JPH01278516A - Adhesive composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition suitable for adhesion and coating of robber good, synthetic resin goods, etc., and capable of forming a coating film excellent in hardwearing properties and adhesion to materials to be coated by mixing a specified polyurethane with a halogenating agent and a silicone oil respectively in specified amounts. CONSTITUTION:(A) 100pts.wt. polyurethane having isocyanate or hydroxyl groups obtained by reacting a mixture of a polyester-based diol (e.g., reaction product between ethylene glycol, etc., and succinic acid, etc.) and a polyether-based diol (e.g., polyoxypropylene glycol) with a diisocyanate (e.g., 2,4-tolylene diisocyanate) and furthermore reacting the resultant reaction product with a diol with low molecular weight (e.g., ethylene glycol), (B) 0.002-20pts.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 and painting rubber products, synthetic resin products, etc.

[Prior art] Conventionally, natural rubber (NR), styrene-butadiene copolymer rubber (Sl13R), phthalene rubber (BR), isobutylene-isoprene copolymer rubber (IIR), chromium rubber:]
Prene rubber (C,R), acryl-conitrile-butadiene copolymer rubber (NBR), isoprene rubber (IR),
Ethylene-propylene-diene copolymer rubber (EPDM)
For surface coating of synthetic rubber such as , ethylene-propylene copolymer rubber (El)T), cotton, rayon, ABS resin, PS, etc., nylon-based, epoxy-based, acrylic, and acrylic-ethylene copolymer-based resin paints are used. Or BR, CR1SB
Rubber paints such as R 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.

[Problems to be solved by the invention] 2. Conventional resin-based paints and comb-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 chloroprene rubber coating 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 problems mentioned in -1- above, to provide an adhesive composition in which the obtained film has excellent abrasion resistance and has good adhesion to adherends.

[Means for Solving the Problems] In order to achieve the above-mentioned objects, the present invention involves reacting a low molecular weight diol with a reaction product of a mixture of polyester diol and polyether diol and diisocyanate. For 100 parts by weight of polyurethane having isocyanate groups or hydro-1-syl groups, 2 to 20 parts by weight of a halosaponizing agent and 10 parts by weight or more of silicone oil are used.

[Detailed Description of Means] The polyester diols used in the present invention include ethylene glycol, propylene glycol, butanediol-1,4, butanediol-1.3, butanediol-2,3, and cyethylene glycol. , dipropylene glycol, triethylene glycol, pentanediol-1.5, hexanethiol-1,6, neopentyl glycol, etc., or a mixture of succinic acid, adipic acid, azelaic acid, sebacic acid,
Those synthesized by reacting one type or a mixture of two or more types of carboxylic acids such as phthalic acid and isophthalic acid are used.

As the polyether diol, polyoxypropylene glycol tyrene glycol, polyte-1-ramethylene oxide glycol, etc. are used.

These polyester diols and polyether diols are used in combination. The mixing ratio of the polyester diol and the polyether diol can be set at an appropriate ratio over a wide range.

The diisocyanate is 2.4-tolylene diisocyanate-1., 65/35 (ratio of 2.4-tolylene diisocyanate and 2.6-1 to lylene diisocyanate-1., the same applies hereinafter) Tolylene diisocyanate I, 80/
20 tolylene diisocyanate, 4,4'-cyphenylmethanesoisocyanate-1-(MDI), dianidine diisocyanate-1-, tridencyisocyane-1-, to;
1-zamethylene diisocyanate, metaxylene diisocyanate *-1-, 1.

5-naphthalene diisocyanate, hydrogenated 4,4'-Schiff Lmethane diisocyanate I, hydrogenated xylene diisocyanate, water iE2.4-l, lylene diisocyanate, hydrogenated 6 5/3 5 1-lylene diisocyanate I
・Hydrogenated 80/201-lylene diisocyanate, isoborone soisocyanate, etc. are used.

This diisocyanate is reacted with the mixture of the polyester diol and polyether diol. At that time, the ratio of the mixture and the diisocyano-I group used is such that the molar ratio of these hydroxyl groups <-0I) to the isocyano-I group (-NGO) is 1; in the range of 2 to 10. or suitable. When the ratio of NGO is less than 2, the polyurethane itself becomes too soft and tends to be unsuitable as an adhesive composition, and when the ratio of -Nco exceeds 10, the polyurethane itself becomes too hard and brittle.
It is likely to be unsuitable as an adhesive composition.

Examples of low molecular weight diols include ethylene glycol, propylene glycol, and butanediol-1.

4, Butanediol-1.3, Butanediol-2,3
, diethylene glycol, dipropylene glycol, I
・Diethylene glycol, pentanediol 1,5,
One or a mixture of two or more of hegysanthiol-1,6, neopentyl glycol, etc. is used.

