JPH0637586B2 - Vinyl chloride polymer composition with improved adhesion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a vinyl chloride polymer composition.

More specifically, it relates to a vinyl chloride polymer composition having improved adhesion to polyurethane.

<Prior Art> and <Problems to be Solved by the Invention> Generally, since an ethylene polymer is non-polar, it has a drawback of poor compatibility with other polymers. However, ethylene-ethylenically unsaturated organic monomer-carbon monoxide-based copolymer (hereinafter may be abbreviated as carbon monoxide copolymer)
Has a highly polar carbon monoxide unit in the molecule,
Polyvinyl chloride, polyamide, cellulose derivatives, etc.
It has a feature that it has excellent compatibility with many polymers having a polar group (Japanese Patent Publication No. 550063).

In particular, carbon monoxide copolymers have been used as permanent plasticizers or modifiers for vinyl chloride resins, instead of conventional liquid plasticizers. The use of such a carbon monoxide copolymer changes the physical properties such as the rigidity of the resin compound due to volatilization or extraction of the liquid plasticizer, which has been a drawback of conventional vinyl chloride resin compounds, and bleeding of the liquid plasticizer. It is characterized in that the stickiness of the molded product due to out and the contamination of other base materials due to migration of the liquid plasticizer are not observed.

One of the uses of the vinyl chloride resin blended with a carbon monoxide copolymer that takes advantage of these characteristics is as an inner lining of a bag or attache case or a skin material for a crash pad of an automobile. In these applications, the vinyl chloride resin compound sheet is used by laminating it with a low to high foam material such as foamed polyurethane or crosslinked polyolefin foam which is a cushioning material. The lamination of the vinyl chloride resin compound sheet and the foam is generally performed by an adhesion method such as dry lamination using a polyurethane adhesive, but polyurethane injection foam molding is also performed for the polyurethane foam.

However, in the case of vinyl chloride-based fat blended sheets containing carbon monoxide copolymer, the affinity with polyurethane is poor,
Even if the conventional method for laminating a sheet of a vinyl chloride resin compound and a high foam is applied as it is, there is a problem that the sheet is not sufficiently adhered. Until now, in order to solve this problem, measures such as corona treatment or flame treatment on the surface of the vinyl chloride resin compound sheet containing carbon monoxide copolymer, or applying the primer solution in advance have been studied. Was done or was done. However, even with these measures, there are drawbacks in that the adhesion improving effect decreases over time in the case of corona treatment or frame treatment, and the adhesive strength varies, and in the case of primer treatment, the cost increases significantly. The current situation is that it cannot be said to be a complete countermeasure.

Therefore, when laminating a vinyl chloride polymer blend containing a carbon monoxide copolymer with a high foam, the affinity of the vinyl chloride polymer blend containing a carbon monoxide copolymer with polyurethane There is a demand for development of a method for improving adhesiveness to obtain an inexpensive and stable adhesive force.

<Means for Solving Problems> The inventors of the present invention have keenly studied a method for improving the adhesiveness with a polyurethane compound, which has been a drawback of a vinyl chloride polymer compound containing a carbon monoxide copolymer. As a result of investigation, it was found that such a problem can be effectively solved by a vinyl chloride polymer composition containing a specific vinyl chloride copolymer having a hydroxyl value of 30 or more.

According to the present invention, based on 100 parts by weight of a vinyl chloride polymer (A) substantially free of a hydroxyl group-containing monomer unit,
Ethylene-ethylenically unsaturated organic monomer-carbon monoxide-based copolymer (B) 10 to 150 parts by weight, and vinyl alcohol and (meth) acrylic acid hydroxyalkyl ester per 100 parts by weight of the copolymer (B). Vinyl chloride copolymer (C) 1 to 100 containing a selected hydroxyl group-containing monomer unit, having a vinyl chloride monomer unit content of 70% by weight or more and a hydroxyl value of 30 or more
A vinyl chloride polymer composition having improved adhesion to polyurethane, which is obtained by blending 1 part by weight thereof.

The ethylenically unsaturated organic monomer used in the production of the ethylene-ethylenically unsaturated organic monomer-carbon monoxide-based copolymer used in the present invention is a saturated carboxylic acid whose acid group has 2 to 18 carbon atoms. Vinyl ester,
Unsaturated mono- or dicarboxylic acids having 3 to 20 carbon atoms, esters of said unsaturated mono- or dicarboxylic acids,
Vinyl alkyl ether whose alkyl group has 1 to 18 carbon atoms, vinyl or vinylidene halide, acrylonitrile, methacrylonitol, norbornene, 3-1.
It is a compound selected from α-olefins having 2 carbon atoms and vinyl aromatic compounds. Preferred organic monomers include vinyl acetate, methyl (meth) acrylate, ethyl, butyl and the like.

In the ethylene-ethylenically unsaturated organic monomer-carbon monoxide copolymer used in the present invention, ethylene is about 40-80% by weight, preferably about 60-70%, and the unsaturated organic monomer is about 15-70% by weight. 60%, preferably about 20
35%, and about 5 to 30% carbon monoxide, preferably about 5
It is copolymerized at a ratio of -15%, and it is possible to further copolymerize other monomers, if necessary. And
For details of the method for producing such a carbon monoxide copolymer,
For example, it is described in JP-B-55-50063.

