KR100503292B1 - Adhesive for vinyl chloride film laminated metal plate - Google Patents

Abstract

The present invention comprises polymethyl methacrylate resin, acrylonitrile butadiene rubber, polyvinyl chloride / polyvinylacetate copolymer resin, saturated aliphatic polyester, epoxy resin as resin components; Contains dicyandiamide as a latent curing agent; Adhesive for vinyl chloride film coated steel sheet in which the resin component and the latent curing agent are dissolved in an organic solvent system containing methyl isobutyl ketone, methyl ethyl ketone, diisobutyl ketone, toluene, xylene, diacetone alcohol and butyl cellosol. This adhesive is a one-part type, easy to use, no gel phenomenon, excellent storage stability, excellent adhesion, impact resistance, water resistance, heat resistance, processability and durability, and at a low temperature (190 ~ 220 ℃) The line speed is high, so productivity is excellent.

Description

Adhesive for vinyl chloride film laminated metal plate

The present invention relates to an adhesive for vinyl chloride film coated steel sheet, and more particularly, to improve the physical and mechanical properties such as water resistance, heat resistance and workability of a chemically treated steel sheet, an electrogalvanized steel sheet, and a cold rolled steel sheet. It relates to an adhesive used to prepare a vinyl chloride film coated steel sheet by adhering to a surface.

Korean Patent Publication No. 78-240 discloses a solvent type comprising a resin composed of methyl methacrylate and epoxy resin in a range of 1: 0.4 to 1.5 as a main component of a coating film forming agent. And methylmethacrylate resin: resol type phenol resin = 1 part: 0.2 to 1 part, methyl methacrylate: reactive plasticizer = 1 part: 0.05 to 0.3 A primer for the arrival of a vinyl resin stratified layer formed in a negative ratio range is described. Korean Patent Publication No. 80-1359 discloses a ratio of methyl methacrylate resin and epoxy resin in one part: 0.4 to 1.5 parts, and methyl methacrylate resin. : Resol type phenol resin = 1 part: 0.2 to 1 part, methyl methacrylate resin: Reactive plasticizer = 1 part: Vinyl resin film and resin for paint as a main component of the film forming agent Resin In forming the film-forming agent of the sintered primer for stratification, the ratio of the methyl methacrylate resin, the methyl methacrylate, ethyl acrylate and acrylic acid terpolymer in the ratio range of 1 part: 1 to 2 parts A primer for the arrival of a vinyl resin film and a vinyl resin layer for coating is described.

However, all of the above-mentioned prior arts are obtained by curing phenol resin and diethylenetriamine with a curing agent using methyl methacrylate resin and epoxy resin as raw materials, and the adhesive is particularly resistant to impact, water resistance, and processability. Since it cannot be used for products that are processed by pressing or impacting vinyl film-coated steel sheet, it was used only for building materials and interior materials for ships. In addition, the primer is a one-part type storage stability is not good and the adhesion temperature is high to 240 ~ 250 ℃ is difficult to matte treatment of vinyl chloride film.

In addition, Korean Patent No. 256218 discloses 0.1 to 0.2 parts by weight of 2-hydroxyethyl methacrylate, 0.1 to 0.3 parts by weight of 2-ethylhexyl methacrylate, and an acrylonitrile copolymer solution 0.6 to 1 part by weight of methyl methacrylate. Grap by weight ratio of -1.0 weight part and glycidyl methacrylate 0.1-0.2 weight part, and methyl ethyl ketone: methyl isobutyl ketone: butyl cellosolve: diisobutyl ketone in a weight ratio of 1: 1: 1: 1: 1 The adhesive for polyvinyl chloride film coated steel sheet superposed | polymerized is proposed. However, these adhesives are not 100% polymerizable, and only 85 to 90% of the polymerization reactions occur and the remaining 10 to 15% remain in the monomer state so that the smell of the monomer is very high. The reaction takes place, the viscosity is high, the gelation phenomenon occurs, the use is inconvenient to be consumed in a short time. In addition, since it is a two-part adhesive, it is inconvenient to stir B liquid (crosslinking agent) immediately before use, and products containing a crosslinking agent cannot be used due to an increase in viscosity if it is not used within 24 hours. There is a ham.

