WO2021124857A1

WO2021124857A1 - Thermoplastic adhesive composition

Info

Publication number: WO2021124857A1
Application number: PCT/JP2020/044541
Authority: WO
Inventors: 洋人児玉
Original assignee: 株式会社アイセロ
Priority date: 2019-12-20
Filing date: 2020-11-30
Publication date: 2021-06-24

Abstract

The present invention addresses the problem of bonding a resin that is difficult to be bonded. As a means for solving the problem, the present invention provides a thermoplastic adhesive composition that contains the components (A) to (C) described below.　(A) a modified polyolefin resin having a functional group (B) a metal alkoxide and/or a metal chelate (C) a thermoplastic elastomer resin

Description

Thermoplastic adhesive composition

The present invention relates to a thermoplastic adhesive composition.

In recent years, the number of cases where different materials are required to be adhered to each other has increased significantly. For example, in the automobile industry, there are cases where some of the members that were conventionally made of metal materials are made into resin for the purpose of saving energy and improving fuel efficiency, and in the electrical and electronic industry, for the purpose of ease of handling and simplification of the manufacturing process. In addition, the proportion of metal-resin adhesion is increasing, such as the need to reduce the weight of the product without reducing its strength.
Here, it is known that two members are integrated by using an adhesive film which has a property of adhering by heating and is composed of one layer, and constitutes an adhesive layer of such an adhesive film. The composition needs to have sufficient adhesive strength to each of the surfaces of the two members.

For example, Patent Document 1 describes a hot-melt adhesive film containing a tackifier as an essential component in a base resin composed of a modified polyolefin copolymer and a styrene-based thermoplastic elastomer, and is a poorly adhesive resin such as a polycarbonate-based resin. Those having sufficient adhesiveness are also described.
Further, Patent Document 2 describes a heat-adhesive film in which the first surface is a surface made of a polyvinyl butyral resin layer and the second surface, which is the opposite surface of the first surface, is a surface made of a thermoplastic resin. It is described that even two members having completely different properties in terms of adhesiveness to a resin can be reliably integrated with one heat-adhesive film.
Further, Patent Document 3 describes a thermoplastic adhesive film containing a thermoplastic olefin elastomer resin, an acid-modified polypropylene resin, a crystal nucleating agent, and a polypropylene resin, which is a polypropylene resin material or a polypropylene resin material. Those capable of reliably integrating adherends of different materials such as the resin material and the metal material are described.

Japanese Unexamined Patent Publication No. 2012-23306 Japanese Unexamined Patent Publication No. 2016-56243 Japanese Patent No. 6234500

Conventional thermoplastic hot-melt adhesives are usually designed in detail for each target adherend. Therefore, it has not been possible to satisfactorily bond the two materials with one thermoplastic hot-melt adhesive. In particular, it was difficult to bond some so-called general-purpose plastics, engineering plastics, super engineering plastics, especially polyester resins, acrylic resins, and resins having strong polarity.
Further, when the acid-modified polyolefin resin is provided as the primer layer, it is necessary to form an adhesive layer composed of two or more layers together with the adhesive layer.
Further, in order to simply obtain an adhesive film containing acid-modified polypropylene or polyolefin resin, it was necessary to bond the adherend together with the adherend by means such as coextrusion at a high temperature.
Therefore, an object of the present invention is to bond a resin that is difficult to bond.

