JPH0273828A - Graft copolymerization and production and use thereof - Google Patents

Abstract

PURPOSE:To obtain the title copolymer having excellent heat resistance and heat adhesion by grafting a polyamide oligomer having a specific amino group at one end thereof to a trunk polymer of an unsaturated carboxylic acid derivative, ethylene and carbon monoxide. CONSTITUTION:(A) A monomer of alpha,beta-unsaturated carboxylic acid ester such as methyl (meth)acrylate or vinylester such as vinyl acetate, preferably of 10-50wt.% is subjected to radical polymerization with (B) ethylene, preferably of 20-89wt.% and (C) carbon monoxide, preferably of 1-30wt.% to afford a trunk polymer. Then (D) a polyamide oligomer, preferably having 600-10,000 number-average molecular weight and containing primary amino group at one end is added to the trunk polymer and reacted with the trunk polymer e.g. at 50-250 deg.C to provide the aimed copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a novel graft copolymer having excellent heat resistance and adhesive properties and having a copolymer consisting of ethylene, vinyl monomers and carbon monoxide as a base polymer. The present invention also relates to a method for producing the above-mentioned novel graft copolymer and its use.

Technical background of the invention and its problems Soft vinyl chloride resin has many excellent properties such as flexibility, transparency, and toughness, and properties such as flexibility can be freely changed by changing the amount of plasticizer added. Because it has the advantage of being adjustable, it is used in an extremely wide range of applications such as films, sheets, and extrusion molded products. However, adhesion of soft vinyl chloride resins is not always easy, and although many studies have been made on adhesives, no satisfactory adhesive has yet been found. Conventionally, solution-based adhesives such as chloroprene rubber, nitrile rubber, and polyester have been commonly used to bond soft vinyl chloride resins.
Since these solution-type adhesives use a solvent, they not only create a poor working environment, but also require a solvent drying process, resulting in high costs.

In order to improve these drawbacks, adhesives are already known that can be used to bond soft vinyl chloride resins that can be thermally bonded without using a solvent. For example, examples of such adhesives include vinyl chloride grafted ethylene/vinyl acetate copolymer (Japanese Patent Application Laid-Open No. 57-1673H), carboxyl-modified ethylene/vinyl acetate copolymer (Japanese Patent Application Laid-Open No. 59-5217).
4) and an ethylene/vinyl acetate/carbon monoxide copolymer (Japanese Unexamined Patent Publication No. 165427/1982) have been proposed.

However, since these copolymers have low melting points, when these copolymers are used as adhesives to bond adherends, they easily break down due to shear forces when the adherends are placed in a high temperature atmosphere. It has an essential drawback of causing adhesive failure, and an improvement has been sought.

In view of the current situation, the inventors of the present invention have conducted repeated studies to obtain an adhesive that has excellent heat resistance and is capable of thermal bonding, and has developed a monomer (a) selected from unsaturated carboxylic acid esters and vinyl esters, ethylene (1)) and carbon monoxide (c
We have discovered that a new copolymer obtained by modifying the core copolymer (A) consisting of As a result, we have arrived at the present invention.

OBJECTS OF THE INVENTION An object of the present invention is to provide a novel graft copolymer having excellent physical properties such as excellent heat resistance and thermal adhesion. Another object of the present invention is to provide a novel graft copolymer that can be thermally bonded to soft vinyl chloride resins and other base materials at low temperatures and has excellent adhesive properties, particularly heat-resistant adhesive properties. .

Another object of the present invention is to improve particularly heat deformation resistance and heat resistant adhesion compared to the raw material backbone copolymer (A), and to improve the plasticity contained in the resin when laminated with a soft vinyl chloride resin. The object of the present invention is to provide a novel graft copolymer that exhibits a reduced tendency to swell due to agents. Other objects of the invention will become more apparent from the description below.

Summary of the Invention The novel graft copolymer according to the present invention is obtained by copolymerizing a monomer (a) selected from unsaturated carboxylic acid esters and vinyl esters, ethylene (b), and carbon monoxide (c). It is characterized in that a polyamide oligomer (B) having a primary amino group at one end is grafted onto the base copolymer (A).