The vinyl chloride polymer used in the present invention is not only a vinyl chloride homopolymer, but also vinyl chloride and other comonomers, for example, α-olefins such as ethylene and propylene, vinyl esters such as vinyl acetate. , Unsaturated carboxylic acid esters such as acrylic acid esters, vinyl ethers such as alkyl vinyl ethers, vinyl bromide,
Copolymers with other vinyl halides such as vinyl fluoride, vinyl compounds such as styrene, acrylonitrile and vinylidene chloride, or vinylidene compounds other than these are used.

The vinyl chloride-based copolymer (C) containing a hydroxyl group-containing monomer unit having a hydroxyl value of 30 or more used in the present invention contains a hydroxyl group-containing monomer unit selected from vinyl alcohol and (meth) acrylic acid hydroxyl ester, and A copolymer having a vinyl monomer unit content of 70% by weight or more and a hydroxyl value of 30 or more as a copolymer.

Examples of the vinyl chloride-based copolymer of the present invention include those obtained by completely or substantially saponifying a vinyl chloride-vinyl ester copolymer.

Examples of the vinyl ester in this case include vinyl acetate and vinyl propionate, and vinyl acetate is most preferably used.

The copolymer of vinyl chloride and vinyl ester is produced, for example, by a suspension polymerization method.

The ratio of both monomers is 70% by weight or more of vinyl chloride monomer.

The saponification reaction of a vinyl chloride / vinyl ester copolymer converts, for example, vinyl ester units into vinyl alcohol units in the presence of an acid or alkaline catalyst in a slurry or solution state.

The concentration of the hydroxyl group-containing monomer unit is 30 or more, preferably 50 or more in terms of hydroxyl value, and the weight% of the vinyl alcohol unit is about 2% or more, preferably about 4% or more.

This hydroxyl group chemically reacts with, for example, an isocyanate group in a polyurethane-based adhesive described later, whereby it is possible to firmly bond the vinyl chloride-based polymer layer and various substrates through the polyurethane-based adhesive layer. Become. The hydroxyl value referred to here is the number of mg of potassium hydroxide required to neutralize the acetic acid necessary for acetylating the free hydroxyl groups contained in 1 g of the sample.

Other examples of the hydroxyl group-containing monomer unit include hydroxyalkyl esters of unsaturated carboxylic acids such as (meth) acrylic acid.

Vinyl chloride-based copolymers containing such vinyl alcohol units are well compatible with vinyl chloride-based polymer blends.

The carbon monoxide copolymer is used in an amount of about 10 parts by weight or more, preferably about 20 to 150 parts by weight, based on 100 parts by weight of the vinyl chloride resin (A) which does not substantially contain a hydroxyl group-containing monomer unit.

If it is less than 10 parts by weight, the plasticity is insufficient, and if it is used in an excessively large amount, it becomes too soft, which is not preferable.

The vinyl chloride-based copolymer (C) containing a hydroxyl group-containing monomer unit depends on the hydroxyl group-containing concentration, but is about 1 to 100 parts by weight, preferably about 2 to 50 parts by weight, per 100 parts by weight of the carbon monoxide copolymer. Used in proportion.

If the use ratio is less than this, the desired effect of improving the adhesiveness cannot be obtained.

On the other hand, if the usage rate is higher than this, the thermal stability is impaired,
The composition discolors during molding.

The composition can be prepared by using a kneader such as a two-roll mill or a Banbury mixer to knead the respective components simultaneously or sequentially. The composition can also be prepared continuously using a continuous kneader such as a twin-screw extruder or a Farrell continuous mixer. In any case, it can be carried out by almost the same operation method as the kneading operation of a usual vinyl chloride resin composition.

The vinyl chloride polymer blend of the present invention contains a vinyl chloride polymer, a carbon monoxide copolymer, a vinyl chloride copolymer having a hydroxyl value of 30 or more, and a liquid plasticizer and a resin modifier, if necessary. It is possible to add stabilizers, pigments and the like.

<Operation> The vinyl chloride-based polymer composition containing the carbon monoxide copolymer and the vinyl chloride-based copolymer having a hydroxyl value of 30 or more according to the present invention has a hydroxyl group and therefore exhibits good adhesion to various substrates. Although shown, in particular, a polyurethane-based polymer containing an isocyanate group is industrially important because the isocyanate group in the polyurethane-based polymer and the hydroxyl group in the composition can chemically bond to each other for stronger adhesion. Is.

For example, paper, cloth, metal, glass, rubber, plastic (polyolefin such as polyethylene, polypropylene, polyester, polyamide, polyvinylidene chloride, saponified polyvinyl acetate, polystyrene, polyacrylonitrile, ABS, etc. May be a foam) or the like and a vinyl chloride polymer composition of the present invention through a two-component polyurethane adhesive. The lamination method is not limited, but a dry lamination method is generally used in which a two-component polyurethane adhesive is applied to a substrate and then the vinyl chloride polymer sheet of the present invention is laminated.