As a result of diligent studies to solve the above problems, the present inventor has found that the problems can be solved by the following means, and has arrived at the present invention.
1. 1. A thermoplastic adhesive composition containing the following (A) to (C).
(A) Modified polyolefin resin having a functional group (B) Metal alkoxide and / or metal chelate (C) Thermoplastic elastomer resin
2. (D) The thermoplastic adhesive composition according to 1, which contains a crystal nucleating agent.
3. 3. The thermoplastic adhesive composition according to 1 or 2, which contains 0.1 to 15.0 parts by weight of (B) with respect to 100 parts by weight of the total amount of (A), (C) and (D).
4. The thermoplastic adhesive composition according to any one of 1 to 3, wherein (B) is a metal alkoxide and / or a metal chelate of aluminum, titanium, zinc, and zirconium.
5. (B) is selected from aluminum tris (acetylacetonate), tetrastearyl titanate, zinc acetylacetoneate, aluminum isopropyrate, aluminum trisethylacetone acetate, and zirconium-mono, di, tri, tetra-acetylacetoneate. The thermoplastic adhesive composition according to any one of 1 to 4, which is one or more.
6. (A) The thermoplastic adhesive composition according to any one of 1 to 5, wherein the modified polyolefin resin having a functional group is a maleic acid-modified polypropylene resin.
A film comprising the thermoplastic adhesive composition according to 7.1 to 6.
8. Polycarbonate resin, acrylic resin, ABS resin, polyamide resin, polyurethane resin, hard vinyl chloride resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, polyphenylene ether resin, polyphenylsulfone resin, polyethersulfone resin, polyetherimide Resins, polysulfone resins, polyether ether ketone resins, polyimide resins, polyamideimide resins, polyacetal resins, polyarylate resins, liquid crystal polymers, polystyrene resins, resin moldings containing polypropylene resins, moldings containing CFRP, CFRTP, GFRP, GFRTP Two selected from body, aluminum, aluminum alloy, iron, iron alloy, titanium, titanium alloy, magnesium, magnesium alloy, stainless steel molded body, and zinc-plated steel plate, ceramic, slab, and wood (even if they are the same material) A composite obtained by bonding substances (which may be different materials) with a thermoplastic adhesive composition containing the following (A) to (C).
(A) Modified polyolefin resin having a functional group (B) Metal alkoxide and / or metal chelate (C) Thermoplastic elastomer resin

According to the thermoplastic adhesive composition of the present invention, a molded product made of a polyester resin such as polycarbonate, an acrylic resin, an ABS resin, a polyurethane resin, a polyphenylene sulfide resin, a vinyl chloride resin, or the like is adhered to the resin material. It is possible to bond between the resin materials or between different materials such as the resin material and the metal material, and it is possible to obtain a composite composite with an unprecedented adhesive force by these bonding. it can.
Further, when the thermoplastic adhesive composition contains a crystal nucleating agent, it is possible to suppress peeling due to poor solidification due to heat history at the time of heat bonding in the step of adhering the adherend, and the polyester resin or It is possible to reliably integrate the molded bodies of the acrylic resin and the adherends of different materials such as the molded body and the metal material.

Hereinafter, preferred embodiments for carrying out the present invention will be described, but the scope of the present invention is not limited to these embodiments.

The thermoplastic adhesive composition of the present invention is used as a hot melt adhesive.
Then, it contains (A) a modified polyolefin resin having a functional group, (B) a metal alkoxide and / or a metal chelate, and (C) a thermoplastic elastomer resin. Further, (D) a crystal nucleating agent can be contained.

(A) Modified Polyolefin Resin Having a Functional Group The modified polyolefin resin having a functional group is a polypropylene resin, an ethylene resin, or an ethylene-propylene resin. Specifically, propylene and / or ethylene, unsaturated carboxylic acids such as maleic acid (including maleic anhydride), itaconic acid, fumaric acid, oleic acid, acrylic acid, and methacrylic acid, imine groups, and imide groups. Examples thereof include copolymers with compounds having an amide group, urethane group, ester group and the like, and polypropylene-based resins graft-polymerized with compounds such as these unsaturated carboxylic acids. Among them, a propylene-ethylene copolymer or a copolymer of polypropylene and maleic acid (or maleic anhydride), particularly a resin obtained by graft-polymerizing maleic acid (or maleic anhydride) with any of these resins is preferable. .. Examples of the acid-modified polypropylene-based resin include DPA manufactured by DuPont, Admer manufactured by Mitsui Chemicals, and Youmex manufactured by Sanyo Chemicals.
Among them, the MFR value (230 ° C./2.16 kg) of the modified polyolefin resin having the (A) functional group was 0.1 to 150 g / 10 min. Is.
The blending amount of the modified polyolefin resin having the (A) functional group in 100 parts by weight of the total amount of (A), (C) and (D) is preferably 15.0 to 98.5 parts by weight, more preferably 20 parts by weight. It is 0.0 to 75.0 parts by weight, more preferably 30.0 to 70.0 parts by weight.

