JPH04298594A - Adhesive composition - Google Patents

Abstract

PURPOSE:To provide an adhesive composition which, when applied to polyolefin materials which are difficult to bond, can adhere to the materials without any pretreatment and attains high bonding strength. CONSTITUTION:An adhesive composition which comprises an isocyanate group- containing polyester urethane, a chloroprene rubber, a polyisocyanate, a halogenating agent, and an ethoxylated amine or/and a propoxylated amine. This adhesive composition tenaciously adheres to polyolefin materials even without any pretreatment such as priming treatment, corona treatment, etc., and gives a cured adhesive showing excellent peel strength under high-humidity conditions.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is applicable to, for example, adhesion of difficult-to-adhesion polyolefin materials used as automobile parts, adhesion of materials for electrostatic flocking, and adhesion of rubber products and synthetic resin products. The present invention relates to an adhesive composition.

0002

[Prior Art] Conventionally, methods for adhering polyolefin-based materials such as polypropylene, which are difficult to adhere to, 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.

0003

[Problems to be Solved by the Invention] 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 degrades workability. Moreover, the adhesive strength was also low.

An object of the present invention is to solve the above-mentioned conventional problems and provide an adhesive composition that can be bonded to polyolefin materials that are difficult to bond without pretreatment and that has high adhesive strength. It's about doing.

[0005]

[Means for Solving the Problems] In order to achieve the above object, the present invention provides a polyester urethane having an isocyanate group (-NCO), a chloroprene rubber, a polyisocyanate, a halogenating agent, an ethoxylated amine or/and a propoxylated The method used was to construct an adhesive composition from an amine.

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, hereinafter the same) tolylene diisocyanate, 80/20 tolylene diisocyanate, 1,5-naphthalene diisocyanate (NDI), 4,4'-diphenylmethane diisocyanate (MDI), dianisidine diisocyanate,
Tridene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate (XDI), metaxylene diisocyanate, 1,6-hexamethylene diisocyanate (1,6HMDI), hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated 2, 4-Tolylene diisocyanate, hydrogenated 65/35 tolylene diisocyanate, hydrogenated 80/2
0-tolylene diisocyanate, isophorone diisocyanate (IPDI), etc. can be used.

In addition to the above-mentioned polyisocyanates, the polyisocyanates to be blended include 4,4',4''-triphenylmethane triisocyanate (TPMT), which is a trifunctional isocyanate, and tris(P-isocyanate phenyl) thiophos. Fate (TIPP) etc. can be used. The blending ratio of this polyisocyanate is preferably in the range of 0.1 to 30 parts by weight based on 100 parts by weight of the solid content of the polyester urethane and chloroprene rubber. This is because if the blending ratio is less than 0.1 parts by weight, the improvement in adhesive strength will be small, and if it exceeds 30 parts by weight, no improvement in adhesive strength can be expected.

[0008] Polyester polyols include polybutylene adipate (PBT), polyethylene butylene adipate (PEBA), and polyethylene adipate (PE
T), polyethylene sebacate (PESE) T, etc. can be used.

In addition, examples of halogenating agents include t-butylhypochloride (t-BHC) as an alkyl hypohalide, sodium hypochlorite and potassium hypochlorite as hypohalites, and sodium hypochlorite and potassium hypochlorite as hypohalites. -CON
As a compound having an X-bond, N-bromosuccinimide (NBSI), trichloroisocyanuric acid (TCIA),
Isocyanuric acid dichloride (DiCIA), antimony pentafluoride, a mixed solution consisting 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 halogenation is small, so the improvement in adhesive strength is small;
This is because if the amount exceeds parts by weight, the stability of the adhesive composition deteriorates.

Examples of ethoxylated amines and propoxylated amines include those shown in Chemical Formula 1, Chemical Formula 2, and Tables 1 and 2.

[0011] Furthermore, the blending ratio of chloroprene rubber is as follows: polyester urethane/chloroprene rubber =
It can be set arbitrarily such as 2-98/98-2.

Incidentally, a chain extender, a solvent and a phenol resin may be used if desired. Examples of the chain extender include butylene glycol (BG), 1,6-hexanediol (1
, 6HD), ethylene glycol (EG), propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,5-pentanediol , 1,6-hexanediol, neopentyl glycol, etc., or a mixture of two or more thereof can be used.

