JPS6126633A - Bonding of adherends at least one of which is polyvinyl chloride - Google Patents

Abstract

PURPOSE:To enable the firm bonding of adherends, and to keep the bonded state even at a high temperature, by adding a specific crosslinking agent to a solvent, applying the obtained adhesive to the titled adherend, and bonding the adherends with each other under hot-pressing. CONSTITUTION:A polyester having a group containing active hydrogen in the molecular chain, or a polyester polyurethane prepared by the chain-extension of said polyester with a polyisocyanate (e.g. toluene diisocyanate) is dissolved in a solvent, and the solution is added with a crosslinking agent having at least one triazine ring and having two or more thiol groups bonded to the C atoms on the ring and represented by the formula [R is -N(CnH2n+1)2, -NHCnH2n+1, -SH, -OCnH2n+1, etc; n is 1-8], preferably an acid acceptor. The resultant adhesive is applied to at least one of the objective adherends, and the adherends are bonded together under hot-pressing. EFFECT:Excellent heat-resistance.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for adhering adherends, at least one of which is made of polyvinyl chloride. This invention relates to an adhesion method that maintains this adhesive force.

(Prior art) Conventionally, an adhesive composition mainly composed of polyester or polyester polyurethane having a hydroxyl group in the molecular chain has been used for the adhesion method of polyester fiber K ([) and polyvinyl chloride. Polyisosifus-1 has been added to achieve this.Using this adhesive composition, it was possible to obtain very excellent adhesive strength even at a high temperature of 100°C after adhesion.

However, in such a method, firstly, polyisoryanate reacts at room temperature, so it is not possible to add polyisoryanate in advance and prepare a large amount of adhesive composition, and secondly, polyisoryanate reacts at room temperature. Because of the high reactivity of the adhesive composition, it has the disadvantage that it must be bonded immediately after applying the adhesive composition to one side of the adherend.

(Problems to be Solved by the Invention) The present invention aims to improve the above-mentioned points, and it not only increases the adhesive strength of an adherend having at least one side made of polyvinyl chloride, but also improves the adhesive strength in a high temperature environment. The objective is to provide an adhesive method that can be maintained even for long periods of time.

(Means for Solving the Problems) That is, the present invention is characterized in that, in a method for adhering adherends in which at least one side is polyvinyl chloride, a group having active hydrogen in the molecule is added to the solvent. A polyester having the following structural formula ( However, R is -N (CJzn+1), , NH
Cnllan++, -5ll.

−0Cn)lλn+1, etc., and N is 1 to 8. )
The adhesive obtained by adding a cross-linking agent represented by is applied to at least one of the adherends, and then the adherends are heated under pressure. Unlike conventional adhesives, the adhesive strength between adherends is improved compared to conventional adhesives because the adhesive is chemically bonded, and since the reaction of the adhesive does not proceed in the absence of polyvinyl chloride, long-term storage is possible. Furthermore, for example, when polyester fibers are subjected to dip treatment, the fibers can be preserved for a long period of time.

The polyester used in the method of the present invention or the polyester polyurethane obtained by chain-extending the polyester with polyisocyanate has groups having active hydrogen in the molecular chain, such as hydroxyl groups, amino groups, carboxyl groups, C=C-CH short units. and easily vaporized solvents, such as ethyl acetate,
It must be soluble in methyl ethyl ketone, toluene, acetone, tetrahydrofuran, chloroform, etc., and is usually added in an amount of 10 to 30% by weight. The average molecular weight of such polyester or polyester polyurethane is usually 1
5,000-25. It is about OOO.

The crosslinking agent used in the present invention is a compound represented by the general formula that forms a triazine ring and has at least two or more thiol groups on carbon hydrogen on the ring, and R of the compound is C-Cl and S
Any substance that does not inhibit the reaction between H or SH and polyisocyanate may be used, for example, -N (
CH3), , -N (C,Hl)L, -N (C
tIt, 1).

-N (C,H, entered, -NHC,H,,, -NIIC
,H,,-NHC6Is,-5ll.

-OC%H? etc. Then, this crosslinking agent is added to the above polyester or polyester polyurethane solution 100%.
It is usually added by 0.5 to 1.5 parts by weight.

Furthermore, polyisoryanate is added,
This can be anything as long as it has two or more isocyanate groups in the molecule, such as toluene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, hexane diisocyanate, isophorone diisocyanate. , diphenylmethane diisocyanate, polymethylene polyphenylene diisocyanate, etc., and is usually added in an amount of 0 to 5 parts by weight per 100 parts by weight of the above polyester or polyester polyurethane solution.

Further additions include an acid acceptor, and preferred examples of the acid acceptor include tertiary amines, oxides or carbonates of magnesium, calcium, barium, zinc, tin, and lead.