This low molecular weight diol is composed of a mixture of the polyester diol and polyether diol and a diisocyanol-1
・Added to the reaction product with. When the proportion of its use increases, the proportion of 1OH becomes greater than the proportion of -NCO, producing polyurethane with terminal -OH, and when it decreases, the proportion of 1NGO becomes relatively greater than the proportion of -0)1. A polyurethane with an NGO terminal is produced, but any one can be used, so the setting is appropriately determined depending on the purpose of use.

A polyurethane having an isocyanate-1 group or a hydroxyl group is obtained by first reacting a mixture of a polyester diol and a polynylene diol with an isocyanate-1 group, and then reacting the reaction product with the above-mentioned reaction product. Obtained by reacting low molecular weight diols.

At this time, a solvent may be used if desired. The same solvents include n-hexane, cyclohexane, Hensen, toluene, xylene, ethyl Hensen, methyl ethyl, methyl isobrovir ketone, methyl isophthyl ketone, tetrahydrocofuran, acetic acid. Methyl, ethyl acetate, isopropyl acetate, isobutyl acetate, methylene chloride, 1.1. ,]-]1-lychloroethanedimethylsulfokinoids, dimethylformamide (DMF), and the like.

As a halogenating agent, N-promsuccinimit (
NBSI), acid imide halogen compounds such as N-Bl'mufthalimite, isocyanuric acid halides such as I-dichloroisocyanuric acid (TCI8), dichloroisocyanuric acid, halokenated hydantoins such as dichlorodimethylhydantoin, alkyl hypohalides, etc. used.

"-Alkylhybohalides are normal, secondary or tertiary alkylhypohalides, particularly stable tertiary alkyl chlorides and bromides, such as tertiary butylhypochloride and tertiary butylhypohalide. Bromide, tertiary aluminum hypobromide and the like are preferred, and further halogen-substituted argyl hypochloride such as dichloro, trichloro or fluoromethyl ibochloride can also be used.

The halosaponizing agent is blended in an amount of 0.002 to 20 parts by weight per 100 parts by weight of the polyurethane.

When the blending ratio is less than 0.002 parts by weight, the degree of chlorination is small, resulting in little improvement in adhesive properties, and when 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, and more preferably 100,000 parts by weight or less. 1
Even if it is blended in an amount exceeding 1,000,000 parts by weight, the effect of improving surface 4 abrasion properties remains unchanged.

[Function] By adopting the configuration described above, the adhesive composition has the characteristics of silicone oil and the characteristics of polyurethane having a predetermined structure using a combination of polyester diol and polyether diol and using a low molecular weight diol. This improves the abrasion resistance of the resulting coating, and also improves the adhesion to the object to be coated, particularly due to the action of the halogenating agent.

[Examples 1 to 6 and Comparative Examples 1 to 10] Examples in which the present invention is embodied in paints will be described below.

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

That is, the vulcanizate contains 00 parts by weight of EPDMI (hereinafter simply referred to as "parts"), 70 parts of carbon blank, 35 parts of mineral oil, 7 parts of zinc oxide, 2 parts of stearic acid, 2 parts of vulcanization accelerator, and 1.5 parts of sulfur. The composition 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: 10100 mm x 100 Number of wear: 100 times (Example 1) PPG (molecular weight approx. 2000) 1.20 parts, polyethylene adipate (molecular weight approx. 2000) 4.4[, MDI1
A mixture of 0.00 parts and 264 parts of trichlorethylene was heated at 80° C. for 13 hours in a stream of dry nitrogen.

Furthermore, 24.8 parts of 1,6-hexanediol, DMF
170 parts were added and heated at 80°C for 20 minutes in a stream of dry nitrogen. As a result, a urethane polymer was obtained.

This urethane polymer 1. For 0 parts of O0, 30 parts of carphone black, 100 parts of toluene, 40 parts of DMF, dinotyl silicone oil [viscosity approximately 10,000 centistokes (
(hereinafter referred to as cSt)] 220 copies'rCIA0.00
Two parts were mixed to obtain a coating composition.

This coating composition was applied to the object to be coated and heated at 100°C for 2 hours.
A test piece was prepared by heat curing for a minute. This test piece was subjected to an abrasion test on the above-mentioned surface. The results are shown in Table 1 below.

(Example 2) Urethane polymer 1 prepared in the same manner as in the above example]
00 parts, carbon black 10 parts, toluene 80 parts
parts, DMF 50 parts, dinotyl silicone oil (viscosity 1
00,000 cSt) and 30 parts of NB5l084 parts were mixed to obtain a coating composition.

This coating composition was applied to the object to be coated and heated at 100° C. for 5 minutes to prepare a U-ζ test piece. This test piece was subjected to the above-mentioned surface/one wear test. Results] 1 The results are shown in Table 1 below.

