JPH04168182A - Adhesive composition - Google Patents

Abstract

PURPOSE:To obtain an adhesive composition, composed of a polyester-based urethane having isocyanate groups, chloroprene rubber, a polyisocyanate, a halogenating agent and a phenolate and having a high bonding strength without requiring pretreatment. CONSTITUTION:The objective composition is composed of (A) a polyesterbased urethane, composed of a polyisocyanate such as 2,4-tolylene diisocyanate and a polyester polyol such as polybutylene adipate and having isocyanate groups, (B) chloroprene rubber, (C) a polyisocyanate such as 4,4',4''-triphenylmethane triisocyanate, (D) a halogenating agent such as tert-butyl hypochlorite and (E) phenolates composed of salts of phenols with group I or II metals.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is applicable to adhesion of polyolefin materials that are difficult to adhere to, such as those used as automobile parts, adhesion of materials for electrostatic flocking, rubber products, and synthetic resins. The present invention relates to an adhesive composition used for adhering products.

<Prior art> Conventional methods for bonding polyolefin materials such as polypropylene, which are difficult to bond, include applying adhesive after surface treatment with a primer such as chloroprene rubber, or applying adhesive after corona discharge treatment. There are known methods to do this.

However, these bonding methods require pretreatment such as primer treatment and corona discharge treatment before bonding polyolefin materials, which increases the number of steps and results in poor workability. Moreover, the adhesive strength was also low.

The purpose of the present invention is to solve the above-mentioned conventional problems, and to provide an adhesive composition that can be bonded to polyolefin materials that are difficult to bond without pretreatment and that has high adhesive strength. be.

Means for Solving the Problems> In order to achieve the above objects, the present invention provides an adhesive composition made of polyester urethane having an isocyanate group (-NCO), chloroprene rubber, polyisocyanate, phenolades, and a halogenating agent. We adopted the method of configuring.

Polyester urethane is composed of polyisocyanate and polyester polyol, and polyisocyanate is a compound having multiple isocyanate groups, such as 2,4-tolylene diisocyanate (TDI).
, 65/35 (ratio of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, the same applies hereinafter) tolylene diisocyanate, 8o/2o tolylene diisocyanate, ■, 5-naphthalene diisocyanate (
SDI), 4,4°-diphenylmethane diisocyanate (MDI), dianisidine diisocyanate, tridene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate (XD■), metaxylene diisocyanate, 1,6-hexamethylene diisocyanate (1°68MDI) , hydrogenated 4,4°-diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated 2,4-tolylene diisocyanate, hydrogenated 65/35 tolylene diisocyanate, hydrogenated 80/20
Tolylene diisocyanate, isoborone diisocyanate (IPDI), etc. can be used.

In addition to the polyisocyanates mentioned above, the polyisocyanates to be blended include trifunctional isonoanate 4
, 4', 4''-triphenylmethane triisocyanate (TPMT), h-lis(P-isocyanate phenyl) thiophosphate (TIPP), etc. can be used.The blending ratio of this polyisocyanate is as follows: A good range is 0.1 to 30 parts by weight based on 100 parts by weight of the solid content of polyester urethane and chloroprene rubber.This is because if the mixing ratio is less than 0.1 part by weight, the adhesive strength will not improve much, and 30 parts by weight. This is because, if the adhesive strength exceeds 100%, the factory with adhesive strength cannot be expected.

Examples of polyester polyols include polybutylene adipate (PBA), polyethylene butylene adipate (PEBA), polyethylene adipate (PEA),
Polyethylene sebacate (PESe) or the like can be used.

Further, as a halogenating agent, for example, as an alkyl hypohalide, t-butylhypochloride ('
t-BHC), as hypohalites, sodium hypochlorite, potassium hypochlorite, -CONX- in the molecule
N-bromosuccinimide (
NBS I), trichloroisocyanuric acid (TCIA),
Isocyanuric acid dichloride (DiCIA), antimony pentafluoride, a mixed solution of sulfur fluoride and bromine, etc. can be used, but among these, alkyl hypohalides, hypohalites, or -CONX in the molecule can be used. - Compounds having a bond are preferred. The blending ratio of the halogenating agent is preferably in the range of 0.002 to 20 parts by weight based on 100 parts by weight of the solid content of the polyester urethane. This is because if the blending ratio is less than 0.002 parts by weight, the degree of chlorination will be small, resulting in little improvement in adhesive strength, and if it exceeds 20 parts by weight, the stability of the adhesive composition will deteriorate.

Phenolades include phenol, cresol, α-naphthol, β-naphthol, etc., and group II compounds such as Li, Na5K, and R.
Refers to salts of beryllium, magnesium, calcium, zinc, strontium, barium, etc. of group B and ■.

In addition, the blending ratio of chloroprene rubber is polyester urethane/chloroprene rubber = 2 to 98/9 by weight.
It can be set arbitrarily, such as from 8 to 2.

