano, cyclohexane, benzene, toluene, gilcine, ethylhenzene, athene, methyl ethyl ketone, methyl isopropylene, methyl isobutyl ketone, tetrahydrofuran, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, Examples include methylene chloride, 1.1.1-trichloroethane, dimethyl sulfoxide, and dimethylformamide (DMF).

Next, as a halogenating agent, acid imide halogen compounds such as N-promsuccinimide (NBS I) and N-bromphthalimide, trichloroisocyanuric acid (TC
IA), isocyanuric acid halides such as dichloroisocyanuric acid, halokenated hydantoins such as dichlorodimethylhydantoin, alkyl hypohalides, etc. are used.

``Alkyl Hypohalides Secondary or tertiary alkyl hypohalides, especially stable tertiary argyl chlorides and bromides, ie tertiary butyl hypochloride (t-Bl
(C), tertiary butyl hypofluorite, tertiary aluminum hypofluorite, tertiary aluminum hypofluorite, etc. are preferred, and furthermore, halogen-substituted alkyl hypochloride such as dichloro, trichloro or fluoromethyl hypofluorite, etc. You can also use

The halosaponizing agent was added in an amount of 0.0% per 100 parts by weight of the polyurethane. 002 to 20 parts by weight are blended.

If the blending ratio is less than 0.002 parts by weight, the degree of chlorination is small, resulting in poor adhesion, and if it exceeds 20 parts by weight, the stability of the adhesive composition deteriorates.

As the silicone oil, dimethyl silicone oil, methyl chloride silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil, etc. are used.

The blending ratio of the silicone oil is 1% of the above polyurethane.
00 parts by weight or more. If the amount is less than 10 parts by weight, the wear resistance cannot be improved. The upper limit is not particularly limited, but is preferably 1,000,000 parts by weight or less, with even better SE L below 100,000 parts by weight. Even if it is blended in an amount exceeding 1 million parts by weight, the effect of improving abrasion resistance remains unchanged, but on the contrary, adhesiveness deteriorates.

[Function] By employing the above means, the adhesive composition has the characteristics such as the lubricity of the silicone oil and the characteristics of the polyurethane, which is composed of polyol, l-liethanolamine and polyisocyanate and has a predetermined structure having an isocyanate group, The abrasion resistance of the resulting coating is improved, and the adhesion to the object to be coated is improved, particularly by the action of the halogenating agent.

[Examples 1 to 6 and Comparative Examples 1 to 10] Examples in which the present invention is embodied as a coating composition will be described below in comparison with comparative examples.

First, the object to be coated is a vulcanized product as shown below.

That is, the vulcanizate contained 100 parts by weight of EPDM (hereinafter simply referred to as parts), 7θ parts of carbon black, 35 parts of mineral oil, 7 parts of zinc oxide, 2 parts of stearic acid, 2 parts of vulcanization accelerator, and 1 part of sulfur.
．． A composition consisting of 5 parts was vulcanized at 160°C for 30 minutes.

In addition, the wear resistance test was conducted by the following method, and the wear resistance was evaluated based on the amount of wear loss.

That is, worn wheel: H-22, load: 1 kg, worn rotation speed:
60 rpm Sample size: lO 100 mm x 100 Number of wear: 1000 times Next, polyol (PO), triethanolamine (TEA), polyisocyanate (PI) shown in Table 1 below
) were mixed in trichlorethylene and reacted at 80° C. for 3 hours in a nitrogen gas atmosphere to synthesize polyurethane. The obtained polyurethane had a solid content of 83% and a trichlorethylene content of 17%.

Table-I The abbreviations in Table-1 represent the following meanings.

PPG 3000: Polypropylene glycol with a number average molecular weight of 3000 PllG 1000: Polypropylene glycol with a number average molecular weight of 1000 Pl'lG 2000: Polypylene glycol TG 3000 with a number average molecular weight of 2000: Triethylene glycol TG 1000 with a number average molecular weight of 13000: Triethylene glycol with a number average molecular weight of 1000 TG 2000: Triethylene glycol with a number average molecular weight of 2000 MDI: 4,4'-diphenylmethane cyisocyanate = 1
to NDIl. , 5-naphthalene isocyanin-1.XDI
: Xylylene diisocyanate I/IPDI: Isoborone diisocyanate Next, the solid content of the above polyurethane is 10
Using a coating composition containing 0 part by weight of a halogenating agent (parts by weight) shown in Table 2 below, adhesive strength was measured using a 5x polyethylene foam as an adherend.

The test pieces used for adhesive strength measurement were two polyethylene 5x foam test pieces coated with the adhesive composition in a 25×25
The adhesive was coated on an adhesive area of mm, heated at 100°C for 2 minutes to evaporate the solvent, and then laminated with a BJ under a load of 5 kg/ct. For this test piece, the tensile shear strength (kg/c+
a) was measured. The results are shown in Table-2.

In addition, the following coating composition was used as a comparative example.

