JPS5986677A - Adhesive resin composition - Google Patents

Abstract

PURPOSE:To provide an adhesive resin having high adhesion to metals and excellent fabricability, with less blocking of films, by incorporating a thermoplastic copolyester resin and an epoxy group-contg. ethylene copolymer. CONSTITUTION:A thermoplastic copolyester resin (A) and an epoxy group-contg. ethylene copolymer (B) and, if necessary, furthermore a thermoplastic resin (C) are melted and kneaded by single-screw extruders, double-screw extruders, Banbury mixers, hot mills, etc. Component A used is yielded by selecting carboxylic acid components and glycol components properly and co-condensing, and its m.p. is pref. 80-200 deg.C. Component B is yielded by copolymerizing ethylene with epoxy group-contg. unsatd. monomers copolymerizable therewith, such as alpha,beta- unsatd. glycidyl esters.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel adhesive resin composition. More specifically, the present invention relates to adhesive resin compositions used for synthetic resins such as polyvinyl chloride resins and polyester resins, and metals.

In general, thermoplastic copolyester resins are widely used as various paints and adhesives because they have excellent flexibility, weather resistance, and adhesion to various substrates. In particular, it is known to have excellent adhesion to synthetic resins such as polyester resins, soft and hard polyvinyl chloride resins, polycarbonate resins, HeB8 resins, and polyurethane resins. It also has adhesion to metals such as aluminum, lead, and iron, but it is not necessarily as satisfactory as the adhesion to synthetic resins. Therefore, if a laminate of synthetic resin and metal is manufactured using thermoplastic copolymerized polyester resin alone as an adhesive, it is difficult to obtain a laminate of synthetic resin and metal that is sufficiently satisfactory for practical use. There is a strong desire to develop a resin with well-balanced and high adhesive properties.

In addition, thermoplastic copolymerized polyester resin can be laminated onto base materials such as films and metals using molding and processing methods used for general plastics (inflation method, T-die extrusion method, extrusion lamination method, etc.). In some cases, it sticks to the cooling roll and cannot be peeled off, making it impossible to mold or process it, or even if it can be molded or processed,
Because of the large blocking of the film, once the film is wound into a coil, when trying to manufacture a laminate again using an offline method, the processability is poor because it is difficult to unwind the film. Therefore, it has excellent moldability and processability, and
There is also a strong desire to develop resins with less film blocking.

In view of these circumstances, the present inventors have developed a thermoplastic copolyester resin that maintains the unique adhesion properties of thermoplastic copolyester resin to various synthetic resins, has high adhesion to metals, has excellent moldability and processability, and The present invention was arrived at as a result of extensive research into adhesive resins with less film blocking.

That is, the present invention provides a novel adhesive resin composition comprising a thermoplastic copolymerized polyester resin (Al and an epoxy group-containing ethylene copolymer fBl, or one or more thermoplastic resins (C1). This is what we provide.

The present invention will be explained in detail below.

The thermoplastic copolymerized polyester resin iAl used in the present invention can be obtained by appropriately selecting a carboxylic acid component and a glycol component and cocondensing them by a conventional method.

Examples of the carboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and 5-sodium sulfoisophthalic acid; for example, succinic acid, adipic acid, Aliphatic dicarboxylic acids such as azelaic acid, sebacic acid, ≠camethylene dicarboxylic acid, timer acid, alicyclic dicarboxylic acids such as l,4-cyclohexanedicarboxylic acid, e.g. P-(2-hydroxyethoxy)benzoic acid Examples include cyclic lactones such as ε-caprolactone. These can be arbitrarily selected and used. The carboxylic acid component is particularly terephthalic acid or terephthalic acid and isophthalic acid.
It is preferable that the amount of dicarboxylic acids other than terephthalic acid and isophthalic acid is 0 to 100 mol % and 60 to 0 mol %.

Glycol components include ethylene glycol, diethylene glycol, polyethylene glycol, 1.2-propylene glycol, 1°8-propylene glycol,
1.4-butanediol, 1.8-butanediol, 1
．． It consists of one or more glycols such as 4-cyclohexane dimetatool, neopentyl glycol, 1,5-bentanediol, 1,6-hexanediol, and N-methyljetanolamine. As the glycol component, ethylene glycol, neopentyl glycol and 1,4-butanediol are particularly preferred.

