JP2012067161A - Adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hot melt type laminate which does not drop out by vibration or shaking on transportation, when laminated on a thermoplastic resin molded article.SOLUTION: There is provided an adhesive resin composition which is modified by a process of melt-kneading in the presence of a radical polymerization initiator (A) 100 pts.wt. of a polyolefin-based resin, (B) polar group-containing vinyl monomers and (C) aromatic vinyl monomers, and is compound with (D) a tackifier to 100 pts.wt. of the modified polyolefin resin, wherein the content of the polar group-containing vinyl monomers is 0.1-5 wt.% based on 100 pts.wt. of the modified polyolefin resin.

Description

  The present invention has an excellent initial adhesiveness that does not fall off from the molded product due to vibration, impact, and shaking up to the bonding process when a film-shaped hot melt is disposed on a thermoplastic resin molded product, and an inexpensive film-shaped hot melt adhesive property. Regarding the sheet.

  Thermoplastic resins such as thermoplastic elastomers, olefin polymers, vinyl polymers, and engineering plastics are excellent in physical properties, moldability, surface properties, etc., so they are used in fields such as automobiles, electrical / electronics, architecture, and miscellaneous goods. Therefore, it is molded and used by processing methods such as extrusion molding, injection molding, and press molding. These molded products are often combined by bonding a plurality of molded products in order to obtain products having a desired shape, or to enhance performance and diversify functions. There is a need for a heat-melt type (hot melt type) adhesive that is simple and excellent in adhesive strength. In recent years, not only adhesion of the same kind of thermoplastic resin but also adhesion of different types of thermoplastic resin or thermoplastic resin to metal or glass, metal to metal, or metal to glass has been required. Patent Document 3 is a method of applying an adhesive or curable adhesive that requires a hot melt applicator in order to attach importance to the adherend, and is a molten adhesive or liquid at room temperature. The method of directly applying the adhesive to the adherend has been adopted, and dedicated equipment for applying the adhesive is required or because it is liquid, it is liquid dripping, uneven film thickness, drying and curing There may be problems such as taking time.

JP-A-2004-284575 (Patent No. 409972) JP 2005-272545 A JP-A-2001-226535 (Patent No. 4155589)

  As a general method for bonding thermoplastic resins, vibration welding, hot plate welding, ultrasonic welding, hot melt adhesive, and two-component curable coating are used. These fusion and adhesion methods require dedicated equipment and molds and applicators (coating equipment) tailored to the design of the molded product, and require millions to tens of millions of initial investment. In the case of vibration welding, hot plate welding, and ultrasonic welding, it is difficult to reduce the weight because the molded product itself is melted and the bonded portion needs to be designed thick. These welding methods are effective only for adhesion between resins having good compatibility, and different types of thermoplastic resins cannot be fused. Also, when applying conventional hot-melt adhesives or two-component curable adhesives, it is possible to bond different types of thermoplastic resins, but it takes time to dry and solidify, and the cycle of the bonding process It is difficult to shorten the time. In addition, there have been reports from users of problems such as dropping off by vibration, impact, shaking, etc. during transportation to the bonding process after placing the hot melt film on the bonding site. There are many requests for applications that require design properties, such as automobile interiors, house interiors, and home appliances, as molding applications, and in order not to impair the design properties, other fusion and bonding technologies are considered effective. It is done.

  As a result of intensive investigations in view of the above-described present situation, the present inventors mixed a modified polyolefin resin made of a polyolefin resin and modified with a polar group-containing vinyl monomer and a tackifier resin into a film shape. Formed and then laminated with a multilayer structure with a metal film sandwiched in close contact with the thermoplastic molded product, and found that it does not fall off due to vibration, impact, shaking, etc. during transportation, and completed the following invention It came to do.

  1) Adhesive resin composition processed into a film, wherein the film has a tackiness of 3/32 inch or more in a ball tack test according to JIS Z0237 (with or without an inclination angle of 5 °), and An adhesive sheet, wherein the film does not fall when the molded product is turned upside down when the film is attached to a thermoplastic molded product.

  2) The adhesive resin composition comprises (B) a polar group-containing vinyl monomer and (C) an aromatic vinyl monomer in the presence of a radical polymerization initiator with respect to (A) 100 parts by weight of a polyolefin-based resin. 1) to 50 parts by weight of a tackifier having a softening point of 180 ° C. or lower with respect to 100 parts by weight of a modified polyolefin resin modified by the step of melt-kneading Adhesive sheet.

  3) The adhesive sheet according to 1) to 2), wherein the polyolefin resin of (A) is 100 to 80 parts by weight of a polypropylene resin in which a propylene unit is a majority amount and 0 to 20 parts by weight of polypropylene.

  4) The adhesive sheet according to 1) to 3), wherein the (C) polar group-containing vinyl monomer is glycidyl methacrylate or maleic anhydride.

  5) The adhesive composition includes (D) a tackifier, and the tackifier is selected from a rosin resin, a terpene phenol resin, a terpene resin, an aromatic hydrocarbon-modified terpene resin, a petroleum resin, and a hydrogenated petroleum resin. The adhesive sheet according to 1) to 4), wherein the adhesive sheet is at least one tackifier.