Examples of the solvent include aliphatic hydrocarbons such as n-hexane, n-heptane, and n-octane, and alicyclic hydrocarbons such as cyclohexane, cyclooctane,
Aromatic hydrocarbons: benzene, ethylbenzene, toluene, xylene; ketones: acetone, methyl ethyl ketone, ethyl propyl ketone, methyl butyl ketone; ethers: tetrahydrofuran; acetic acid esters: methyl acetate, ethyl acetate, isopropyl acetate, halogens Examples of carbonized hydrocarbons include methylene chloride, 1,1,1-trichloroethane, trichloroethylene, dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), and the like. 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.

As the phenol resin, as a novolak type alkylphenol, for example, Tamanol 510, Tamanol 515, Tamanol 803 manufactured by Arakawa Chemical Co., Ltd.
, Tamanol 526, Tamanol 528, resol type alkylphenol, Tamanol 520S, Tamanol 52
1, Tamanol 573, Tamanol 577, Tamanol 586
, Tamanol 80 as a terpene type alkylphenol
3 etc. can be used.

[0015]

[Operation] According to the above-described structure, even if the adhesive composition is directly applied between two polyolefin materials that are difficult to bond to each other without any pretreatment, these polyolefin materials can be firmly bonded.

[0016]

[Examples] Hereinafter, examples using the adhesive composition of the present invention will be explained in comparison with comparative examples.

First, a polyester urethane having an isocyanate group was synthesized using the following blending ratio.

Polyester urethane ■ PBA (number average molecular weight 500) 66.56 per 100 parts by weight of MDI
Parts by weight were mixed in trichlorethylene and reacted for 3 hours at 80 OC in a dry nitrogen gas atmosphere to synthesize a polyester-based urethane prepolymer. after that,
This polyester urethane prepolymer has BG20.
40 parts by weight was added and reacted at 80 OC for 20 minutes to synthesize polyester urethane. The obtained polyester urethane had a solid content of 25% and a trichlorethylene content of 75%.
%Met.

Polyester urethane ■PEBA (number average molecular weight 2000) 266% for 100 parts by weight MDI
．． 31 parts by weight were mixed in trichlorethylene and reacted for 3 hours at 80 OC in a dry nitrogen gas atmosphere to synthesize a polyester-based urethane prepolymer. After that, 1,
26.76 parts by weight of 6HD was added and reacted at 80 OC for 20 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 1000) 191.
94 parts by weight were mixed in trichlorethylene and reacted for 3 hours at 80OC in a dry nitrogen gas atmosphere to synthesize a polyester-based urethane prepolymer. after that,
This polyester urethane prepolymer has EG44.
09 parts by weight was added and reacted for 20 minutes at 80OC to synthesize polyester urethane. The obtained polyester urethane had a solid content of 25% and a trichlorethylene content of 75%.
%Met.

[0021] Polyester urethane ■1,6HMDI
PESe (number average molecular weight 1000 parts by weight)
) 99.10 parts by weight are mixed in trichlorethylene,
A polyester-based urethane prepolymer was synthesized by reacting for 3 hours at 80 OC in a dry nitrogen gas atmosphere. Thereafter, 28.92 parts by weight of EG was added to this polyester urethane prepolymer and reacted at 80 OC 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 ■ PEA (number average molecular weight 1000) 266.
31 parts by weight were mixed in trichlorethylene and reacted for 3 hours at 80OC in a dry nitrogen gas atmosphere to synthesize a polyester-based urethane prepolymer. after that,
This polyester urethane prepolymer has an EG5.7
9 parts by weight were added and reacted at 80 OC for 20 minutes to synthesize polyester urethane. The obtained polyester urethane had a solid content of 25% and a trichlorethylene content of 75%.
%Met.

Next, chloroprene rubber, polyisocyanate, a halogenating agent, and a phenol resin were blended in predetermined proportions to the solid content of the polyester urethanes shown in (1) to (4) to obtain an adhesive composition.

(Example 1) 2 parts by weight of chloroprene rubber (CR), 0.1 part by weight of MDI, and 1 part by weight of ethoxylated amine (1) (shown in Table 1) to 98 parts by weight of polyester urethane (1). , and 0.002 parts by weight of t-BHC to obtain an adhesive composition.