Incidentally, a chain extender, a solvent, and a phenol resin may be used if desired, and examples of the chain extender include butylene glycol (BG), 1,6-hexanediol (1,6HD
), ethylene glycol (EG), propylene glycol, butanediol 1,4, butanediol 1,3,
One or a mixture of two or more of butanediol 2.3, diethylene glycol, dipropylene glycol, triethylene glycol, bentanediol 1,5, hexanediol 1,6, neopentyl glycol, etc. can be used.

Examples of solvents include aliphatic hydrocarbons such as n-hexane, n-heptane, and n-octane; ring hydrocarbons such as cyclohexane and cyclooctane; and aromatic hydrocarbons such as benzene, ethylbenzene, toluene, xylene, and ketones. As acetone, methyl ethyl ketone, ethyl propyl ketone, methyl butyl ketone, as ethers, tetrahydrofuran, as acetic acid ester, as methyl acetate, ethyl acetate, isopropyl acetate, as halogenated hydrocarbon, methylene chloraroite, 1,1.
Examples include i-trichloroethane, trichlorethylene, dimethyl sulfoxide (DMSO), and dimethylformamide. These solvents may be used alone or as a mixed solvent of two or more, and the blending ratio of the adhesive composition and these solvents may also be set arbitrarily.

Examples of phenolic resins include novolak-type alkylphenols such as Tamanol 510, Tamanol 515, Tamanol 803, and Tamanol 5 manufactured by Arakawa Chemical Co., Ltd.
26, Tamanol 528, resol type alkylphenol such as Tamanol 520S, Tamanol 521, Tamanol 573, Tamanol 577, Tamanol 586, and terpene type alkylphenol such as Damanol 803 can be used.

Effect> According to the above-described configuration, even if the adhesive composition is directly applied between two polyolefin materials that are difficult to adhere to without pretreatment, these polyolefin materials are firmly adhered.

<Examples> Examples using the adhesive composition of the present invention will be described below in comparison with comparative examples.

First, a polyester urethane having isocyanate groups was synthesized at the following blending ratio.

Polyester urethane■ PBA (number average molecular weight 5
00) 66.56 parts by weight were mixed in trichlorethylene and reacted at 80°C for 3 hours in a dry nitrogen gas atmosphere to synthesize a polyester-based urethane prepolymer. Thereafter, 20.40 parts by weight of BG was added to this polyester urethane prepolymer and reacted at 80° C. for 20 minutes to synthesize a polyester urethane. The obtained polyester urethane had a solid content of 25% and a trichlorethylene content of 75%.

Polyester urethane■ 266.31 parts by weight of PEBA (number average molecular weight 2000) was mixed with 100 parts by weight of MDI in trichlorethylene, and the mixture was heated at 80°C in a dry nitrogen gas atmosphere for 30 minutes.
A polyester-based urethane prepolymer was synthesized by reacting for a period of time. Then, 268.76 parts by weight of 1,6HD was added to this polyester-based urethane prepolymer and
C for 20 minutes to synthesize polyester urethane. The obtained polyester urethane has a solid content of 25%,
The trichlorethylene content was 75%.

Polyester urethane■ PEA (number average molecular weight 1
000) were mixed in trichlorethylene and reacted at 80° C. for 3 hours in a dry nitrogen gas atmosphere to synthesize a polyester-based urethane prepolymer. Thereafter, 44.09 parts by weight of EG44.0 was added to this polyester-based urethane prepolymer and reacted at 80°C for 20 minutes to synthesize a polyester-based urethane. The obtained polyester urethane had a solid content of 25% and a trichlorethylene content of 75%.

Polyester urethane■ 1.6HMD 1100 parts by weight and PE5e (number average molecular weight 1000) 99.10 parts by weight were mixed in trichlorethylene and reacted at 80°C for 3 hours in a dry nitrogen gas atmosphere to form a polyester urethane preform. The polymer was synthesized. Then, 28.92 parts by weight of EG was added to this polyester-based urethane prepolymer and
The reaction was carried out for 0 minutes to synthesize polyester urethane. The obtained polyester urethane had a solid content of 25% and a trichlorethylene content of 75%.

Polyester urethane■ PEA (number average molecular weight 1
000) were mixed in trichlorethylene and reacted at 80°C for 3 hours in a dry nitrogen gas atmosphere to synthesize a polyester-based urethane prepolymer. Thereafter, 5.79 parts by weight of EG was added to this polyester urethane prepolymer and reacted at 80° C. for 20 minutes to synthesize a polyester urethane. The obtained polyester urethane had a solid content of 25% and a trichlorethylene content of 75%.

Next, for the solid content of polyester urethane shown in these ■～■, chloroprene rubber, polyisocyanate,
An adhesive composition was obtained by blending a halogenating agent and phenolads a-i shown in Table 1 in predetermined proportions.

(Example 1) To 98 parts by weight of polyester urethane (2), 2 parts by weight of chloroprene rubber (CR), 1 part by weight of MDIo, 1 part by weight of phenolad ao, and t-BHCo, 002
Parts by weight were blended to obtain an adhesive composition.