  6) Adhesive resin characterized by being a laminate having a three-layer structure in which a metal foil or plate having a thickness of 1 to 200 μm is sandwiched and laminated on the adhesive sheet according to any one of 1) to 5) Composition laminate.

  7) The adhesive resin composition according to 6), wherein the metal foil or plate is a metal such as gold, silver, copper, iron, tin, lead, aluminum, or silicon and / or an alloy containing these metals. Product laminate.

  8) A method of using the adhesive resin composition laminate, wherein electromagnetic induction heating is used to fuse the laminate according to any one of 6) to 7) and the adherend.

  The adhesive resin composition laminate of the present invention can ensure excellent adhesion to a thermoplastic resin molded article substrate, and the adhesive laminate falls due to vibration during transportation to the adhesion process. There is to not. In addition, the adhesive resin composition laminate after fusion exhibits, of course, the same material as each other and an excellent adhesive force between different materials.

Details of the present invention will be described below.
The present invention is an adhesive sheet processed into a film shape, and the sheet has a tackiness of 3/32 inches or more in a ball tack test according to JIS Z0237 (with or without an inclination angle of 5 °), and When the film is attached to a thermoplastic molded product, the adhesive sheet is characterized in that the film does not fall even if the molded product is inverted. Originally, the tilt angles in the ball tack test are 20 °, 30 °, and 40 °. However, in the case of a slightly sticky material such as the adhesive resin composition of the present invention, the tilt angle may be relaxed for evaluation. . When evaluating with a run-up, the run-up path is defined as 100 mm and JIS Z0237. Regarding the evaluation method, the ball is rolled on the film surface, and the maximum size at which the ball stops on the film surface for 5 seconds or more is recorded.

  In addition, the evaluation of sticking to a molded product (injection molded body) is our original evaluation method. When the film is cut into a 1cm x 10cm strip and pasted by hand, the molded product is turned upside down. This is to check whether the attached film does not fall.

<< About polyolefin resin >>
Examples of the (A) polyolefin resin used in the present invention include polyethylene, polypropylene, poly-1-butene, polyisobutylene, random copolymer or block in any ratio of propylene and ethylene and / or 1-butene. Copolymers, ethylene-propylene-diene terpolymers having a diene component of 50% by weight or less in all ratios of ethylene and propylene, copolymers of polymethylpentene, cyclopentadiene and ethylene and / or propylene, etc. And a cyclic copolymer, a random copolymer of ethylene or propylene and 50% by weight or less of a vinyl compound, a block copolymer, and the like. Among them, polypropylene, polyethylene, polyisobutylene, and ethylene-propylene copolymer are preferable, and ethylene having a majority of propylene units in that heat resistance, rigidity, high impact resistance, and industrial scale can be produced at low cost. A propylene copolymer or a mixture of an ethylene-propylene copolymer and polypropylene is more preferable. The ethylene-propylene copolymer having a majority of propylene units means a copolymer containing 50% by weight or more of propylene units.

  In addition, among the polyolefin resins listed above, if the copolymer has a Shore A hardness of 80 or less, even if it is other than an ethylene-propylene copolymer having a majority propylene unit, it provides tackiness. It is preferable because it is easy to do.

  In the present application, the ethylene-propylene copolymer having a majority of propylene units is 100 to 80 parts by weight, and when the blending amount is less than 80 parts by weight, the adhesive resin composition processed into a film form becomes a molded product. Since it falls, it is not preferable. Furthermore, the amount of polypropylene is 0 to 20 parts by weight. If the blending amount exceeds 20 parts by weight, it is not preferable because it falls from the molded product as described above.

  Regarding the propylene component in the polyolefin resin, it is preferable that the propylene unit is a majority amount in that radicals are easily generated in the polyolefin resin. The majority amount here means that the propylene component with respect to the polyolefin resin is 50% by weight or more.

Moreover, the polyolefin resin in which the polar group was introduce | transduced can also be used at the point which is compatible with the unsaturated carboxylic acid monomer which has a polar group. Specific examples of polyolefin resins having polar groups introduced include ethylene / vinyl chloride copolymers, ethylene / vinylidene chloride copolymers, ethylene / acrylonitrile copolymers, ethylene / methacrylonitrile copolymers, ethylene / vinyl acetate. Copolymer, ethylene / acrylamide copolymer, ethylene / methacrylamide copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / maleic acid copolymer, ethylene / methyl acrylate copolymer Copolymer, ethylene / ethyl acrylate copolymer, ethylene / isopropyl acrylate copolymer, ethylene / butyl acrylate copolymer, ethylene / isobutyl acrylate copolymer, ethylene / 2-ethylhexyl acrylate copolymer, ethylene / Methyl methacrylate copolymer, Ethylene / Ethyl methacrylate copolymer, ethylene / isopropyl methacrylate copolymer, ethylene / butyl methacrylate copolymer, ethylene / isobutyl methacrylate copolymer, ethylene / 2-ethylhexyl methacrylate copolymer, ethylene / anhydrous malein Acid copolymer, ethylene / ethyl acrylate / maleic anhydride copolymer, ethylene / acrylic acid metal salt copolymer, ethylene / methacrylic acid metal salt copolymer, ethylene / vinyl acetate copolymer, or saponified product thereof Ethylene / α-olefin / ethylene / vinyl propionate copolymer, ethylene / glycidyl methacrylate copolymer ethylene / ethyl acrylate / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, etc. Polarity such as vinyl monomer copolymer Group-containing ethylene copolymers; chlorinated polyolefins such as chlorinated polypropylene and chlorinated polyethylene. Also, a polyolefin obtained by graft polymerization of a polar group-containing vinyl monomer can be used. These polar group-introduced polyolefin resins may be used alone or in combination.
These polyolefin resins may be in the form of particles or pellets, and the size and shape are not particularly limited.