Therefore, the object of the present invention is a one-component, excellent storage stability, excellent adhesion, impact resistance, boiling resistance, heat resistance, durability, processability, etc. than two-component, new vinyl chloride that can be easily bonded at low adhesion temperature It is to provide an adhesive for film-coated steel sheet.

According to the present invention for achieving the above object, 10 to 30 parts by weight of acrylonitrile butadiene rubber, 20 to 60 parts by weight of polyvinyl chloride / polyvinylacetate copolymer resin, based on 100 parts by weight of polymethyl methacrylate resin as a resin component, 20 to 50 parts by weight of saturated aliphatic polyester and 20 to 50 parts by weight of epoxy resin; Dicyandiamide as a latent curing agent, containing 5 to 10 parts by weight based on 100 parts by weight of polymethylmethacrylate resin; In the mixed organic solvent system wherein the resin component and the latent curing agent contain methyl isobutyl ketone, methyl ethyl ketone, diisobutyl ketone, toluene, xylene, diacetone alcohol and butyl cellosol moiety (ethylene glycol mono butyl ether). An adhesive for vinyl chloride film coated steel sheet is provided, which is dissolved.

According to the present invention, the mixed organic solvent system is methyl isobutyl ketone: methyl ethyl ketone: diisobutyl ketone: toluene: xylene: diacetone alcohol: butyl cellosol portion = 0.8: 0.3 to 0.7: 0.8: 1: 1: Provided is an adhesive for coating vinyl chloride coated steel sheet, which is composed of a weight ratio of 1: 1: 1.6.

Hereinafter, the present invention will be described in more detail.

The adhesive for vinyl chloride film coated steel sheet of the present invention is a one-component adhesive mainly composed of a resin component, a latent curing agent and an organic solvent.

The adhesive contains polymethyl methacrylate resin, acrylonitrile butadiene rubber, polyvinyl chloride / polyvinylacetate copolymer resin, saturated aliphatic polyester and epoxy resin as resin components.

As for the polymethyl methacrylate resin which is a base resin among the resin components of this adhesive agent, about 50,000-150,000 weight average molecular weights are suitable.

The content of acrylonitrile butadiene rubber in the resin component of the present adhesive is appropriately 10 to 30 parts by weight based on 100 parts by weight of the polymethyl methacrylate resin. When the content of acrylonitrile butadiene rubber is less than 10 parts by weight, the impact resistance may be poor, and when more than 30 parts by weight, the adhesion and the applicability may be poor. Particularly preferred acrylonitrile butadiene rubbers for use are those having a Mooney viscosity of 40 to 90.

The content of the polyvinyl chloride / polyvinylacetate copolymer resin is suitably 20 to 60 parts by weight based on 100 parts by weight of the polymethyl methacrylate resin. When the content of the polyvinyl chloride and polyvinylacetate copolymer resin is less than 20 parts by weight, the adhesion to the PVC film may be poor, and more than 60 parts by weight may be poor heat resistance. Particularly preferred polyvinylchloride / polyvinylacetate copolymer resins for use are copolymerized in a proportion of 60 to 85% by weight of the polyvinylchloride component and 15 to 40% by weight of the polyvinylacetate component.

The content of saturated aliphatic polyester is suitably 20 to 50 parts by weight with respect to 100 parts by weight of the polymethyl methacrylate resin. When the content of the polyester is less than 20 parts by weight, the impact resistance may be poor, and when more than 50 parts by weight, the resin compatibility may be poor. Particularly preferred saturated aliphatic polyesters for use are those having a weight average molecular weight of 10,000 to 50,000.

The content of the epoxy resin is suitably 20 to 50 parts by weight with respect to 100 parts by weight of the polymethyl methacrylate resin. If the content of the epoxy resin is less than 20 parts by weight may be poor durability, if more than 50 parts by weight may be poor impact resistance. Particularly preferred epoxy resins for use are those having an epoxy equivalent of 150 to 250.

The adhesive also contains dicyandiamide as a latent curing agent. This adhesive, which contains dicyandiamide, a latent curing agent, into a one-component form, has excellent storage stability because the reaction does not occur at room temperature but a curing reaction occurs when heated to a temperature of 150 ° C. or higher. The content of dicyandiamide in the present adhesive depends on the content of the resin components, and preferably 5 to 10 parts by weight based on 100 parts by weight of the polymethyl methacrylate resin.