(Comparative Example 1) 100 parts of liquid polybutadiene (product name (1) Hikari Seal AB-700W, manufactured by Idemitsu Petrochemical Industries, Ltd.),
Coating O 1 was prepared by mixing the MDIIO part. This paint was applied to the object to be coated and cured at room temperature to prepare a test piece. This test piece was subjected to the abrasion resistance test described above.

The results are shown in Table 3 below.

(Comparative Example 2) 100 parts of liquid polyphtadiene (trade name: Idemitsu Seal AB-100, manufactured by Idemitsu Petrochemical Industries Co., Ltd.), MD I 1
0 parts were mixed to prepare a paint. This paint was applied to the object to be coated and cured in chamber 7□11 to prepare Test J4. Regarding this test 111, the above-mentioned wear resistance test was conducted.

The results are shown in Table 3 below.

(Comparative Example 3) A 70% solution of N-methylated nylon (trade name: Resin M-20, manufactured by Teikoku Kagaku Sangyo Co., Ltd.) was applied to the object to be coated and cured at room temperature to prepare a test piece. did. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 3 below.

(Comparative Example 4) 100 parts of epoxy resin (trade name: Araldite PZ820, manufactured by Nippon Chiha Geigy Co., Ltd.), polyaminoamide (
Product name: Hardener T (Z) manufactured by Nippon Chiha Geigy Co., Ltd.
100 parts were mixed to prepare a paint. This paint was applied to the object to be coated and cured at room temperature to prepare a test piece. This test piece was subjected to the above-mentioned 19 wear resistance test. The results are shown in Table 3 below.

(Comparative Example 5) Epoxy resin (trade name: Araldite GY250, manufactured by Nippon Chiha-Geigy Co., Ltd.) and 30 parts of polyaminoamide (trade name, Hardener Hz, manufactured by Chiha-Geigy Co., Ltd.) were mixed to prepare a paint. This paint was applied to the object to be coated and cured at room temperature to prepare a test piece. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 3 below.

(Comparative Example 6) As a paint, a 74% toluene solution of 1-1 μm of l:I Ulprene (product name: Pon, manufactured by Iniji Co., Ltd.) “G2”
) was applied to the object to be coated and cured at room temperature to prepare a test piece. This test piece was subjected to the abrasion resistance test described above.

The results are shown in Table 3 below.

(Comparative Example 7) SBR (trade name: Diabond 5010, manufactured by Nogawa Gemical Co., Ltd.) was applied to the object to be coated, and cured at room temperature to prepare a test piece. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 3 below.

(Comparative Example 8) As a paint, an acrylic resin emulsion with a nonvolatile content of 70% (trade name: Diapon, manufactured by Tsuga Noghemical Co., Ltd.)
DA-830A) was applied to the object to be coated and cured at room temperature to prepare a test piece. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 3 below.

(Comparative Example 9) As a paint, an acrylic-ethylene modified emulsion (manufactured by Sunstar Chemical Co., Ltd., trade name: Penguin Semen 138) with a non-volatile content of 55% was applied to the object to be coated and cured at room temperature to prepare a test piece. did.

This test piece was subjected to the abrasion resistance test described above.

The results are shown in Table 3 below.

(Comparative Example 10) As a paint, a polyurethane paint (trade name: Diabond DA700E, manufactured by Nogawa Chemical Co., Ltd.) was applied to the object to be coated and cured at room temperature to prepare a test piece. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 3 below.

Table-2 The abbreviations in Table-2 represent the following meanings.

DMSi Nidimethyl silicone oil*: Viscosity 10,000 centistokes (C3t)*; Viscosity 60,000 cSt*: Viscosity 100,000 cSt Further, the amount of wear is expressed in mg/1000 times.

Table 3 As can be seen from Table 2 above, the coating compositions of each example had an abrasion loss of 6 to 2 even after 1000 abrasion tests.
It is extremely small at 1 mg.

The reason why the coating compositions of each example exhibit such excellent abrasion resistance is due to the lubricity and other properties of silicone oil and the properties of polyurethane consisting of a predetermined amount of polyol, triethanolamine, and polyisonoanate. This is thought to be based on characteristics such as rigidity.

In addition, the coating compositions of each example exhibited excellent adhesion to the coated object, especially due to the action of the halogenating agent halogenating the coating composition itself and the coated object to improve mutual bonding strength. .

On the other hand, as can be seen from Table 3, the coating compositions of each comparative example had a large abrasion loss of 469 to 2060 mg, and had poor abrasion resistance.

[Examples 7 to 12 and Comparative Examples] 1 and 12 Examples 1 and 12 Next, examples will be described in which the present invention is applied to paints used for automobile weather strips.

The base material constituting Weathers I Lip is usually polyolefin vulcanized rubber. Specifically, E1) DM, ethylene-propylene cobylene copolymer rubber (EPM), and the like can be mentioned. Furthermore, an amount within a range that does not impair the properties of these copolymer combs, for example, 1/2 of the above polyolefin vulcanized rubber.
It is also possible to use compounds containing other rubber components in amounts of not more than parts by weight. Other rubber components include the above-mentioned NR, SBR, N
Examples of BI include IR, CRX I IR, etc.