(B) Metal alkoxide and / or metal chelate The metal alkoxide and metal chelate used in the present invention include acetylacetonate metal compounds, stearyl-based metal compounds, metal alkylate-based compounds and / or acetoacetate-based metal compounds. As the metal, aluminum, titanium, zirconium, zinc and the like are used. However, aliphatic and aromatic monocarboxylic acid metal salts are not preferable.
Of these, aluminum tris (acetylacetoneate), zinc acetylacetonate, tetrastearyl titanate, aluminum isopropyrate, aluminum trisethylacetone acetate, zirconium-mono, di, tri, and tetra-acetylacetoneate are preferable.
The blending amount of (B) metal alkoxide and / or metal chelate is preferably 0.1 to 15.0 parts by weight, more preferably, with respect to 100 parts by weight of the total amount of (A), (C) and (D). Is 0.2 to 10.0 parts by weight, more preferably 0.3 to 7.0 parts by weight.

(C) Thermoplastic Elastomer Resin The (C) thermoplastic elastomer resin used in the present invention preferably has a fusion enthalpy of 35 J / g or less as measured by a differential scanning calorimeter.
When the melting enthalpy is 35 J / g or less, it becomes particularly easy to get wet with the surface of the adherend when heated for adhesion, and improvement in work efficiency can be expected.
Further, by using the elastomer under this condition, the elasticity of the elastomer makes it difficult for the elastomer to peel off from the adherend due to the peeling stress after bonding, and the adhesive strength can be improved.
Examples of such thermoplastic elastomer resins include polyolefin resins, polystyrene resins, vinyl chloride resins, polyamide resins, polyurethane resins, polyester resins, acrylic resins, polybutadiene resins, fluororesins, and dynamic resins. A vulture-based resin can be mentioned. Here, polyolefin-based materials are generally superior to polystyrene-based products in terms of cost, light weight, and heat resistance, and polystyrene-based products are excellent in flexibility and resilience.
Further, a type (reactor type) in which an uncrosslinked or partially crosslinked ethylene-propylene rubber or ethylene-propylene-diene rubber is dispersed as a soft segment in a homozygous or random hard segment of polypropylene during the polymerization of the hard segment. A type in which a hard segment of a homo or random polypropylene and a soft segment of an uncrosslinked or partially crosslinked ethylene-propylene rubber or ethylene-propylene-diene rubber are dynamically cross-linked during kneading, a propylene-butene copolymer, propylene. -Ethylene-butene copolymer, propylene-butadiene copolymer, propylene-ethylene-butadiene copolymer, syndiotactic polypropylene, α-olefin copolymer and the like can be mentioned.
Examples of the thermoplastic elastomer resin include PRIME TPO series (R110MP, R110E, T310E, M142E) manufactured by Prime Polymer Co., Ltd., Thermolan manufactured by Mitsubishi Chemical Corporation, and the like.
Among the thermoplastic elastomers, as a polyolefin type, specifically, the ENGAGE series manufactured by Dow Chemical (8003, 8100, 8130, 8137, 8150, 8180, 8200, 8207, 8400, 8407, 8401, 8402, 8411, 8440, 8450, 8452, 8480, 8540, 8842, 7270, 7277, 7447, 7467), INFUSE series (9000, 9007, 9100, 9500, 9507, 9530, 9807, 9817), or ESPOLEX TPE Series (3675) manufactured by Sumitomo Chemicals. , 3785, 3775, 3858, 3255, 901, 4675, 4785, 4855, 820, 822, 821), or Mitsubishi Chemicals ZELAS series (MC717R4, MC721AP), Thermolan (dynamic cross-linking type, low hardness type, cross-linked Type Medium / High Strength Series) or LEOSTOMER SE Series (LQR7382Q, LQR7382P, LQR7382N, LQR7511N) manufactured by RIKEN TECHNOS, Toughmer DF Series (DF605, DF610, DF640, DF110, DF710, DF740, DF7350) manufactured by Mitsui Chemicals (A1085S, A-4085S, A-20805S, A-4090S, A-20090S), PN series (PN-2070, PN-3560, PN-2060, PN-20300), XM series (XM5070, XM-5080, XM) -5090, XM-7070, XM-7080, XM-7090) and the like.
Among the thermoplastic elastomers, as polystyrene-based products, specifically, Asahi Kasei's Tough Tech H series (H1041, H1041G, H1043, H1051, H1052, H1053, H1062, H1081, H1221, H1517, H1521), M series (M1943, M1911). , M1913, MP10), P series (P1083, P1500, P5051, P2000), Mitsubishi Chemical Corporation Tefablock SJ series (SJ4300C, SJ5300C, SJ6300C, SJ7300C, SJ8300C, SJ9300C).
Among the thermoplastic elastomers, polyester-based ones, specifically, Tefablock A series and B series manufactured by Mitsubishi Chemical Corporation.
The MFR value (230 ° C./2.16 kg) of this thermoplastic elastomer resin is preferably 0.1 to 150 g / 10 min. Is.