The adhesive exhibits excellent corrosion resistance with the introduction of epoxy resin and dicyandiamide, a thermosetting latent curing agent, and excellent heat and impact resistance with the introduction of acrylonitrile butadiene rubber.

A specially designed organic solvent system is required to dissolve the latent curing agent and resin components contained in the present adhesive. The organic solvent system used in this adhesive is mixed with organic solvents methyl isobutyl ketone, methyl ethyl ketone, diisobutyl ketone, toluene, xylene, diacetone alcohol and butyl cellosol moiety. The mixing ratio of each organic solvent depends on the mixing ratio of the latent curing agent and the resin components to be dissolved, and the preferred mixing ratio is generally methyl isobutyl ketone: methyl ethyl ketone: diisobutyl ketone: toluene: xylene: diacetone alcohol: Butyl cellosol portion = 0.8: 0.3 to 0.7: 0.8: 1: 1: 1: 1.6 weight ratio is suitable.

In addition to the above-described components, the present adhesive may contain other conventional additives in an appropriate amount without departing from the object of the present invention. Examples of such other additives include antioxidants, stabilizers, plasticizers, and the like.

Hereinafter, the method of the embodiment of the present invention will be described. However, the present invention is not limited to the following examples.

  Example 1

11.0% by weight of polymethyl methacrylate resin (Paraloid A-11), 2.0% by weight of acrylonitrile butadiene rubber (Mooney viscosity 60), polyvinyl chlorite / polyvinylacetate copolymer resin (Wacker products) H40 / 50) 5.5 wt%, saturated aliphatic polyester (ES-300; molecular weight 26000) 3.2 wt% and epoxy resin (epoxy equivalent 200) 3.6 wt%; 0.8% by weight dicyandiamide as the thermosetting latent curing agent; As organic solvent system, methyl isobutyl ketone 8.6% by weight, methyl ethyl ketone 4.3% by weight, diisobutyl ketone 8.6% by weight, toluene 11.4% by weight, xylene 11.4% by weight, diacetone alcohol 11.4% by weight and butyl cellosol part 17.8% by weight %Wow; As other additives, an adhesive for a vinyl chloride film coated steel sheet having 0.1 wt% of antioxidant, 0.1 wt% of stabilizer, and 0.2 wt% of plasticizer was prepared.

Three specimens were prepared in accordance with KS M3343, using the prepared adhesive, and peeling test, Ericsson test, impact test, bending test, cold resistance test, boiling water resistance test, and corrosion resistance test were carried out by the following methods. . The test results are shown in Table 2. Each test result is represented by the average grade code for the three specimens, indicating that the grade code +++ is the most favorable, ++ is good and the + is normal.

* Peel test

Specimen Fabrication: Width 20㎜, Length 150㎜

The specimen should be peeled about 90 mm from one end and bend the vinyl layer 180 °. Apparatus and apparatus are measured using a tensile strength tester and subjected to a tensile load at a rate of 50 mm per minute to measure the maximum load at the time of peeling, and at the time of breaking when the vinyl layer is broken.

Ericsson Exam

Specimen Fabrication: 90mm in width, 90mm in length

The test piece is cut out of the vinyl layer with a sharp knife two horizontally and vertically each 50 mm long at 2.5 mm distance from the center line. The Ericsson tester uses the apparatus specified in KS B 5529 (Ericsson Tester). Operation is to test the PVC film peeled by expanding the vinyl chloride film coated steel sheet so that the center of the test piece coincides with the die center and the punch speed is 5 to 20 mm / min and the radius is 6 mm. At this time, observe the state that the cross-cut PVC film is broken at the expanded center.

* Flexural test

Specimen Fabrication: 50mm wide, 150mm long

PVC film shall not break when the specimen is folded at 180 ° at 25 ± 5 ° C in accordance with KS B 0804 (Metal Bending Test Method).

* Cold resistance test

It is the same as the specimen in the bending test, and the specimen is kept at 0 ± 1 ℃ for at least 1 hour, and again in the same manner as the bending test.

* Boiling water resistance test

Specimen Fabrication: 20mm wide, 100mm long

Put 2 ~ 3 small pieces of porcelain into a beaker of 200ml or more and put clean water to a depth of 130mm and heat it. 0 Boil 2-3 bubbles per second. After 60 minutes, take out in cold water for 5 minutes to cool and dry. At this time, check that the PVC film is peeled off.