In addition to the above-mentioned components, trivalent or higher acid acids such as trimellitic acid and trimethylolpropane, or trivalent or higher alcohol components may be added as necessary.

Thermoplastic copolymerized polyester resin (Al
The first method is not particularly limited, and can be carried out according to a conventional method.

For example, there is a method in which terephthalic acid, isophthalic acid, other dicarboxylic acids, or ester-forming derivatives thereof are added with glycols and a catalyst, and then (5) directly esterified or transesterified, and then polymerized. In addition, the thermoplastic copolymerized polyester resin tAl of the present invention can be obtained by adding glycols to polyethylene terephthalate resin to perform a depolymerization reaction and a recondensation reaction based on transesterification reaction with the glycols. A modified ether type polyester resin in which ethylene glycol is partially replaced with glycol can be used.

The melting point of the thermoplastic copolymerized polyester resin (Al) of the present invention is preferably 80 to 200°C. If the melting point exceeds 200°C, processability will be poor, and if the melting point is below 50°C, even the composition of the present invention will not provide a blocking-free film. do not have.

The epoxy group-containing ethylene copolymer used in the present invention (Bl is an epoxy group-containing unsaturated monomer that can be copolymerized with ethylene by a known method such as high-pressure radical polymerization, solution polymerization, or emulsion polymerization) For example, it can be obtained by copolymerizing α,β-unsaturated glycidyl varnish (6) with an unsaturated monomer such as α,β-unsaturated glycidyl ether.Specific examples of unsaturated monomers include is glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 2-
Examples include methylallyl glycidyl ether.

The amount of the epoxy group-containing unsaturated monomer in the copolymer is generally 0.01 to 20 mol%, preferably 0.1-20 mol%.
It is 10 mol%. Furthermore, the ethylene copolymer tB1 can also be produced by graft-modifying polyethylene or a copolymer with ethylene with the aforementioned unsaturated monomer.

Epoxy group-containing ethylene copolymer f used in the present invention
Bl is not limited to the above two-component copolymer. That is, as the eighth component, an unsaturated ester monomer, for example, an unsaturated carboxylic acid ester such as methyl acrylate, ethyl acrylate, methyl methacrylate, or butyl acrylate, and an unsaturated vinyl ester such as vinyl acetate or vinyl propionate. A copolymer obtained by copolymerizing 13 or more selected from the following can also be used.

The melt index of the epoxy group-containing ethylene copolymer (Bl) may generally be within a range that is easy to process, and is usually 0.
．． 1-800P/10 minutes, preferably 0.5-80)
/10 minutes.

The thermoplastic resin (C) used in the present invention is 1 g or 2 or more selected from vinyl aromatic hydrocarbon polymers, (meth)acrylic acid ester polymers, rubbery substances, and ethylene polymers. be.

The vinyl aromatic hydrocarbon polymer, which is one of the thermoplastic resins +01, may be a single or copolymer of vinyl aromatic hydrocarbons having 8 to 2 carbon atoms, particularly 8 to 12 carbon atoms, and specifically, polystyrene, These include poly-α-methylstyrene, polyvinyltriene, poly-β-methylstyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, and the like. A preferred vinyl aromatic hydrocarbon polymer is polystyrene.

The (meth)acrylic acid ester polymer, which is one of the thermoplastic resins (C1), has the general formula (wherein R represents hydrogen or a methyl group, and R2 represents an alkyl group having 1 to 4 carbon atoms. ) It is a homopolymer or a copolymer.

Specifically, they include methyl acrylate polymer, methyl methacrylate polymer, ethyl acrylate polymer, butyl acrylate polymer, methyl methacrylate-butyl acrylate copolymer, and the like. In the present invention 1, the most preferred (meth)acrylic acid ester polymer is a methyl methacrylate polymer and a copolymer mainly composed of methyl methacrylate. The (meth)acrylic acid ester polymer may be one further copolymerized with other unsaturated monomers such as styrene, acrylonitrile, etc. (9).

