JPS60255871A - Bondable resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having excellent adhesion to various materials, by mixing a chlorinated fatty acid ester with a polymer obtd. by graft- polymerizing vinyl chloride onto an ethylene/vinyl acetate copolymer by suspension polymn. CONSTITUTION:60-95pts.wt. polymer obtd. by graft-polymerizing 5-60pts.wt. vinyl chloride or monomer mixture mainly composed of vinyl chloride onto 40- 95pts.wt. ethylene/vinyl acetate copolymer having a melt index of 0.1-500g/ 10min and a vinyl acetate content of 1-60wt% by suspension polymn. is mixed with 5-40pts.wt. chlorinated paraffin having a chlorine content of 35-70wt% obtd. by chlorinating n-praffin contg. an average of 11-16 carbon atoms separated from paraffin wax contg. an average of 22-26 carbon atoms, petroleum kerosine or gas oil fraction by using molecular sieves, or chlorinated fatty acid ester obtd. by chlorinating a fatty acid ester.

Description

[Detailed Description of the Invention] Related. More specifically, ethylene-vinyl acetate copolymer (hereinafter abbreviated as KVA) K is a polymer obtained by suspension graft polymerization of vinyl chloride or a heptanomer mixture mainly composed of vinyl chloride (hereinafter referred to as B V A / V O
It is abbreviated as Graftomer. ) and a chlorine-containing plasticizer.

The target areas are organic polymer materials and metals.

To obtain a resin composition having excellent adhesion to various materials such as inorganic materials and cellulose-based natural materials [6]. Among others, films made from saturated polyester,
It is an object of the present invention to obtain a resin composition having excellent adhesion to sheets and various molded products.

Conventionally, an enormous number of techniques have been proposed for adhesives. Based on their main components, they can be broadly divided into natural product-based, inorganic-based, thermoplastic resin-based, thermosetting resin-based, and rubber-based.

Adhesives first began to be used in large quantities industrially for the production of plywood, and subsequently grew rapidly with the development of synthetic resins and synthetic rubber. One of the synthetic resins closely related to such adhesives is polyester resin.

Polyester resin has excellent mechanical strength and water resistance.

It has gas barrier properties and is widely used as a laminate film for food packaging and retort pouches.

On the other hand, since polyester resin has poor adhesive properties, hot melt adhesives, film adhesives, and the like are not currently satisfactory as adhesives, and methods such as dry lamination of polyurethane have had to be used.

However, this method has many problems, such as insufficient adhesive strength, the use of solvents, which poses problems such as atmospheric pollution and the risk of explosion, and the resulting film has a solvent odor. was.

It is also known to hydrolyze the surface of polyester resin with alkali to improve its adhesion, but this method also requires large-scale hydrolysis equipment and is expensive. A rise was inevitable.

As described above, hot-melt adhesives and film adhesives for polyester resins are not well known at present, and their appearance has been awaited.

The present inventors were considering a method for improving the adhesive performance of s In VA/VO graftomer, and surprisingly found that a specific ratio of HV A/VO graftomer and a specific chlorine-containing plasticizer f. It was discovered that the composition of the present invention can be obtained by mixing the polyester resin with a polyester resin.

That is, the present invention uses EVA with a vinyl acetate content of 1 to 60% by weight.
40-layered part: 95 parts by weight or less, 5 parts by weight or more of vinyl chloride or a 7-mer mixture mainly composed of vinyl chloride, 6
0 parts by weight or less tS turbidity graft polymerization (BVA/Va graftomer) 60 parts by weight or more and 95 parts by weight or less and paraffin wax or petroleum kerosene or light oil fraction having an average carbon number of 22 to 26 From 5 parts by weight to 40 parts by weight of at least one type of chlorinated paraffin or fatty acid ester obtained by chlorinating n-paraffin having an average carbon number of 11 to 16 separated with a molecular sieve. This is an adhesive resin composition.

The present invention will be explained in detail below.

The IVA used in the present invention is produced by either a high-pressure radical polymerization method or a solution or emulsion polymerization method, and has a vinyl acetate content of 1 to 60% by weight.
Melt index (M engineering) is α1~5009/1
0 minutes, commercially available KVA that satisfies this condition.
can be used.

I! used in the present invention! The iVA/V O graftomer is obtained by suspension graft polymerization of 5 to 60 parts by weight of vinyl chloride to 40 to 95 parts by weight of 1iVA (as described above).