The blending amount of the (C) thermoplastic elastomer resin in 100 parts by weight of the total amount of (A), (C) and (D) is preferably 1.5 to 85.0 parts by weight, more preferably 25.0. It is ~ 80.0 parts by weight, more preferably 30.0 to 70.0 parts by weight. When the weight is other than 1.5 to 85.0 parts by weight, the adhesive strength may decrease.

(D) Crystal Nucleating Agent In the present invention, the compounding of the (D) crystal nucleating agent is not essential, but when compounding, as the crystal nucleating agent that can be used, known ones that are particularly effective for polypropylene resins are used. It can be used, and examples thereof include dibenzylidene sorbitol derivatives, phosphate ester metal salts, benzoate metal salts, piperin metal salts, rosin metal salts, quinacridone, cyanine blue, talc, calcium carbonate, naphthalene type, and amide type.
The blending amount of the crystal nucleating agent (D) in 100 parts by weight of the total amount of (A), (C) and (D) is preferably 0.01 to 10.00 parts by weight, more preferably 0.05 to 8 parts by weight. It is 0.000 parts by weight, more preferably 0.08 to 5.00 parts by weight. When the amount added is other than 0.01 to 10.00 parts by weight, the adhesive strength may decrease. Further, when the crystal nucleating agent is used particularly in this range, the thermoplastic adhesive composition can be used to be melted and solidified immediately after the adherend is adhered, so that the bonding process can be accelerated. It can be carried out.
Examples of the crystal nucleating agent include crystal nucleating agent MB (PF430V manufactured by SunAllomer Ltd.), gelol manufactured by Shin Nihon Rika, NJester NU-100, and ADEKA STAB manufactured by Adeka.

The thermoplastic adhesive composition of the present invention contains near-infrared absorbing materials such as carbon black, graphene, graphite, diimonium salt, aminium salt, cyanine compound, phthalocyanine compound, dithiol metal complex, naphthoquinone compound, azo compound and talc. It can be contained, and as a result, it can be bonded by irradiating it with infrared rays such as laser light and heating it.
However, it is not necessary to contain an epoxy compound or an isocyanate compound.

For the purpose of enhancing the adhesion prevention when the thermoplastic adhesive composition of the present invention is formed into a film, talc, calcium carbonate, sepiolite, boehmite, bentonite, silica, mica, kaolin, diatomaceous earth, titanium oxide, zinc oxide, etc. It is possible to contain glass beads, inorganic fillers such as metal fibers such as aluminum, nickel and copper, and organic fillers such as polymer beads.

A tackifier may or may not be added to the thermoplastic adhesive composition of the present invention. Further, chlorinated polyolefin, chlorinated modified polyolefin, epoxy resin, styrene resin and plasticizer may or may not be added.

The thermoplastic adhesive composition of the present invention is previously formed into a film shape of an arbitrary thickness, and this film is sandwiched between two adherends and heat-melted to be bonded, or the melted thermoplastic adhesive composition. Can be sandwiched between two adherends and pressed to adhere.
Further, it is also possible to heat and melt the thermoplastic adhesive composition having an arbitrary shape instead of the film shape and supply it to the surface of the adherend from a dispenser or the like.
As a modification of the film shape, it is possible to obtain a multilayer film or a multilayer sheet in which the layer made of the thermoplastic adhesive composition of the present invention is provided on one side or both sides of the base material layer.
The base material layer is adopted for the purpose of adjusting the physical properties and thickness of the thermoplastic adhesive composition of the present invention such as bending strength, stiffness, heat resistance, etc., and is made of polypropylene-based resin, polyethylene terephthalate-based resin, or polyamide-based resin. Resin can be used.

(Production method)
The thermoplastic adhesive composition of the present invention can be obtained by known melt extrusion molding, and a film can be formed by extracting and cooling and solidifying the resin composition from a T die, a circular die or the like. Further, for the purpose of improving the surface wettability of the thermoplastic adhesive composition, it is possible to apply corona discharge treatment, plasma discharge treatment, UV / ozone treatment, flame treatment, etc. on the surface of the thermoplastic adhesive composition. Is.