It is also effective when the surface of various molded articles of the vinyl chloride polymer of the present invention is coated with polyurethane paint.

Further, when the vinyl chloride polymer composition sheet of the present invention is formed by vacuum forming or the like, and then two-component polyurethane is injected and foamed therein, a high adhesive strength with the polyurethane foam is exhibited, and therefore, for example, crash of automobile parts. It can be used in the production of pads.

Examples 1 to 3 and Comparative Examples 1 to 2 Dry blends having the blending ratios shown in Table 1 were prepared, and 150 g of the dry blends were used for the roll surface temperature of 165-1.
It was obtained by kneading with a 6 inch roll at 70 ° C. for 10 minutes. A dispensing sheet of about 0.5 mm of the vinyl chloride resin composition was obtained. About 100 g of a two-component polyurethane adhesive (made by Bond KU10 Konishi Co., Ltd.) is applied to the obtained two dispensing sheets.
After applying / m ² , these dispensing sheets were stuck together. After leaving at room temperature for 3 days, the laminated sheet is slit into a width of 25 mm and T-shaped peeling (peeling speed 50 mm / min) is performed.
The state of peeling was visually observed to evaluate the adhesiveness of the vinyl chloride resin composition. In Table 1, cohesive failure of the adhesive layer is indicated by O, and interfacial peeling between the adhesive and the dispensing sheet is indicated by X.

Examples 4 to 7 and Comparative Examples 3 to 5 Dry blends having the blending ratios shown in Table 2 were prepared, and 150 g of the dry blends were used at a roll surface temperature of 165 to 165.
The mixture was kneaded with a 6 inch roll at 170 ° C. for 10 minutes to obtain a dispensing sheet of about 0.5 mm of the obtained vinyl chloride resin composition. The obtained divided sheet is cut into a size of 9 cm in length and 12 cm in width and placed on the bottom of the die. 100 g of solution A (premix) and 53 g of solution B (4,4-diphenylmethane diisocyanate) prepared in the following mixing ratios are weighed in a plastic beaker. The measured solution A is added to solution B, and rapidly stirred at 4000 rpm for 10 seconds using a lab mixer. At this time, the temperature is controlled to 20 ± 2 ° C. The mixed solution is added to the mold within 10 seconds and the mold lid is closed. 20
After minutes, the foamed urethane foam is removed from the mold.
The taken-out foam was slit into a width of 25 mm and subjected to T-type peeling (peeling speed 50 mm / min), and the peeled state was visually observed to evaluate the adhesiveness of the vinyl chloride resin compound.

Composition of liquid A (premix) 100 parts by weight polypropylene glycol (5000 molecular weight) 100 parts by weight triethanolamine 3.5 parts by weight ethylene glycol 2.5 parts by weight Silicone emulsion (Shin-Etsu Chemical L-5305) 1.0 parts by weight water 0.6 parts by weight pentamethyldiethylenetriamine 0.
1 part by weight Triethylenediamine 0.2 part by weight In Table 2, the one in which the urethane layer was destroyed is ○, and the one in which the interface between the urethane layer and the dispensing sheet is peeled off is ×.
Displayed as.

Example 8 In Example 5, instead of the vinyl chloride-vinyl acetate-vinyl alcohol copolymer (A), a vinyl chloride-2-hydroxyethyl acrylate copolymer (average degree of polymerization 1300,
A dispensing sheet of the vinyl chloride resin composition was obtained in the same manner as in Example 5 except that the vinyl chloride unit content was 90% by weight and the hydroxyl value was 50), and the adhesiveness to urethane foam was evaluated in the same manner. .

As a result, it was confirmed that it had good adhesiveness.

Claims (3)

[Claims] 1. An ethylene-ethylenically unsaturated organic monomer-carbon monoxide copolymer (B) 10 to 100 parts by weight of a vinyl chloride polymer (A) substantially free of a hydroxyl group-containing monomer unit. 150 parts by weight and, based on 100 parts by weight of the copolymer (B), a hydroxyl group-containing monomer unit selected from vinyl alcohol and (meth) acrylic acid hydroxyalkyl ester, and a vinyl chloride monomer unit content of 70% by weight. Above, vinyl chloride-based copolymer (C) 1 to 100 having a hydroxyl value of 30 or more
A vinyl chloride polymer composition having improved adhesion to polyurethane, which is obtained by blending 1 part by weight. 2. The ethylene-ethylenically unsaturated organic monomer-carbon monoxide-based copolymer (B) is an ethylene-vinyl acetate-carbon monoxide-based copolymer.
5. A vinyl chloride polymer composition having improved adhesion to polyurethane according to the item. 3. The ethylene-ethylenically unsaturated organic monomer-carbon monoxide-based copolymer (B) is an ethylene-ethylenically unsaturated carboxylic acid ester-carbon monoxide-based copolymer. A vinyl chloride polymer composition having improved adhesion to polyurethane according to item 1.