(Example 3) 140 parts of PPG (molecular weight approximately 2000), 60 parts polyethylene adipate (molecular weight approximately 2000), MD I 1
00 parts and 300 parts of trichlorethylene were reacted in the same manner as in Example 1, and then 1,6-hexanediol 24
．． 2 parts and 246 parts of DMF were added and reacted in the same manner as in Example 1 to synthesize a urethane polymer.

To 100 parts of this urethane polymer, 30 parts of carbon blank, 100 parts of benzene, 50 parts of DMF, 30 parts of dimethyl silicone oil (viscosity 100,000 C3t), i''
A paint & J1 composition was prepared by blending 0.1 part of CI A.

This coating composition was applied to the object to be coated, and
A test piece was prepared by heating for a minute. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 1 below.

(Example 4) 60 parts of PPG (molecular weight 2000), 140 parts PEBΔ]2 (molecular weight approximately 2000), 100 parts MDI, and 300 parts trichlorethylene were mixed and reacted in the same manner as in Example 1 to obtain polyurethane. .

For 100 parts of this polyurethane, 189 parts of 1,4-butanediol, 246 parts of I) MF, TCIAI
Part O, dimethyl silicone oil (viscosity 60,000 cst) 3
A coating composition was prepared by blending 5 parts.

Using this coating composition, a test piece was prepared in the same manner as in Example 3 described below. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 1 below.

(Example 5) PPG (molecular weight approximately 2000) 60 parts, PBA (molecular weight approximately 2000) Ii, 0 parts, M II) 1100 parts, I
- 300 parts of chlorethylene was mixed and reacted in the same manner as in Example 1 to obtain polyurethane.

For 100 parts of this polyurethane, ethylene glycol: J
-/L/ 12.2 parts, DMF 300 parts, TCIA
20 parts, dimethyl silicone oil (viscosity 1 million cSt)
) to prepare a coating composition.

A test piece was prepared in the same manner as in Example 1 using this coating composition. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 1 below.

(Example 6) 140 parts of PPG (molecular weight approximately 2000), P E I3
A (molecular weight approximately 2000) 60 parts, MDI 100 parts, trichlorethylene 300 parts, ethylene glycol 12.2
The components were mixed and reacted in the same manner as in Example 1 to obtain polyurethane.

For 100 parts of this polyurethane, l) 300 parts of MF,
TCIAIO part, dimethyl silicone oil (viscosity 10
A coating composition was prepared by blending 50 parts of 10,000 cSt).

A test piece was prepared in the same manner as in Example 1 using this coating composition. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 1 below.

(Comparative Example 1) Liquid polybutadiene (trade name: Idemitsu Seal AB-700W, manufactured by Idemitsu Petrochemical Industries, Ltd.)1. O0 part, MDIIO
A paint was prepared by mixing the two parts. The 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 1 below.

(Comparative Example 2) 1.00 parts of liquid polyphtatsuene (product name: Idemitsu Seal AB-100, manufactured by Idemitsu Petrochemical Industries, Ltd.) and part MDIIO were mixed to prepare a paint. This coating ζI 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 1 below.

(Comparative Example 3) 70% of N-methoxymethylated nylon? Younya (trade name: Resin M-20, manufactured by Teikoku Kagaku Sangyo Co., Ltd.) was applied to the coated object and cured at room temperature to prepare a test piece. The above-mentioned abrasion resistance test was conducted on the test piece. The results are shown in Table 1 below.

(Comparative Example 4) 100 parts of epoxy resin (trade name: Araldai 1-PZ820, manufactured by Chiha Geigy Corporation), 100 parts of polyaminoamide (trade name: Hardener H2, manufactured by Chiha Geigy Corporation, Japan)
) 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 surface 4 wear test. The results are shown in Table 1 below.

(Comparative Example 5) 1.00 parts of epoxy resin (trade name: Araldite GY250, manufactured by Nippon Chiha Geigy Co., Ltd.), polyaminoamide (trade name, Hardener 1 (trade name, manufactured by Nippon 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 1 below.

(Comparative Example 6) As a paint, a 74% solution of chloroprene rubber in toluene (product name Pon, manufactured by Konishi Co., Ltd.) "C; 2) was applied to the object to be coated and cured at room temperature to prepare a test piece. The above-mentioned abrasion resistance test was conducted on the test piece.The results are shown in Table 1 below.

(Comparative Example 7) SBR (trade name: Diapond 5010, manufactured by Nogawa Chemical Co., Ltd.) was applied to the coated object 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 1 below.

(Comparative Example 8) As a paint, an acrylic resin emulsion with a non-volatile content of 70% (trade name: Diaponl manufactured by Nogawa Chemical Co., Ltd.) was used as a paint.
)A-830A) was applied to the coated object 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 1 below.