Such a novel graft copolymer can be produced by copolymerizing the above-mentioned base copolymer (A) with the above-mentioned polyamide oligomer, and this novel graft copolymer is It exhibits excellent properties when used as an adhesive, especially as an adhesive for polyvinyl chloride.

DETAILED DESCRIPTION OF THE INVENTION The novel graft copolymer of the present invention, its manufacturing method, and its uses will be specifically described below.

The novel graft copolymer according to the present invention comprises a monomer (a) selected from the group consisting of unsaturated carboxylic acid esters and vinyl esters, ethylene (b), and carbon monoxide (
This copolymer is obtained by graft-polymerizing a polyamide oligomer (B) having a primary amine at one end to a core copolymer (A) obtained by copolymerizing c).

The monomer (a) used when producing the backbone copolymer (A)
) is selected from the group consisting of unsaturated carboxylic esters and vinyl esters as described above.

Such unsaturated carboxylic acid esters are preferably α,β-unsaturated carboxylic esters, and the α,β-unsaturated carboxylic acid components used include acrylic acid, methacrylic acid, maleic acid, etc. As the alcohol component, linear or branched alcohols having about 1 to 10 carbon atoms are preferable, and specific examples include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, and 5ee-butanol. , n-
Hexanol, n-octatool, 2-ethylhexanol, n-decanol, etc. are used.

Specifically, such unsaturated carboxylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate. 2-ethylhexyl acid, phenyl (meth)acrylate, dimethyl maleate, etc. are used.

Further, as the vinyl ester, specifically, vinyl formate, vinyl acetate, vinyl propionate, etc. are used.

In such a backbone copolymer (A), the monomer (a) is 1
Ethylene (b) in an amount of 0 to 50% by weight, preferably 20 to 40% by weight, and 20 to 89% by weight, preferably 40 to 78% by weight.
Preferably, carbon monoxide (e) is copolymerized in an amount of 1 to 30% by weight, preferably 2 to 20% by weight. If the content of carbon monoxide (c) in this core copolymer (A) is less than 1% by weight, it will be difficult to increase the amount of polyamide oligomer grafted onto this core copolymer (A), and therefore , it is difficult to obtain a graft copolymer with good performance. Moreover, if the content exceeds 30 weight, the resulting graft copolymer will have poor weather stability, which will limit the field of use of the graft copolymer. In addition, when using the graft copolymer according to the present invention in an adhesive, it is preferable to use a backbone copolymer (A) having an oxygen atom content of about 5 to 20% by weight.

The molecular weight of the backbone copolymer (A) varies depending on the use of the graft copolymer, but the weight average molecular weight measured by gel permeation chromatography (CPC) is 10 to 10.
In particular, it is preferably 10 to 5×105. In addition,
The average molecular weight by GPC is a value measured at 135° C. using orthodichlorobenzene as a solvent and converted to the molecular weight of polystyrene.

Such a backbone copolymer (A) is already well known, and generally the reaction temperature is 150 to 250°C and the reaction pressure is 50°C.
It can be obtained by radical copolymerization of monomer (a), ethylene (b) and carbon monoxide (c) using a bulk polymerization method under conditions of 0 to 3000 kg/c-, and can also be produced by solution polymerization or emulsion polymerization. is possible.

In the novel graft copolymer according to the present invention, a polyamide oligomer (B) having a primary amino group at one end is graft-polymerized to the above-mentioned base copolymer (A), and the polyamide oligomer (B) is derived from a polyamide oligomer. The side chains of the base copolymer (A) are bonded to the base copolymer (A).

The polyamide oligomer (B) used in the present invention has a structure in which one end is a primary amino group and the other end is an inactivated carboxyl group, and the terminal carboxyl group is usually capped with a primary amine. has been done. In the present invention, graft copolymerization is carried out by reacting the primary amino group at one end with the carbonyl group of the base copolymer.