(Adhesion method)
The thermoplastic adhesive composition of the present invention preferably starts melting at 100 to 250 ° C. When the surface of the adherend is made of a thermoplastic resin, the bonding temperature, which is the heating temperature at the time of bonding, is (melting temperature of the thermoplastic resin on the surface of the adherend)> (bonding temperature) ≧ (melting temperature of the modified polypropylene resin)- By setting the melting temperature to 20 (however, the melting temperature is a value measured by a differential scanning calorimeter), deformation of the adherend can be suppressed and adhesion can be performed.

(Tensile shear strength)
The adhesive strength of the thermoplastic adhesive composition of the present invention is determined by a strong elongation tester (AG-1S manufactured by Shimadzu Corporation) at room temperature under a tensile speed of 100 mm / min. Is measured and obtained. In order to sufficiently bond the adherend, the tensile shear strength needs to be 3 MPa or more, more preferably 5 MPa or more, and even more preferably 7 MPa or more.

(Use)
The use of the thermoplastic adhesive composition of the present invention is not particularly limited, and is used for adhering two adherends whose at least one adherend is a resin or an inorganic substance to each other.
The adherend at this time is made of polyester resin, polycarbonate resin, acrylic resin, ABS resin, polyamide resin, polyurethane resin, polyphenylene sulfide resin, hard or soft vinyl chloride resin, or the like, and if necessary, fibers such as glass fibers. Alternatively, these resin molded bodies filled with a filler may be used. In addition, metals and alloys such as aluminum, aluminum alloys, iron, iron alloys, nickel, nickel alloys, zinc, zinc alloys, titanium, titanium alloys, magnesium alloys, copper and copper alloys, and inorganic substances such as ceramics, glass and carbon. Is most suitable for adhering as an alloy. Among these adherends, the same type of adherends may be adhered to each other, or different materials may be adhered to each other.
In particular, it is possible to bond a combination of molded bodies of materials that have been difficult to bond and integrate in the past. Such combinations include polycarbonate resin, acrylic resin, ABS resin, polyamide resin, polyurethane resin, hard vinyl chloride resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, polyphenylene ether resin, polyphenyl sulfone resin, and polyether. Sulfur resin, polyetherimide resin, polysulfone resin, polyetheretherketone resin, polyimide resin, polyamideimide resin, polyacetal resin, polyarylate resin, liquid crystal polymer, polystyrene resin, resin molded body containing polypropylene resin, CFRP (carbon fiber reinforced) Molds containing (plastic), CFRTP (carbon fiber reinforced thermoplastic), GFRP (glass fiber reinforced plastic), GFRTP (glass fiber reinforced thermoplastic), aluminum, aluminum alloys, iron, iron alloys, titanium, titanium alloys, Examples include magnesium, magnesium alloys, stainless steel moldings, and combinations of two selected from zinc-plated steel plates, ceramics, slabs, and wood (the two may be the same or different materials).
Then, it is preferable that these combinations are made into a composite formed by bonding with a thermoplastic adhesive composition containing the following (A) to (C).
(A) Modified polyolefin resin having a functional group (B) Metal alkoxide and / or metal chelate (C) Thermoplastic elastomer resin Further, the thermoplastic adhesive composition of the present invention is bonded to the above-mentioned footwear. It can be used to manufacture interior parts for automobiles, footwear such as shoes and sandals, furniture, housings for smartphones / tablet terminals / PCs, housings for home appliances, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples. Examples show one embodiment of the invention, and the present invention is not limited thereto.

(Example 1)
As shown in Table 1, 40 parts by weight of maleic anhydride-modified polypropylene, 60 parts by weight of polypropylene elastomer, and 0.5 parts by weight of a cross-linking agent (aluminum tris (acetylacetonate)) were added to Laboplast Mill (manufactured by Toyo Seiki Co., Ltd.). ) At 200 ° C., 50 rpm for 5 minutes to obtain a thermoplastic adhesive composition.

(Examples 2 to 18, Comparative Examples 1 to 6)
The conditions described in Example 1 were replaced with the conditions described in Table 1, and Examples 2 to 18 and Comparative Examples 1 to 6 were performed. In addition, the numerical value in the column of each component of all Examples and Comparative Examples is a part by weight.