Suspension graft polymerization is carried out using IVA using an organic peroxide as an initiator.
KVA is dissolved in vinyl chloride and then subjected to graft polymerization, or the production technique disclosed in Japanese Patent Publication No. 4B-163146, etc., is a method in which KVA is not dissolved in vinyl chloride at a pressure lower than the saturated vapor pressure of vinyl chloride. , a method of graft polymerization in a swollen state can be used.

When the amount of graft polymerization exceeds 60 parts by weight, or when the vinyl acetate content in 1 cVA as the backbone polymer is 1% by weight
If it is less than that, the adhesiveness of the composition of the present invention will be significantly lower than that of the composition of the present invention.

In addition, when the amount of graft polymerization is less than 5 parts by weight, or when the amount of graft polymerization is less than 5 parts by weight, or 1! The vinyl acetate content in iVA is 6
When the amount exceeds 0% by weight, the resulting composition tends to stick to processing machines, etc., which is inconvenient.

The present invention (paraffin wax with an average carbon number of 22 to 26 or petroleum kerosene used) or n-
Chlorine content by chlorination of paraffin is 35-70% by weight
At least one type of chlorinated paraffin or chlorinated fatty acid ester obtained by chlorinating a fatty acid ester can be used, and commercially available chlorine-containing plasticizers that meet this condition, such as Toyoparax (Toyo Soda Kogyo #product), Niesizer (
NOF ■products) can be used.

In the composition of the present invention, KVA/VC! The quantitative ratio of the graftomer and chlorine-containing plasticizer depends on the specific application of the resin composition, its melt viscosity, and processability.

It is determined by comprehensively considering mechanical strength and other factors.

Specifically, the chlorine-containing plasticizer is zvA/vc graftomer 6.
5 parts by weight or more and 40 parts by weight or more for 0 parts by weight or more and 95 parts by weight or less
It is used in a range of parts by weight or less. Within this range, a resin composition with improved adhesiveness can be obtained and has properties that can be used in resin films for extrusion coating and adhesives.

As described above, the composition of the present invention is particularly effective as an adhesive between polyester and polyester or between polyester and other materials.

The composition of the present invention can be used in either a film or pellet form to effectively exhibit its effects. Needless to say, it can also be used as a film (sheet) or a multilayer film (sheet) by coating other materials (especially polyester resin). Usage form (as well as known additives, e.g. heat stabilizers).

Antioxidants, antiblock agents, slip agents, antistatic agents, colorants, etc. may be added.

Other plasticizers and inorganic fillers can also be added to the composition of the present invention to the extent that their effects are not impaired.

These components may be mixed using, for example, Banbury mixer 2.
Mixing can be done using a known method such as using two rolls or an extruder. The kneading temperature is determined in relation to the melting point 9 decomposition temperature of the v v a / v c graftomer and the melting point 9 decomposition temperature of the chlorine-containing plasticizer. Specifically, the temperature is preferably 100°C or more and 200°C or less.

The kneading time may be selected so as to provide a uniformly mixed resin composition. Specifically, 5 minutes or more is suitable.

As described above, the composition of the present invention is particularly useful as an adhesive for polyester resins, and its contribution to industries including packaging materials is extremely large.

The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to the present invention in any way.

Reference Example I Production of KVA/VO Graftomer (A) In a 701 stainless steel vinyl chloride polymerization vessel equipped with a stirring device, 90% of pure water was added. EVA (melt index 30ri/
For 10 minutes, saponified polyvinyl acetate 509 was charged into 5 (vinyl acetate content: 52% by weight) for 1 minute, the lid was closed, the air was replaced with nitrogen, and then the vinyl chloride monomer (vinyl acetate content 52% by weight) 509 was charged under vacuum pressure.
I introduced it.

Start raising the temperature without stirring, and when it reaches 60°C, 2.
2'-7:/His-2,4-dimethylvaleronitrile 5
g was added to initiate polymerization. Polymerization was carried out for 8 hours while introducing vinyl chloride monomer so as to keep the pressure constant at s Vda, and a v, vA/vc graftomer ((transform)) containing 81.7% by weight of EVA was obtained, which was used as a trap material in the following examples. did.

Reference example 2 EVA/VC! graft-r-(B),
(Cri, (D)+7) 70t equipped with manufacturing stirring equipment
In a stainless steel vinyl chloride polymerization container, add 27.9% of pure water. x
vA (melt index 509/1" 0 minutes, vinyl acetate content 32 parts) 9. Qkg, 50 g of partially saponified polyvinyl acetate was charged, the lid was closed, the air was replaced with nitrogen, and then the vacuum was applied to the vinyl chloride 7. 9 was introduced into -9,0.