(Comparative Example 9) As a paint, an acrylic-ethylene modified emulsion (trade name: Penguin Semen, manufactured by Sunstar Chemical Co., Ltd. 1.38) with a non-volatile content of 55% was applied to the object to be coated, cured at room temperature, and tested. A piece was made.

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

The results are shown in Table 1 below.

(Comparative Example 10) As a paint, a polyurethane paint (trade name: Diapond 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 1 below.

Table 1: For 0 wear tests, the wear amount of the test piece coated with the paint of each comparative example was as large as 482 cm or more, whereas the wear amount of the test piece coated with the paint composition of the present invention was large. It is very small, less than 16 square meters, and has excellent wear resistance. This is thought to be due to the precipitation of silicone oil in the coating composition on the surface and the polyurethane having a specific structure.

Moreover, the paints of each example have excellent adhesion to the object to be coated.

[Examples 7 to 12 and Comparative Examples 11 and 12] Next, examples will be described in which the present invention is applied to a paint used for automobile weather strips.

The base material constituting the weather strip is usually polyolefin vulcanized rubber. Specifically, EPDM, ethylene-propylene copolymer rubber (IEI) M), etc. can be mentioned. Furthermore, the amount of the copolymer rubber within a range that does not impair the properties of the copolymer rubber, for example, 1/
It is also possible to use other rubber components in an amount of 2 parts by weight or less. Other rubber components include the above-mentioned NR, SBR,
Examples include NBR3IR, CR, l IR, etc.

- Various vulcanized combs contain commonly used compounds such as vulcanizing agents, vulcanization accelerators, anti-aging agents, antioxidants, antiozonants, fillers, plasticizers, blowing agents, and blowing assistants. Agents and the like are appropriately added 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-mercaptohendithiazole, zinc dimethyldithiocarbamate, and te-1-ramethylthiuram disulfide.

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

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

Examples of the plasticizer include dioctyl sebaque-1, mineral oil, and the like.

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

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

Examples of foaming aids include urea and salicylic acid.

Now, as a base material for a weather strip, an EPDM compound having the composition shown in Table 2 below was extruded and then vulcanized at 160 DEG C. for 30 minutes to produce a weather strip for an automobile. A test piece was prepared by coating the same weatherstrip with a coating composition according to each of the following examples. This test piece was subjected to an abrasion test of 50,000 times in accordance with Examples 1 to 5 above.

The results are shown in Table-3.

Table-2 (Example 7) The coating composition described in Example 1 above was used.

(Example 8) The coating composition described in Example 2 above was used.

(Example 9) The coating composition described in Example 3 above was used.

(Example] 0) The coating composition described in Example 4 above was used.

(Example 11) The paint & iii composition described in Example 5 above was used.

(Example 12) The coating composition described in Example 6 above was used.

(Comparative Example 11) In the coating composition of Example 1, the blending ratio of TAIC as a halogenating agent was varied from 0.002 parts to 25 parts.

(Comparative Example 12) In the coating composition of Example 2, the blending ratio of NBSI as a halogenating agent was varied from 0.4 parts to 30 parts.

○ in Table 3 indicates that the amount of wear is small and the wear resistance is good.

As can be seen from Table 3, in Comparative Examples 11 and 12, the coating composition itself turned into kelp, whereas in Examples 7 to 1,
No. 2 has sufficient wear resistance for 50,000 times and has no wear problems. Therefore, the coating composition of this example is suitable as a coating composition for weather stripping.

[Examples 13 to I8 and Comparative Examples 13 and 141 Next,
An example in which the present invention is embodied in an adhesive composition used for electrostatic flocking will be described.

In each of the following cases, the adhesive compositions of the following Examples were applied to an EPDM base material, electrostatic flocking was performed, and test pieces were prepared. 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-4.

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

Table 4 In Table 4, the circle in the column for the number of wears indicates that the amount of wear was small and the results were good.

As can be seen from Table 4, in Comparative Example 13.14, the adhesive composition itself gelled, whereas in Example 1
3 to 18, it can withstand abrasion of 30,000 times and there is no problem with abrasion.

Therefore, the adhesive composition of this example is suitable as an adhesive composition for electrostatic flocking.

[Effects of the Invention] The adhesive composition of the present invention has the effect that the resulting film has excellent IT P7 abrasion resistance and also has good adhesion to adherends.

Claims (1)

[Claims] 1. For 100 parts by weight of polyurethane having isocyanate groups or hydroxyl groups, which is obtained by reacting a low molecular weight diol with a reaction product of a mixture of polyester diol and polyether diol and diisocyanate,
An adhesive composition containing 0.002 to 20 parts by weight of a halogenating agent and 10 parts by weight or more of silicone oil.