* Corrosion Resistance Test

Specimen Fabrication: 50mm in width, 100mm in length

The cut part of the test piece shall be covered with a transparent tape of about 5 mm and attached, and tested according to KS D 9502 (Saline Spray Test Method). The test time is 1000 hours.

[Examples 2 to 5]

Except for changing the content of the composition as shown in Table 1, the same procedure as in Example 1 was repeated to prepare an adhesive composition, and the properties of the prepared composition was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Ingredient Content (% by weight) Example 2 Example 3 Example 4 Example 5 Polymethyl methacrylate 11.0 11.0 11.0 11.0 Acrylonitrile Butadiene Rubber 1.0 1.5 2.5 3.0 Polyvinyl chloride / polyvinylacetate copolymer resin 2.0 3.0 5.0 6.0 Saturated aliphatic polyester 5.0 4.0 3.0 2.0 Epoxy resin 5.0 4.0 3.0 2.0 Dicyanamide 1.0 0.8 0.6 0.4 Antioxidant 0.1 0.1 0.1 0.1 stabilizator 0.1 0.1 0.1 0.1 Plasticizer 0.2 0.2 0.2 0.2 Methyl Isobutyl Ketone 8.6 83.6 8.6 8.6 Methyl ethyl ketone 5.4 6.1 5.3 6.0 Diisobutyl ketone 8.6 8.6 8.6 8.6 toluene 11.4 11.4 11.4 11.4 xylene 11.4 11.4 11.4 11.4 Diacetone alcohol 11.4 11.4 11.4 11.4 Butyl Cellosol Part 17.8 17.8 17.8 17.8 system 100 100 100 100

Comparative Example 1

8.5% by weight of methyl methacrylate, 0.8% by weight of 2-hydroxyethyl methacrylate, 0.8% by weight of 2-ethylhexyl methacrylate, 5.1% by weight of acrylonitrile copolymer, glycidyl methacrylate An adhesive was prepared containing 0.8% by weight, 15.5% by weight of methyl ethyl ketone, 16.5% by weight of methyl isobutyl ketone, 18% by weight of diisobutyl ketone, 16.5% by weight of toluene and 16.5% by weight of butyl cellosolve. Was evaluated in the same manner as in Example 1. The evaluation results are presented in Table 2.

Test Items Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Peel Test +++ +++ +++ +++ +++ +++ Ericsson Exam +++ +++ +++ +++ +++ +++ Impact test +++ ++ +++ +++ +++ ++ Flexural test +++ +++ +++ +++ +++ +++ Cold resistance test +++ +++ +++ +++ +++ ++ Boiling Water Resistance Test +++ +++ +++ +++ +++ +++ Corrosion Resistance Test +++ +++ +++ +++ +++ ++

As described above, the adhesive prepared according to the present invention is a one-part type, which is easy to use, has no gel phenomenon, has excellent storage stability, excellent adhesion, impact resistance, water resistance, heat resistance, processability and durability, and low temperature (190). ˜220 ° C.) has advantages such as high line speed and excellent productivity.

Claims (2)

10 to 30 parts by weight of acrylonitrile butadiene rubber, 20 to 60 parts by weight of polyvinyl chloride / polyvinylacetate copolymer resin, 20 to 50 parts by weight of saturated aliphatic polyester, based on 100 parts by weight of polymethyl methacrylate resin as a resin component, 20 to 50 parts by weight of an epoxy resin; Dicyandiamide as a latent curing agent, containing 5 to 10 parts by weight based on 100 parts by weight of polymethylmethacrylate resin; The above-mentioned resin component and the latent curing agent are dissolved in a mixed organic solvent system containing methyl isobutyl ketone, methyl ethyl ketone, diisobutyl ketone, toluene, xylene, diacetone alcohol and butyl cellosol moiety. Adhesive for vinyl film coated steel sheet. The mixed organic solvent system according to claim 1, wherein the mixed organic solvent system is methyl isobutyl ketone: methyl ethyl ketone: diisobutyl ketone: toluene: xylene: diacetone alcohol: butyl cellosol portion = 0.8: 0.3 to 0.7: 0.8: 1: Adhesive for coating a vinyl chloride film coated steel sheet, characterized in that the weight ratio of 1: 1: 1.6.