Note that a conventionally known method can be employed to seal the other end carboxyl group of the polyamide oligomer (B) with a primary amine.

Such a reaction between the carbon monoxide component in the backbone copolymer (A) and the primary amino group in the polyamide oligomer (B) can be carried out by grafting by a pyrrole ring formation reaction or a Schiff base formation reaction as shown in the following formula. It is assumed that the

Alternatively, the production of a C-0+H2N-, C-N- graft copolymer can be confirmed, for example, by thin layer chromatography. For example, by spotting the graft copolymer of the present invention on a thin silica gel plate,
Toluene-2,2,2-) refluoroethanol (1/
When 1) is expanded, it appears as an R1 value different from that of the raw material. For example, polyamide oligomers and backbone copolymers typically have R4 values of 0 and 0.3 to 0.8, respectively.
On the other hand, the Rr value of the graft copolymer is usually 0.
．． It is about 1 to 12.

The number average molecular weight of the polyamide oligomer (B) is 600
-1.0000, particularly preferably 600-4000. The number average molecular weight of the polyamide oligomer (B) is 6
If it is less than 00, the effect of improving the heat resistance of the resulting graft copolymer will not be sufficient, and if it exceeds 1,0000, the grafting reaction will be slow and it will be difficult to increase the grafting efficiency.

Various polyamide oligomers (B) can be used, including various lactams, ω-aminocarboxylic acids,
A homopolymer or copolymer such as nylon salt is used, and one end of this polyamide oligomer (B) has 1 carbon number.
It is sealed with ~20 primary amines.

Specifically, such polyamide oligomers (B) include homopolymers or copolymers of caprolactam, laurolactam, and hexamethylene diammonium adipate, such as nylon 6, nylon 66, nylon 11, nylon 12, and nylon 6. /66, nylon 6/
12, one end of an oligomer such as nylon 46 is used as a sealant such as n-butylamine, rhohexylamine, n-
A polyamide oligomer sealed with octylamine or the like can be used. It is preferable that such a polyamide oligomer (B) has a melting point of about 130 to 230°C. The melting point can be adjusted by the type of monomers used, and in the case of copolymerized oligomers, the ratio of monomers used.

If a polyamide oligomer whose one end is not capped with a primary amine is used as the polyamide oligomer (B), the molecular weight of the oligomer will increase during graft modification.
It is difficult to efficiently obtain a desired graft copolymer.

Also, when using an oligomer with amino groups at both ends,
Because crosslinking occurs during graft modification, it is difficult to obtain graft copolymers with good processability.

In the graft copolymer according to the present invention, the polyamide oligomer (B) is 1 to 40 parts by weight relative to 60 to 99 parts by weight, particularly 70 to 98 parts by weight, of the base copolymer (A), although it varies depending on the purpose of use. It is particularly preferable to graft in an amount of 2 to 30 parts by weight. If the amount of grafting of component (B) is too small, the effect of improving heat resistance will not be sufficient. If the grafting ratio of component (B) exceeds the above range, the heat resistance will be excellent, but the adhesive force will be low when used for adhesion of soft vinyl chloride resin.

The graft copolymer can be produced by bringing the base copolymer (A) and polyamide oligomer (B) into close contact in the presence or absence of a solvent. The reaction temperature is, for example, in the range of 50 to 250°C. In the reaction using a solvent, it is preferable to use a solvent that dissolves both raw materials, for example, 1, 1. i, R3,3
Fluorine-containing alcohols are used, such as -hexafluoroinpropertool, 2,2.2-)refluoroethanol. In addition, in the case of a reaction that does not use a solvent, it is preferable to adopt a method of melting and kneading both raw materials at a temperature higher than their melting points so that both components come into sufficient contact with each other.

In the reaction of graft polymerizing the polyamide ribomer (B) onto the base copolymer (A) as described above, a catalyst is not particularly required, but the reaction speeds up when the polymerization reaction is carried out in the presence of an acid. . As such acids, inorganic salts such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as p-toluenesulfonic acid, chloroacetic acid, and trifluoroacetic acid can be used.