(Example 2) CR2 for 80 parts by weight of polyester urethane
0 parts by weight, MD I 30 parts by weight, phenolad bO,
'01 part by weight and 1 part by weight of t-BHC were blended to obtain an adhesive composition.

(Example 3) CR4
0 parts by weight, XDIIO parts by weight, phenol) co, 01
Parts by weight and parts by weight of NBSII were blended to obtain an adhesive composition.

(Example 4) CR6 to 40 parts by weight of polyester urethane
0 parts by weight, TDIIO parts by weight, phenolad do, o1
Parts by weight and parts by weight of TCTAI were blended to obtain an adhesive composition.

(Example 5) CR8 for 20 parts by weight of polyester urethane (1)
0 parts by weight, IPDIIO parts by weight, phenolade eo, 0
An adhesive composition was obtained by blending 1 part by weight and 20 parts by weight of TCIA.

(Example 6) CR98 to 2 parts by weight of polyester urethane (2)
Parts by weight, 0 parts by weight of TPMT I, 10 parts by weight of phenolad.
An adhesive composition was obtained by blending 1 part by weight and 1 part by weight of TCIAI.

(Example 7) CR4 for 60 parts by weight of polyester urethane
0 parts by weight, TPMTIO parts by weight, phenolad g0.1
Part by weight, part by weight of TCIAI, and 1 part by weight of Tamanol 520S were blended to obtain an adhesive composition.

(Example 8) CR4 for 60 parts by weight of polyester urethane (1)
0 parts by weight, TlPP10 parts by weight, phenolad hO,1
Parts by weight, parts by weight of TCIAI, and 20 parts by weight of Tamanol 803 were blended to obtain an adhesive composition.

(Example 9) CR4 for 60 parts by weight of polyester urethane
0 parts by weight, 0 parts by weight of TlPPl, 1 part by weight of TCIA, 10.1 parts by weight of phenolad, and 10 parts by weight of Tamanol 340 were blended to obtain an adhesive composition.

Next, in order to examine the adhesive strength of the adhesive composition obtained as described above, the following moisture-resistant peel test was conducted.

The test pieces used for this moisture peeling test were two test pieces made of 5x polyethylene foam, coated with an adhesive composition on an adhesive area of 25 x 25 mm, and heated at 100°C.
After heating for 2 minutes to evaporate the solvent, the bonded 5
kg/crl at 50°C and 98% relative humidity.
The film was left to stand for 0 hours, and then pulled at a tension speed of 50 mm/min to measure the moisture resistance peel strength. The results are shown in Table-2.

(Hereinafter, blank space) 1 Oki = Mijin -1 Table 2 Comparative Examples 1 to 3 were obtained using the following formulations.

(Comparative Example 1) Adhesive composition obtained only from polyester urethane (1).

(Comparative Example 2) For 100 parts by weight of CR, 50 parts by weight of MDI, TCIA
An adhesive composition obtained by blending I parts by weight.

(Comparative Example 3) CR4 for 60 parts by weight of polyester urethane
An adhesive composition obtained by blending 0 parts by weight and MDIIO parts by weight.

As is clear from Table 1, the adhesive composition containing isocyanate group-containing polyester urethane, chloroprene rubber, polyisocyanate, and a halogenating agent causes the foam to rupture five times as much as the polyethylene adherend. It can be seen that the higher the peel strength, the greater the peel strength.

The reason why the adhesive composition of the present invention exhibits such excellent adhesive strength is that the halogen in the halogenating agent halogenates the non-polar polyolefin of the adherend, and the polyester-based adhesive composition in the adhesive composition By halogenating the urethane, the intermolecular force between the two is increased, and the peel strength is improved by using the flexible and elastic chloroprene rubber. This is thought to be due to a synergistic effect that further improves the adhesive strength.

On the other hand, as shown in Comparative Examples 1 to 3, when any of the aforementioned polyester urethane, chloroprenecomb, polyisocyanate, and halogenating agent is not blended, the stability of the adhesive composition is poor. It can be seen that the adhesive strength is extremely low.

Now, in this example, not only can polyethylenes, which are difficult to adhere to each other, be easily adhered to each other without using a conventionally used primer, but also the adhesive strength is extremely high. Therefore, the adhesive composition of this example is suitably used for, for example, automobile moldings, substrates for electrostatic flocking, interior parts, rubber products, etc., which use polyolefin materials.

<Effects of the Invention> As detailed above, the adhesive composition of the present invention is not only capable of adhering to polyolefin materials that are particularly difficult to adhere to without pretreatment, but also has excellent adhesive strength. It has an excellent effect of being extremely high.

Claims (1)

[Claims] 1. An adhesive composition comprising a polyester urethane having an isocyanate group (-NCO), chloroprene rubber, polyisocyanate, a halogenating agent, and phenolads.