As a rubber-like substance that is one of the thermoplastic resin TO+,
Ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber, ethylene-butene copolymer comb, poly-1-butene copolymer rubber, ethylene-isobutylene copolymer rubber, polyisobutylene, poly These include isoprene, polybutadiene, styrene-butadiene random copolymer rubber, styrene-butadiene block copolymer rubber, hydrogenated products of styrene-butadiene copolymer rubber, natural rubber, atacti, polypropylene, and the like.

Among them, ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber, ethylene-propylene copolymer rubber,
Butene copolymer rubber and polybutadiene are particularly preferred.

The ethylene copolymer, which is one of the thermoplastic resins (C1), is at least one polymer selected from polyethylene and ethylene-unsaturated ester copolymers. , no particular limitations, high-pressure radical polymerization method, solvent polymerization method,
Known methods such as solution polymerization can be applied.

Examples of the ethylene-unsaturated ester copolymer include ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, ethylene-methyl methacrylate copolymer, and ethylene-vinyl ester copolymer.
Examples include ethylene-unsaturated carboxylic acid ester copolymers such as methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer. When this ethylene polymer is a copolymer, its ethylene content is 50 mol% or more, preferably 7
It is 0 to 99 mol%. The melt index of the ethylene copolymer is 0.01 to 800y/10 min, preferably 0.
．． 1 to 80y/10 minutes.

Although the proportion of each component in the adhesive resin composition of the present invention is not particularly limited, the thermoplastic copolymerized polyester resin (
Al content is 80-90! ffi%, preferably 40-8
0% by weight, the total amount of the epoxy group-containing ethylene copolymer (13) component and the thermoplastic resin (component 01 is 70 to IO% by weight, preferably 60 to 20% by weight, and the epoxy group-containing ethylene copolymer Coalescence (Bl component and thermoplastic resin (
The proportion of the epoxy group-containing ethylene copolymer fBl component in the total amount of component C) is 3 to 100% by weight. If the thermoplastic copolymerized polyester resin (Al component is less than 30% by weight) or the epoxy group-containing ethylene copolymer (the total amount of the Bl component and thermoplastic resin 1cI component exceeds 70% by weight), various types of thermoplastic copolymerized polyester resin IAI specific to Adhesion to synthetic resins, especially soft polyvinyl chloride resins, is significantly reduced.In addition, epoxy group-containing ethylene copolymer fB
If the total amount of the l component and the thermoplastic resin (C'l component is less than 10% by weight and the thermoplastic copolymerized polyester resin fAl component exceeds 90% by weight, not only will no adhesion improvement effect with metal be observed, but also thermal The extrusion processability of the plastic copolyester resin tAl and the blocking property of the film cannot be improved.Furthermore, the composition of the thermoplastic copolyester resin fAl component and the thermoplastic resin tc+ component without the addition of the epoxy group-containing ethylene polymer concave component cannot be improved. Adhesiveness to various substrates decreases with respect to materials.

The adhesive resin composition of the present invention comprises a thermoplastic copolyester resin (Al and an epoxy group-containing ethylene copolymer (B).
Although an improvement effect is observed even in a composition with 1, it is better to use a composition consisting of one or more of thermoplastic copolyester resin tAl, epoxy group-containing ethylene copolymer FB+, and thermoplastic resin lot. The improvement effect is significant.

That is, by adding one or more thermoplastic resins (C1), the effect of improving extrusion processability, film blocking properties, and adhesion to metals is remarkable.In particular, vinyl aromatic resins It is preferable to use a combination of one selected from hydrocarbon polymers, (meth)acrylic acid ester polymers, and rubbery substances and one selected from ethylene polymers.Vinyl aromatic hydrocarbon polymer The addition of a (meth)acrylic acid ester polymer and a rubbery substance is very effective in achieving the object of the present invention (1B), but if too much is added, the flowability during processing and The strength of the film decreases.Therefore, by further adding an ethylene polymer, flowability and film strength during processing can be appropriately controlled.

The adhesive resin composition of the present invention can be produced using a method of melt-kneading in a -screw extruder, twin-screw extruder, Banbury mixer 1 hot roll, or the like. The components may be mixed simultaneously or in batches. The temperature required for melt cross-ferring is 100 to 250°C, and a sufficient time is 80 seconds to 10 minutes.