2.Various vulcanized rubbers contain commonly used compounds such as vulcanizing agents, vulcanization accelerators, anti-aging agents, antioxidants, anti-ozonants, fillers, plasticizers, blowing agents, and blowing assistants. Agents and the like are appropriately blended depending on the purpose.

Examples of the vulcanizing agent include sulfur, morpholine, disulfide, dicumyl peroxide, and the like.

Examples of the vulcanization accelerator include 2-mercaptobenzothiazole, zinc dimethyldithiocarbamate, and tetramethylthiuram disulfide.

As anti-aging agents, antioxidants, and ozone deterioration inhibitors,
Examples include phenyl-α-naphthylamine and 2,6-di-t-butyl-p-cresol.

Examples of the filler include carbon black, hydrated silicic acid, magnesium carbonate, and clay.

Examples of plasticizers include dioctyl sebacate and mineral oil.

As a blowing agent, N,N'-dinitrosopentamethylenetetramine, N,N'-dimethyl-N.

N'-dinitrosoterephthalamide, azodicarbonamide, azobisisobutyronitrile, benzenesulfonylhydrazide, p,p'-oxybis(benzenesulfonylhydrazide), toluenesulfonylhydrazide, and the like.

Examples of foaming aids include urea and salicylic acid.

Now, after extrusion molding an EPDM compound having the composition shown in Table 4 below as a base material for a weather strip, it was heated at 160°C.
The mixture was vulcanized for 30 minutes to produce a weather strip for automobiles.

Table 4 The coating compositions of the Examples and Comparative Examples shown in Table 5 below were applied to the Weathers I Lip to prepare test pieces. This test piece was subjected to an abrasion resistance test using a glass edge abrasion tester, which is an improved version of the Gakushin abrasion tester, under the following conditions.

(Conditions) Friction element Nigaras < rrt height 5 mm) Friction element cycle: 60 times/min Friction element stroke near 0 mm (Test method) Normal wear - Attach the base material to the above testing machine, rub the base material and check the Examine the abrasion properties of

Table-5 The abbreviations in Table-5 represent the following meanings.

○: The amount of wear is small and the wear resistance is good.

×: Amount of wear is large and wear resistance is poor.

DMSi: Dimethyl silicone oil, viscosity 10,000C
5t *: Viscosity 60,000 cSt *: Viscosity 100,000 cSt In addition, in Table 5 above, polyurethane ■ and ■
For example, it was synthesized in the same manner as in Examples 1 to 6 above using raw materials having the compositions shown in Table 6 below.

As can be seen from Table 5 above, in Comparative Examples 11 and 12, the coating compositions themselves were kelized or had poor abrasion resistance, whereas in Examples 7 to 12, the coating compositions were not worn after 50,000 times. It is durable and has no wear problems.

In addition, weather strips coated with the coating compositions of the above-mentioned Examples were bent by 180 degrees to examine their conformability. As a result, the flexibility and flexibility, which are the characteristics of polyolefin vulcanized rubber as a base material, are not impaired in any way.
It showed good followability.

Therefore, the coating compositions of Examples 7 to 12 are suitable as coating compositions for weather stripping.

[Examples 13 to 18 and Comparative Examples 13 and 14] Next,
An example in which the present invention is embodied in an adhesive composition used for electrostatic flocking will be described.

On each side below, the adhesive compositions of the following Examples were applied to an EPDM base material, and electrostatic flocking was performed to prepare a test piece. This test piece was subjected to an abrasion test of 30,000 times under a load of 5 kg according to Examples 1 to 6 above.

The results are shown in Table-7.

(Example 13) The adhesive composition described in Example 7 above was used.

(Example 14) The adhesive composition described in Example 8 above was used.

(Example 15) The adhesive composition described in Example 9 above was used.

(Example 16) The adhesive composition described in Example 10 above was used.

(Example 17) The adhesive composition described in Example 11 above was used.

(Example 18) The adhesive composition described in Example 12 above was used.

(Comparative Example 13) The adhesive composition described in Comparative Example 11 above was used.

(Comparative Example 14) Using the adhesive composition described in Comparative Example 12, Table 7 In the column of the number of wears in Table 7, ○ indicates a small amount of wear and is good, and × indicates a large amount of wear. , indicates a defect.

As can be seen from Table 7, in Comparative Examples 13 and 14, the adhesive composition itself turned into clay or had poor abrasion resistance, whereas in Examples 13 to 18, the adhesive composition It has sufficient resistance to wear and there is no problem with wear.

Therefore, the adhesive compositions of Examples 13 to 18 are suitable as adhesive compositions for electrostatic flocking.

[Effects of the Invention] The adhesive composition of the present invention has the effect that the resulting film has excellent abrasion resistance and also has good adhesion to adherends.

Claims (1)

[Claims] 1. Consisting of polyol, triethanolamine and polyisocyanate, the molar ratio of polyol:triethanolamine is 1:0.05-2.0, and the hydroxyl group (
-OH): molar ratio of isocyanate group (-NCO) is 1
:1.5 to 7 polyurethane and the same polyurethane 1
An adhesive composition comprising 0.002 to 20 parts by weight of a halogenating agent and 10 parts by weight or more of a silicone oil.