The temperature was started to rise without stirring, and KVA was dissolved in the vinyl chloride monomer at 60°C for 5 hours.

Next, 5 parts of 2,2'-azobis-2,4-dimethylvaleronitrile was added to start polymerization, which was carried out for 8 hours to form a KVA/VC containing 62-5% by weight of EVAi.
Graftomer (B) was obtained.

Similarly, I! Okibe A graph including 1VA54 Jukeichi)
f-(0), EvA/vC containing 50% by weight of KVA
Graftomer (D) was obtained and used in the following examples.

Examples 1-1 to 1-7 HVA/VC graph (A) produced in Reference Example 1-2 at 150°C using a 6-inch roll
l (B).

(0) After melting a composition in which 2 parts by weight each of stabilizers N-2000IC (manufactured by Nitto Kasei ■) and K-101 (manufactured by Tokyo Fine Chemical ■) were added to each prescribed amount, a prescribed amount of chlorine-containing plasticizer was added. and kneaded for 5 minutes. As chlorine-containing plasticizers, chlorinated paraffin (Toyoparax A-40 (chlorine content 40% by weight) manufactured by Toyo Soda Kogyo ■) and chlorinated fatty acid ester (Newsizer 1005A (pentachlorinated methyl stearate) manufactured by NOF ■) were used. used.

A film of this composition f 11 am was sandwiched between l15m polyester resin, 150°C, 100J1
9/d for 5 minutes, and the T peel knotness was measured. The results are shown in Table-1.

Example 2-1 Using a 6-inch roll, 2 parts by weight each of stabilizers N-2000 and E-101 were added to 70 parts by weight of the RVA/VO graftomer (B) produced in Reference Example 2 at 150°CK. After the added composition was melted, 20 parts by weight of dioctyl terephthalate and 10 parts by weight of chlorinated paraffin (Toyoparax A-40) were added and kneaded for 5 minutes. This composition was made into a film of α1 seaweed, sandwiched between α3 seaweed polyester resins, and hot-pressed at 150°C, 9100kVe-d for 5 minutes, and the T-peel knotness of the film was measured. The results are shown in Table IK.

Comparative Examples 1-1 to 1-2 HVA/V produced in Reference Example 1゜2 at 130°C using a 6-inch roll (!gra,yt-r-(
A), (B), 100 parts by weight each with stabilizer + N-200
01. The compositions to which 2 parts by weight of each Ei-101 were added were melted and then kneaded for 5 minutes.

This composition was made into an α11Is film, sandwiched between l131m polyester resins, and heated at 150°C for 100 minutes.

Thermocompression bonding was carried out for 5 minutes, and the T-peel knotness was measured.

The results are shown in Table 1.

Comparative Example 2-1 Using a 6-inch roll, gvA/vc graftomer @70 produced in Reference Example 2 at 130°C was coated with Anjugyobu N.
-2000E,! After melting a composition to which 2 parts by weight of each of -101 was added, chlorinated paraffin (Toyoharax A-4
0) 50 parts by weight were added and kneaded for 5 minutes.

This composition was made into a film of α1 size, sandwiched between Q, 5m polyester resin, and 150″C, 100~.

Thermocompression bonding was carried out for 5 minutes, and the T-peel knotness was measured.

The results are shown in Table IK.

As is clear from the results in Table 1, it can be seen that the adhesive resin composition of the present invention is extremely effective as an adhesive for polyester resins and metals.

Patent applicant: Toyo Soda Kogyo Co., Ltd.

Claims (1)

[Claims] 1) (1) Melt index (L1 to 5009/1
0 minutes, ethyne-vinyl acetate copolymer with a vinyl acetate content of 1 to 60% by weight 40 parts by weight or more and 95 parts by weight or less of vinyl chloride or a monomer mixture mainly composed of vinyl chloride 5
60 parts by weight to 95 parts by weight of a polymer obtained by suspension graft polymerization of 60 parts by weight to 60 parts by weight, and (2) paraffin wax having an average carbon number of 22 to 26, petroleum liquerocin, or molecular polymer from gas oil fraction.・
5 parts by weight or more of at least one type of chlorinated paraffin with a chlorine content of 55 to 70% by weight obtained by chlorinating n-paraffin having an average carbon number of 11 to 16 separated by a sieve or chlorinated fatty acid ester obtained by chlorinating fatty acid ester 4
An adhesive resin composition comprising 0 weight or less.