The adhesive resin composition of the present invention may contain antioxidants, stabilizers such as ultraviolet absorbers, lubricants, inorganic fillers, surfactants, antistatic agents, copper inhibitors, flame retardants, foaming agents, etc., as necessary. Coloring agents such as pigments, plasticizers, etc. can be added and mixed for use.

The adhesive resin composition of the present invention includes olefinic polymers such as polyethylene, ethylene-unsaturated ester copolymer, polyfuro (14) pyrene, ethylene-α-olefin copolymer, vinyl chloride resin, vinylidene chloride resin,
Copolymers of vinyl chloride and vinyl acetate, vinylidene chloride or acrylic acid ester monomers, vinyl chloride grafted ethylene-vinyl acetate copolymers, chlorinated polyolefins, chlorosulfonated polyolefins, ethylene-
Halogen-containing polymers such as tetrafluoroethylene copolymers and ethylene-hexafluoropropylene copolymers, polyester resins, polyamides, saponified ethylene-vinyl acetate copolymers, ABS resins, polycarbonate resins, and synthetic resins such as polyurethane resins. It can be used to bond metals such as aluminum, iron, nickel, zinc, copper, and chromium, glass, ceramics, paper, and wood. Among these, it has particularly suitable adhesion to both synthetic resins such as soft and hard polyvinyl chloride resins, polyester resins, ABS resins, polycarbonate resins, and polyurethane resins, and metals such as aluminum, iron, lead, and copper. It is something that we have.

In addition, the adhesive resin composition of the present invention can be applied to molding and processing methods used for general plastics (inflation method, T
-Die extrusion method, extrusion lamination method, etc.), it has excellent molding and processability and has little film blocking.

The method for producing a laminate using the adhesive resin composition of the present invention is not particularly limited, and any known technique such as a known lamination method, a coating method, or a combination of both can be applied. For example, the adhesive resin composition of the present invention is interposed between base materials in the form of a film, sheet, powder, pellet, etc., and heated to a temperature higher than the melting temperature,
Alternatively, the adhesive resin composition of the present invention may be coated on the surface of one base material by extrusion coating method, tri-laminate method, coextrusion molding method, or by applying powder or solution and heating. There are methods such as stacking the base material on the other base material, heating the base material to a temperature higher than the melting temperature, and pressing the base material together.

The bonding temperature is generally 1-7°C to 250°C.

The adhesive resin composition of the present invention has extremely industrial significance, as it can be used, for example, as an adhesive layer for metal wrap cables (for communications and power) made of aluminum, lead, copper, etc. that have a sheath layer made of soft polyvinyl chloride resin. It's big.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. In addition, in the examples, physical properties were measured by the following method.

(1) Adhesion between soft polyvinyl chloride resin and aluminum (8-PVO/A/) An adhesive resin composition film (
50 to 60μ), and then connected under the conditions of 180°C x 5 minutes x 101m.
/ was bent at an angle of 1800, and the peel strength was measured at a tensile speed of 10 (1 m/min).

(17) (2) Extrusion processability 201 mφ T-tie processing machine (manufactured by Tanabe Plastics)
The temperature was set at 40° C., and the processability was evaluated based on the adhesion to the cooling roll during molding of a 50 to 60 μm film.

Sticks to the cooling roll and cannot be processed: × Slightly sticks to the cooling roll: Δ No sticking to the cooling roll
20(3) Blocking properties of the film (2) Form into a film of 50 to 60 μm in a forward direction using a T-die processing machine set at 140° C. and wind it into a coil. 1
After being left in the sun, the film was unrolled, and the ease of unwinding was used as a guideline to evaluate the locking property.

Very difficult to unwind: × Somewhat difficult to unwind: △Very easy to unwind
20 Also, the base materials used in the above adhesion test are as follows.

0 Soft aluminum (18) J I 8- H4000, A-105OR-0 (15
0μ tape) 0 Soft polyvinyl chloride resin Polyvinyl chloride resin: Sumilit 5X-18 (manufactured by Sumitomo Chemical) 100 parts by weight, 60 parts by weight of dioctyl terephthalate, parts by weight of calcium carbonate loM, 8 basic lead sulfate (tribase) 8 parts by weight of dibasic lead sulfite and 1 part by weight of dibasic lead sulfite were kneaded for 5 minutes using a roll at 150°C, and then extruded into a sheet having a thickness of two layers.