The adhesive used in the present invention is prepared by adding a crosslinking agent to polyester or polyester polyurethane dissolved in a solvent, or by adding a crosslinking agent and, if necessary, a polyisoryanate to polyester or polyester polyurethane dissolved in a solvent. Good too. In this case, it is preferable to add the crosslinking agent after adding the polyisoryanate to the polyester or polyester polyurethane, whereby the crosslinking agent can be bonded to the polyester or polyester polyurethane using polyisocyanate-1 as a medium.

At least one of the adherends used in the present invention is polyvinyl chloride, and the polyvinyl chloride has a polymerization ratio of 500 to 5,000 and a polyester plasticizer of 60 to 120. It is a known product including parts by weight.

In addition, other adherends include polyester, metals, etc. Polyesters include polyethylene terephthalate and polyethylene terephthalate (7) 2 [base acids partially replaced with isophthalic acid, cehatic acid, adipic acid,
and some of the glycol components are diethylene glycol,
It is substituted with tetraethylene glycol, hexamethylene glycol, or 1.4 cyclohexane dimetatool, and its form may be a cord, a fabric, or a film.

Next, the present invention will be explained in detail (Examples 1 to 3 and Comparative Examples 1 to 3).
5000/l
Including system stabilizers, hardness is JT record 70T: 0.6mm
A thick sheet was used.

To prepare the adhesive composition, first, polyhexamethylene adipate with an average molecular weight of 1t2000 was chain-extended with methylene diisocyanate, and a polyester polyurethane with a molecular weight of 20,000 and having two hydroxyl groups at the molecular ends was converted into methyl edyl ketone. After adding an isocyanate crosslinking agent, an acid acceptor, etc. to this polyester polyurethane solution and stirring thoroughly, apply it uniformly at 50g/n (in the case of 50g/n) to a polyester canvas using a doctor knife. , then 120
Dry for 2 minutes at °C. The treated canvas thus obtained was preheated at 175°C for 5 minutes.
It was pressed for 5 seconds at a pressure of 0 kg/cJ. Using the method described above, peel force measurements at 100° C. were obtained according to the formulations and conditions shown in Tables 1 and 2. The result is the third
Shown in the table.

Margin Table 1 below (@
Position: Length Table 2 Table 3 (kg/inch) Length m'l
'Mataj Kuma igW Rock/"゛"In Example 1,
When using an adhesive in which a crosslinking agent is previously bonded to the polyester polyurethane terminals, excellent peeling force is exhibited even in the absence of polyisoryanate compared to Comparative Example 1. Furthermore, even under conditions C and D, the peeling force does not decrease, but rather tends to improve.

In Example 2, when 1 part by weight of an acid acceptor is added to the formulation of Example 1 to promote the crosslinking reaction with polyvinyl chloride, the peeling force is further improved. Further, under conditions C and D, as in Example 1, the peeling force improved with time.

In Example 3, when polyisocyaners 1 to 1 are added to the formulation of Example 2 in order to improve the strength of the adhesive, under conditions A and B, the peeling force is improved. but,
Conditions C and D tend to get worse.

In Comparative Example 1, when only polyester polyurethane was used as the adhesive, only polyester polyurethane broke at 100'C, and the peeling force was also very low.

In Comparative Example 2, in order to improve the strength of the adhesive at 100°C, 1 part by weight of polyisoryanate was added to polyester polyurethane. Although the adhesive broke at 100°C, Its peeling force is significantly improved. However, when adhesive-coated polyester cloth is adhered after being left for 70 minutes, the peeling force tends to decrease.

In Comparative Example 3, when polyisocyanate-1 was increased to 3 parts by weight in order to further increase the strength of the adhesive, the peeling force was further improved, and the adhesive no longer broke, but the polyvinyl chloride began to break. However, under conditions C and D similar to Comparative Example 2, the peeling force decreased and the rate of change was much greater than in Comparative Example 2.

(Effects of the invention) As shown in these examples, the method of the present invention has superior heat resistance compared to the conventional method, and the adherend after applying the adhesive can coexist with substances containing active hydrogen such as water. It has the advantage of being able to tolerate the
When adhering a film or the like to a soft polyvinyl chloride or the like, even if the polyester to be adhered is subjected to dip treatment, the polyester can be stored for a long period of time, and has extremely excellent effects.

Claims (1)

[Claims] 1. In a method for adhering an adherend in which at least one side is polyvinyl chloride, a polyester having a group having an active hydrogen in the molecular chain in a solvent or a chain extension of the polyester with a polyisoryanate is used. The following structural formula ▲ Numerical formulas, chemical formulas, tables, etc. are included▼ (However, R is − N(C_nH_2_n_+_1)_2
, -NHC_nH_2_n_+_1, -SH, -OC_
After attaching an adhesive obtained by adding a crosslinking agent represented by nH_2_n_+_1, etc., where N is 1 to 8 to at least one of the adherends, the adherends are heated under pressure. A method for adhering an adherend in which at least one side is made of polyvinyl chloride.