Maleic anhydride-modified polypropylene (MFR 5.7 g / 10 minutes (230 ° C, 2.16 kg), density 0.89 g / cm ³ )
Polypropylene elastomer (MFR 1.5 g / 10 minutes (230 ° C / 2.16 kg), density 0.88 g / cm ³ )
Polyolefin-based elastomer 1 (MFR 7.0 g / 10 minutes (230 ° C / 2.16 kg), density 0.87 g / cm ³ )
Polyolefin-based elastomer 2 (MFR 6.0 g / 10 minutes (230 ° C / 2.16 kg), density 0.89 g / cm ³ )
Polystyrene elastomer 1 MFR 6.0 g / 10 minutes (230 ° C / 2.16 kg, density 0.89 g / cm ³
Polystyrene elastomer 2 MFR 4.5 g / 10 minutes (230 ° C / 2.16 kg), density 0.89 g / cm ³
Random polypropylene (MFR 1.2 g / 10 minutes (230 ° C / 2.16 kg), density 0.89 g / cm ³ )
Crystal nucleating agent MB
(MFR 4.0 g / 10 minutes (230 ° C / 2.16 kg), density 0.89 g / cm ³ ) Contains 10% dibenzylidene sorbitol.

<Measurement of tensile shear strength>
In Examples and Comparative Examples, the tensile shear strength was measured under the conditions shown in the following tensile shear strengths 1 to 10, and it was judged that 3 MPa or more was effective.
Tensile shear strength 1:
The thermoplastic adhesive composition was melt-pressed with a hot plate press (manufactured by Shinto Kogyo Co., Ltd.) at 200 ° C. and 14 kN to obtain a film having a thickness of 80 to 120 μm. The obtained film was cut into a size of 20 mm × 10 mm.
Upper adherend: Polycarbonate resin (PC) (3 mm thickness x 20 mm width x 75 mm length) and lower adherend: Galvanized steel plate (GA) (0.8 mm thickness x 20 mm width x 75 mm length) The above-mentioned thermoplastic adhesive film is arranged between them to obtain a three-layer structure, which is subjected to thermal pressure bonding at an upper side: 50 ° C., a lower side: 180 ° C., 0.5 kN with a hot plate press machine. This was done to obtain an adhesive sample.
The portion of the adhesive sample bonded by the adhesive film is 20 mm in the width direction and 10 mm in the length direction of the sample.
The obtained sample was measured for tensile shear strength (MPa) under room temperature conditions with a strong elongation tester (AG-1S manufactured by Shimadzu Corporation).
The unbonded ends of the upper and lower adherends were gripped with a jig up to 50 mm from that end. The lower adherend was fixed, and the jig holding the upper adherend was pulled upward at a tensile speed of 100 mm / min.
The strength at the time when the bonded portion was broken, one of the adherends was broken, or the interface was peeled off at the bonded portion was obtained, and this was divided by the bonding area to obtain the tensile shear strength (MPa).

Tensile shear strength 2:
The tensile shear strength (MPa) was measured under the same conditions as the tensile shear strength 1, except that the upper adherend was made of ABS resin (ABS) (2 mm thick × 20 mm width × 75 mm length).

Tensile shear strength 3:
The upper adherend was made of acrylic resin (3 mm thick × 20 mm width × 75 mm length), and heat pressure bonding was performed at an upper side: 150 ° C., a lower side: 200 ° C., 0.5 kN with a hot plate press machine. In other cases, the tensile shear strength (MPa) was measured under the same conditions as the tensile shear strength 1.

Tensile shear strength 4:
The tensile shear strength (MPa) was measured under the same conditions as the tensile shear strength 1, except that the upper adherend was a glass fiber-containing polyamide resin (GFNy) (3 mm thickness × 20 mm width × 75 mm length).

Tensile shear strength 5:
The tensile shear strength (MPa) was measured under the same conditions as the tensile shear strength 1, except that the upper adherend was a polyurethane resin (PU) (0.35 mm thickness × 20 mm width × 75 mm length).
However, the tensile shear strength could not be measured because the polyurethane resin itself broke before the bonded portion broke due to the pulling of the polyurethane during the measurement. However, from this result, it was understood that the polyurethane resin body adheres with stronger cohesive force and adhesive force at the time of tension.

Tensile shear strength 6:
The upper adherend is polycarbonate resin (PC) (3 mm thickness x 20 mm width x 75 mm length), and the lower adherend: stainless steel plate (SUS304) (SUS) (1.6 mm thickness x 20 mm width x 75 mm length). The tensile shear strength (MPa) was measured under the same conditions as the tensile shear strength 1.