Before the reaction, either tri-blend the two components in advance, or
Alternatively, a composition of the two can be prepared by intimately mixing them under conditions where almost no reaction occurs, and when used, the composition is reacted while being melted and extruded, and the melt is molded into a predetermined shape or adhered. It can be applied to the body.

The structure of the novel graft copolymer obtained in this way is determined by 13C nuclear magnetic resonance absorption spectrum (13C-NMR), infrared absorption spectrum (IR), as described below.
, confirmed based on the temperature-melt viscosity curve, etc.

The graft copolymer according to the present invention has a higher heat distortion temperature and excellent heat resistance than the base copolymer as a raw material,
In many cases, the tensile strength at break of the graft copolymer is equal to or higher than that of the base copolymer. Furthermore, this graft copolymer exhibits good adhesion to soft vinyl chloride resin or other base materials, and also has excellent heat resistance at the bonded portion. Furthermore, when this graft copolymer was laminated with a soft vinyl chloride resin, the migration of the plasticizer was less than when using the base copolymer (A), which resulted in less rigidity of the soft vinyl chloride resin and less surface roughness. Another advantage is that it can reduce problems such as deterioration.

The graft copolymer according to the present invention can be used alone or blended with various additives or other materials as an adhesive or heat sealing material for various base materials. When the graft copolymer according to the present invention is used as an adhesive, the adherends include polyvinyl chloride, polyvinylidene chloride, polyester resin, polyamide resin metal,
Examples include wood, cloth, polyolefin foam, etc. Application to these adherends can be done by extrusion coating the graft copolymer as described above onto the adherend, or by preparing a graft copolymer film in advance and thermocompression bonding this film onto the adherend. A method such as a method of coating the graft copolymer onto an adherend using a roll coater can be employed. When this graft copolymer is used as a hot melt adhesive, a tackifying resin, a plasticizer, a wax, etc. may be appropriately blended into the graft copolymer.

Furthermore, the graft copolymer according to the present invention can be used as a modifier for various polymers. For example, it can be blended as a modifier into polyvinyl chloride, polyamide resin, polyester resin, polycarbonate, and the like.

The graft copolymer according to the present invention may contain weathering stabilizers, antioxidants, pigments, dyes, antistatic agents, various fillers, and the like.

Effects of the Invention The novel graft copolymer according to the present invention has a high heat distortion temperature and excellent heat resistance, and also has excellent adhesive properties. Such a novel graft copolymer is useful as an adhesive, and exhibits particularly excellent adhesion to soft vinyl chloride, with little transfer of plasticity from the soft vinyl chloride to the graft copolymer.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

The present invention is illustrated by examples of some preferred embodiments thereof, in which all parts, proportions, and percentages are by weight unless otherwise indicated.

Determination of Characteristics of Base Copolymer (1) Determination of Copolymer Composition Ratio The copolymer composition ratio was determined by 18NMR. The chemical shift of 10-0- carbon in vinyl acetate is 172 ppm
, acrylic acid, n-butyl -C-O- carbon is 175
pp11, carbon monoxide, C-0 is 214 ppm.

]　8 (2) Melt flow rate Measurement was carried out at a load of 2160 g and a temperature of 190°C.

(8) PS equivalent weight average molecular weight The copolymer was dissolved in 0-dichlorobenzene, measured at 135°C using a Waters gel permeation chromatograph, and calculated from the distribution curve.

Characteristic determination of polyamide oligomer (1) Sulfuric acid viscosity Based on JIS K 8810, dissolved in 98% concentrated sulfuric acid,
Measured with an Ostwald viscometer.

(2) Number average molecular weight The number average degree of polymerization was calculated from the sulfuric acid viscosity and converted into a number average molecular weight. The copolyamide was calculated as nylon 6.

(Degree of polymerization) - (viscosity - 1,05)

(4) Amount of terminal amino group Determined by titration.