Examples 1 to 6 and Comparative Examples 1 to 8 As a thermoplastic copolymerized polyester resin, Vylon ■ 80P manufactured by Toyobo ■ (hereinafter referred to as (A-1)): melting point 12
5°C, an epoxy group-containing ethylene copolymer having a melt index of 7 y/10 min, an ethylene copolymer containing 2.2 mol% of glycidyl nucleate and 1.8 mol% of vinyl acetate (hereinafter referred to as (B-1)) ). and,
As the thermoplastic resin, polystyrene 22 (19) manufactured by Nippon Police Co., Ltd., Chiren Kogyo ■, or an ethylene-vinyl acetate copolymer (hereinafter referred to as (C-2)) containing tto weight % of vinyl acetate and a melt index of 65'/10 min. ) were mixed and re-granulated at a temperature of 170° C. using a 20 mm diameter extruder. The obtained adhesive resin composition was molded into a 50 to 60 μm film using a 20 μm T-die processing machine. Table 1 shows the results of an adhesion test using this film.

As a comparative example, Table 1 shows the results of using (A-1) and CB-1> alone.

(21) Examples 7 to 13 and Comparative Example 4 The thermoplastic copolyester resin (A
-1), epoxy group-containing ethylene copolymer (B-1),
Mix thermoplastic resins (C-1) and (C-2),
Re-granulation was performed using a Qmφ extruder at a temperature of 190°C.

Note that (C-1) was prepared by preparing a composition of (A-1) and (0-1) in an amount of 1 part by weight in an 80-diameter extruder, and added in a masterbatch method. The obtained adhesive resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 2.

As a comparative example, the results when CB-1) is not added are shown in the second example.
Shown in the table.

(22) Examples 14 to 17 and Comparative Example 5.6 As a thermoplastic copolymerized polyester resin, Byron "0M900 (hereinafter referred to as (A-2)) manufactured by Toyobo ■: melting point 118 ° C., epoxy group-containing ethylene copolymer As a combination,
Ethylene copolymer (B-1) having a melt index of 79,710 minutes and containing 2.2 mol% of glycidyl methacrylate and 1.8 mol% of vinyl acetate, and polystyrene manufactured by Nippon Polystyrene Kogyo ■ as a thermoplastic resin:
Nisblai 1)s(0-1) and ethylene-vinyl acetate copolymer (C-2) with a vinyl acetate content of 10% by weight and a melt index of 6 g/10 min were mixed, and 80Wφ
Re-granulation was performed using an extruder at a temperature of 190°C. In addition,(
For 0-1), a composition of 1:1 part by weight of (A-2) and ((3-1)) was prepared in advance using an 80 mφ extruder and added in a masterbatch method.The obtained adhesive resin composition was evaluated in the same manner as in Example 1.

The results are shown in Table 8.

As a comparative example, Table 8 shows the results when (A-2) alone and when (B-1) was not added.

(z5) (26) Examples 18 to 22 As the thermoplastic copolymerized polyester resin, (
A-1) 50% by weight, 20% by weight of (B-1) of Example 1 as an epoxy group-containing ethylene copolymer, and thermoplastic resin (0) were combined, and 15% by weight of each was mixed. The pellets were re-granulated at a temperature of 190° C. using an 80 mm diameter extruder. The obtained adhesive resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 4.

Written amendment (method) % formula % 1. Indication of the case 1982 Patent Junso No. 197275 2. Name of the invention Adhesive resin composition 3. Person making the amendment Relationship to the case Patent applicant address Higashi-ku, Osaka City Kitahama 5-15 address name (
2OC+) Sumitomo Chemical Co., Ltd. Representative Sat
Mr. Takeshi 4, Agent Address: Sumitomo Chemical Co., Ltd., 5-15 Kitahama, Higashi-ku, Osaka

Claims (1)

[Claims] An adhesive resin composition comprising a thermoplastic copolymerized polyester resin body) and an epoxy group-containing ethylene copolymer (Bl, or further a thermoplastic resin (01).