(Example 2) 20 parts by weight of chloroprene rubber (CR), 30 parts by weight of MDI, 1 part by weight of ethoxylated amine (3) (shown in Table 1), and An adhesive composition was obtained by blending 1 part by weight of t-BHC.

(Example 3) 40 parts by weight of chloroprene rubber (CR), 10 parts by weight of XDI, 5 parts by weight of ethoxylated amine (4) (shown in Table 1), and An adhesive composition was obtained by blending 1 part by weight of NBSI.

(Example 4) 60 parts by weight of chloroprene rubber (CR), 10 parts by weight of TDI, 10 parts by weight of ethoxylated amine (5) (shown in Table 1), and An adhesive composition was obtained by blending 1 part by weight of TCIA.

(Example 5) 80 parts by weight of chloroprene rubber (CR), 10 parts by weight of IPDI, and 20 parts by weight of TCIA were blended with 20 parts by weight of the polyester urethane (2) to obtain an adhesive composition.

(Example 6) 98 parts by weight of chloroprene rubber (CR), 10 parts by weight of TPMT, 5 parts by weight of ethoxylated amine (2) (shown in Table 1), propoxy amine (1) (
(shown in Table 2) and 1 part by weight of TCIA were blended to obtain an adhesive composition.

(Example 7) 40 parts by weight of chloroprene rubber (CR), 10 parts by weight of TPMT, propoxylated amine (2) to 60 parts by weight of polyester urethane (2)
(shown in Table 2) and 1 part by weight of TCIA were blended to obtain an adhesive composition.

(Example 8) 40 parts by weight of chloroprene rubber (CR), 10 parts by weight of TIPP, and propoxylated amine (3) to 60 parts by weight of the polyester urethane (2)
An adhesive composition was obtained by blending 1 part by weight (shown in Table 2), 1 part by weight of TCIA, and 20 parts by weight of Tamanol 803.

(Example 9) To 60 parts by weight of polyester urethane (2), 40 parts by weight of chloroprene rubber (CR), 10 parts by weight of TIPP, and ethoxylated amine (3) (
Shown in Table 1) 5 parts by weight, propoxylated amine (2)
An adhesive composition was obtained by blending 5 parts by weight (shown in Table 2), 1 part by weight of TCIA, and 10 parts by weight of Tamanol 340.

Next, in order to examine the adhesive strength of the adhesive composition thus obtained, the following moisture peel test was conducted.

[0034] The test pieces to be subjected to this moisture-resistant peeling test were two test pieces made of polyethylene 5x foam, on which the adhesive composition was applied to an adhesion area of 25 x 25 mm.
After heating at 0 OC for 2 minutes to evaporate the solvent, 5 kg
/cm2, and the obtained test piece was heated at 50 OC in 98% relative humidity.
The sample was left to stand for 00 hours, and then pulled at a tensile speed of 50 mm/min to measure the moisture resistance peel strength. The results are shown in Table-3.

Comparative Examples 1 to 3 were obtained using the following formulations.

(Comparative Example 1) An adhesive composition obtained using only the polyester urethane (2).

(Comparative Example 2) Chloroprene rubber (CR) 1
An adhesive composition obtained by blending 00 parts by weight with 50 parts by weight of MDI and 1 part by weight of TCIA.

(Comparative Example 3) An adhesive composition obtained by blending 40 parts by weight of chloroprene rubber (CR) and 10 parts by weight of MDI with 60 parts by weight of polyester urethane.

As is clear from Table 3, isocyanate
It can be seen that an adhesive composition containing a polyester urethane having a group, chloroprene rubber, a polyisocyanate, and a halogenating agent has a peel strength so high that a foam 5 times that of polyethylene as an adherend bursts.

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 also By halogenating the polyester-based urethane, the intermolecular force between both is increased, and the peel strength is improved by the flexible and elastic chloroprene rubber. This is thought to be due to the synergistic effect with the base to further improve the adhesive strength.

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

[0042] 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, base materials for electrostatic flocking, interior parts, rubber products, etc. in which polyolefin materials are used.

[0043]

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

[0044]

[Chemical formula 1]

[0045]

[Case 2]

[0046]

[0047]

[0048]

[0049]

Claims (1)

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