In addition, r6J in the skeleton structure representation in the table is a polymer of ε-caprolactam, r6/66J is a copolymer of ε-caprolactam and hexamethylene diammonium adipate, r
6/12J represents a copolymer of ε-caprolactam and ω-laurolactam, rl, 2/66J represents a copolymer of ω-laurolactam and hexamethylene diammonium adipate.

Graft Reaction A Toyo Seiki Labo Blast Mill (capacity: 50 m1) was heated to a predetermined temperature, a total of 50 g of the base copolymer and polyamide oligomer was put therein, and the mixture was kneaded at a rotor rotation speed of 50 rpm for 10 minutes and then taken out.

Performance evaluation of graft copolymers (1) Creation of performance evaluation sheet Compression molding was performed at 180°C.

(2) Melt flow rate 21.60g, 190°C and 2160g.

Measured at 230°C.

(3) Tensile strength at break and elongation at break Measured using a 4-bow dumbbell specified in JIS K 6801 at a tensile rate of 200/min.

(4) Melting point Measured using DuPont DSC.

(5) Adhesive strength to soft PVC The graft copolymer was heat-pressed to form 0.2mmmm Lenosheet, soft PVC (PVC/DOP-100/[
10 thickness 0.2 dragon), 120℃, 1 kg /
C. Heat sealed for 5 seconds.

The initial adhesive strength was measured at 23° C. for 1 day, and the change over time was 50 days. After 3 months, the film was left at 23° C. for 1 day, and then a T-peel test was conducted.

T-type peeling was performed using a Shimabara Seisakusho Autograph at a crosshead speed of 300-17 minutes.

(B) A graft copolymer sheet with a shear adhesive failure temperature of 0.2mm thickness at 75f/rrf
Craft, heat sealed at 120℃, 1kg/cj, 5 seconds to create a sample, JIS K
6844, the temperature was raised at 24° C./hour with a load of 1 kg.

(7) Dop swelling degree A 1 mm sheet of the graft copolymer was punched out into 30 x 10 pieces, immersed in DOP (dioctyl phthalate, plasticizer), left at 23°C for 14 days, and then weighed.
Weight increase rate was calculated.

(8) 18c nuclear magnetic resonance absorption spectrum graft copolymer 600 tag 3cc toluene/2.2.24
It was measured by dissolving it in refluoroethanol (1/1).

Equipment - JEOL Ltd. (JEOI) JNM-GX270
87.8 MHz Measurement temperature: 63.0°C Number of integrations: 30,000 times (9) Fourier transform infrared absorption spectrum The graft copolymer was made into a 0.1 mm press sheet and measured.

Device n BIORAD FTS-40 Resolution: 4. Ocm-' Number of integration: 264 times (10) Melt viscosity device: Instron capillary rheometer Measurement temperature: ] 70.190.210.230°C Shear rate: 15.8.52.7.158.527.1580 .5
266 1/sec Example 1 Ethylene-vinyl acetate-carbon monoxide terpolymer (63% by weight of ethylene, 28% by weight of vinyl acetate, 96% by weight of carbon monoxide, melt flow rate 35g/10 min (190% by weight)
°C), polystyrene equivalent weight East direction molecular weight 141,000) 9
Gravender Plast at a ratio of 5 parts by weight of nylon 6 oligomer (number average molecular weight 1960, NH2 content 5.1 x 10-4 mol/g, melting point 213°C) sealed with n-butylamine to 5 parts by weight. Prepared in the graph, 230
The mixture was kneaded and reacted at 50 rpm for 10 minutes. Table 1 shows the results of performance evaluation of the obtained graft copolymer.

Examples 2 to 5 The same procedures as in Example 1 were conducted except that the types and proportions of polyamide oligomers used and the reaction temperature were changed as shown in Table 1.

The results are shown in Table 1.

Note that for the graft copolymer obtained in Example 4, toluene/2,2.2-trifluoroethanol (1/1
), spotted on a thin silica gel plate, and developed with toluene/2,2,2-trifluoroethanol (1/l), the Rr value was 0.1.