Tensile shear strength 7:
The tensile shear strength (MPa) was measured under the same conditions as the tensile shear strength 1, except that the lower adherend was aluminum (Al) (A5052P) (1.6 mm thickness × 20 mm width × 75 mm length).

Tensile shear strength 8
The tensile shear strength (MPa) was measured under the same conditions as the tensile shear strength 1, except that the upper adherend was a hard vinyl chloride resin (vinyl chloride) (2 mm thick × 20 mm width × 75 mm length).

Tensile shear strength 9
The upper adherend is polybutylene terephthalate resin (PBT) (2 mm thickness x 20 mm width x 75 mm length), the lower adherend is polyphenylene sulfide resin (PPS) (2 mm thickness x 20 mm width x 75 mm length), and a hot plate. The tensile shear strength (MPa) was measured under the same conditions as the tensile shear strength 1, except that the press machine temperature was set to 180 ° C. on both the upper and lower sides.

Tensile shear strength 10
The upper adherend is polypropylene resin (PP) (3 mm thickness x 20 mm width x 75 mm length), the lower adherend is polycarbonate resin (PC) (3 mm thickness x 20 mm width x 75 mm length), and the hot plate press temperature. The tensile shear strength (MPa) was measured under the same conditions as the tensile shear strength 1 except that the temperature was set to 160 ° C. on both the upper and lower sides.

According to each example, it was possible to bond to various adherends so as to have a sufficiently strong tensile shear strength.
On the other hand, according to (B) Comparative Examples 1, 4, 5 and 6 containing no metal alkoxide and / or metal chelate, the adhesion could not be sufficiently strong. Similarly, in Comparative Examples 2 and 3 containing (A) a modified polyolefin resin having a functional group and (C) a thermoplastic elastomer resin, sufficient strong adhesion could not be achieved.

In particular, the thermoplastic adhesive composition of the present invention enables adhesion of polycarbonate resin and acrylic resin molded bodies by heating and pressurizing with a hot plate press, ultrasonic waves, high frequencies, lasers, and the like. It can be used for adhesive molding of automobiles, interior / exterior parts for automobiles, building material parts, smartphone / home appliance housings and parts.

Claims

A thermoplastic adhesive composition containing the following (A) to (C):
(A) Modified polyolefin resin having a functional group,
(B) Metal alkoxide and / or metal chelate,
(C) Thermoplastic elastomer resin.
(D) The thermoplastic adhesive composition according to claim 1, which contains a crystal nucleating agent.
The thermoplastic adhesive composition according to claim 1 or 2, which contains 0.1 to 15.0 parts by weight of (B) with respect to 100 parts by weight of the total amount of (A), (C) and (D). Stuff.
The thermoplastic adhesive composition according to any one of claims 1 to 3, wherein (B) is a metal alkoxide and / or a metal chelate of aluminum, titanium, zinc, and zirconium.
(B) is selected from aluminum tris (acetylacetonate), tetrastearyl titanate, zinc acetylacetoneate, aluminum isopropyrate, aluminum trisethylacetone acetate, and zirconium-mono, di, tri, tetra-acetylacetoneate. The thermoplastic adhesive composition according to any one of claims 1 to 4, which is one or more of them.
(A) The thermoplastic adhesive composition according to any one of claims 1 to 5, wherein the modified polyolefin resin having a functional group is a maleic acid-modified polypropylene resin.
A film comprising the thermoplastic adhesive composition according to claims 1 to 6.
Polycarbonate resin, acrylic resin, ABS resin, polyamide resin, polyurethane resin, hard vinyl chloride resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, polyphenylene ether resin, polyphenylsulfone resin, polyethersulfone resin, polyetherimide Resins, polysulfone resins, polyether ether ketone resins, polyimide resins, polyamideimide resins, polyacetal resins, polyarylate resins, liquid crystal polymers, polystyrene resins, resin moldings containing polypropylene resins, moldings containing CFRP, CFRTP, GFRP, GFRTP Two selected from body, aluminum, aluminum alloy, iron, iron alloy, titanium, titanium alloy, magnesium, magnesium alloy, stainless steel molded body, and zinc-plated steel plate, ceramic, projecting plate, wood (these two are the same material) A composite in which the substances (which may be different materials) are bonded by a thermoplastic adhesive composition containing the following (A) to (C):
(A) Modified polyolefin resin having a functional group,
(B) Metal alkoxide and / or metal chelate,
(C) Thermoplastic elastomer resin.