The Rr value of the backbone copolymer spotted at the same time is 0.3 to 0.
, 7, and the polyamide NMR chart is shown in FIG.

Comparative example 1 Table 1 shows the performance evaluation of the raw material copolymer.

Example 6 90 parts of the terpolymer Pere Soto of Example 1 and 10 parts of the polyamide oligomer powder of Example 1 were triblended,
Using a 30 mm single screw extruder (L/D-32, Dalmage screw), extrusion was carried out at a cylinder temperature of 230° C. and a screw rotation speed of 40 revolutions/min while reacting to obtain a graft copolymer.

The results are shown in Table 1.

- Examples 7 to 14, Comparative Example 2 Ethylene-acrylic acid lobate-carbon monoxide copolymer (60% by weight of ethylene, 30% by weight of n-butyl acrylate, 10% by weight of carbon monoxide, The same procedure as in Example 1 was carried out, except that the melt flow rate was 6 g/1.0 min (190°C), the polystyrene equivalent weight average molecular weight was 420,000), and the polyamide oligomers shown in Table 2 were reacted at a predetermined blending ratio. I did it.

The results are shown in Table 2.

For comparison, performance evaluations of the raw material core copolymers are also shown in Table 2. Further, the infrared absorption spectra of the graft copolymers of Examples 9 and 10 are shown in FIGS. 2 and 3, and the melting behavior of the graft copolymers of Example 9 is shown in FIG. As is clear from Figure 4, the viscosity decrease occurs as the temperature rises, but it is quite severe near the melting point, and becomes gradual again when the temperature rises above the melting point.
This shows melting behavior unique to graft copolymers.

Examples 15 to 18 Example 9 except that the backbone copolymer was changed to those in Table 3.
A similar graft copolymerization was carried out.

The results are shown in Table 3.

[Brief explanation of the drawing]

FIG. 1 is a drawing showing an example of a 13c nuclear magnetic resonance absorption spectrum of the graft copolymer of the present invention, and FIGS. 2 and 3 are drawings showing an example of an infrared absorption spectrum. FIG. 4 is a drawing showing an example of the melting characteristics of the graft copolymer of the present invention.

Claims (9)

[Claims] (1) A core copolymer (A) formed by copolymerizing a monomer (a) selected from unsaturated carboxylic acid esters and vinyl esters, ethylene (b) and carbon monoxide (c),
Polyamide oligomer (B
) is grafted thereon. (2) The backbone copolymer (A) has 10 to 5 monomers (a).
The graft copolymer according to claim 1, which is a copolymer in which ethylene (b) is copolymerized in a proportion of 0% by weight, ethylene (b) is copolymerized in a proportion of 20 to 89% by weight, and carbon monoxide (c) is copolymerized in a proportion of 1 to 30% by weight. Polymer. (3) The weight average molecular weight of the backbone copolymer (A) is 10^4
The graft copolymer according to claim 1 or 2, which has a molecular weight of 10^6. (4) The number average molecular weight of the polyamide oligomer (B) is 6
The graft copolymer according to claim 1, which has a molecular weight of 00 to 10,000. (5) The graft copolymer according to any one of claims 1 to 4, wherein the polyamide oligomer (B) is grafted at a ratio of 1 to 40% by weight with respect to the base copolymer (A). . (6) A core copolymer (A) consisting of a monomer (a) selected from unsaturated carboxylic acid esters and vinyl esters, ethylene (b) and carbon monoxide (c) has a primary amino group at one end. A method for producing a graft copolymer, which comprises graft polymerizing a polyamide oligomer (B). (7) A core copolymer (A) consisting of a monomer (a) selected from unsaturated carboxylic acid esters and vinyl esters, ethylene (b) and carbon monoxide (c) has a primary amino group at one end. A raw material composition for producing a graft copolymer comprising a polyamide oligomer (B). (8) An adhesive comprising the graft copolymer according to any one of claims 1 to 5. (9) The adhesive according to claim 8, which is used for adhering polyvinyl chloride.