  << Polar group-containing vinyl monomer >> Examples of the polar group contained in the polar group-containing vinyl monomer include carboxylic acid groups, carboxylic acid anhydride groups, carboxylic acid ester groups, carboxylic acid halide groups, and carboxylic acids. Examples include an amide group, a carboxylic acid imide group, a carboxylic acid group, a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid chloride group, a sulfonic acid amide group, a sulfonic acid group, an epoxy group, an amino group, and an oxazoline group. Of these, a carboxylic acid group, a carboxylic acid anhydride group, and a carboxylic acid ester group are preferable.

  The polar group-containing vinyl monomer used in the present invention is not particularly limited, but is preferably an unsaturated carboxylic acid containing the above polar group and / or a derivative thereof. As unsaturated carboxylic acid or its derivative (s), unsaturated mono- or dicarboxylic acid, or these derivatives are mentioned, for example. Specific examples of these derivatives include anhydrides, esters, halides, amides, imides, and salts of carboxylic acids. Specific examples of unsaturated mono- or dicarboxylic acids include acrylic acid, methacrylic acid, maleic acid, endo-bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid (endic acid), fumaric acid Tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid and the like. Specific examples of the unsaturated carboxylic acid derivative include maleenyl chloride, maleimide, maleic anhydride, endic acid anhydride, methyl acrylate, acrylic acid amide, methyl methacrylate, glycidyl methacrylate, methacrylic acid amide, citraconic anhydride, Itaconic anhydride, nadic anhydride, monomethyl maleate, dimethyl maleate, monomethyl fumarate, dimethyl fumarate and the like can be mentioned. Among these unsaturated carboxylic acids or derivatives thereof, preferably acrylic acid, methacrylic acid, maleic anhydride, glycidyl methacrylate, and more preferably maleic anhydride, glycidyl methacrylate, from a low cost point, modified Glycidyl methacrylate is particularly preferred because it can be easily removed in the subsequent drying step. These may be used individually by 1 type, and may be used in combination of 2 or more types.

  (B) The addition amount of the polar group-containing vinyl monomer is preferably 0.2 to 100 parts by weight and more preferably 0.5 to 50 parts by weight with respect to 100 parts by weight of the polyolefin resin. preferable. If the amount added is too small, the adhesiveness tends not to be improved sufficiently, and if the amount added is too large, a by-product of free polymer that does not contribute to grafting tends to increase, and it is obtained as a resin composition having a suitable shape and appearance. There is a tendency not to.

<< About the aromatic vinyl monomer >>
(C) Although it does not restrict | limit especially as an aromatic vinyl monomer, Preferably it is C4-C20, More preferably, it is a C6-C15 aromatic vinyl monomer. For example, styrene; methyl styrene such as o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, β-methyl styrene, dimethyl styrene, trimethyl styrene; o-chloro styrene, m-chloro Chlorostyrene such as styrene, p-chlorostyrene, α-chlorostyrene, β-chlorostyrene, dichlorostyrene, trichlorostyrene; o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene, tribromostyrene, etc. Bromostyrene; fluorostyrene such as o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, difluorostyrene, trifluorostyrene; o-nitrostyrene, m-nitrostyrene, p-nitrostyrene, dinitrostyrene, Nitrostyrene such as renitrostyrene; vinylphenols such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene; o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, etc. 1 type, or 2 or more types, such as divinylbenzene; diisopropenylbenzene, such as o-diisopropenylbenzene, m-diisopropenylbenzene, p-diisopropenylbenzene; Of these, methylstyrene such as styrene, α-methylstyrene, and p-methylstyrene, divinylbenzene monomer, or divinylbenzene isomer mixture is preferable in that it is inexpensive.

  The amount of the aromatic vinyl monomer (C) added is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 40 parts by weight, based on 100 parts by weight of the polyolefin resin. The amount is preferably 1 to 30 parts by weight. If the amount added is too small, the graft ratio of the polar group-containing vinyl monomer to the polyolefin resin tends to be poor. On the other hand, when the addition amount exceeds 50 parts by weight, the graft efficiency of the polar group-containing vinyl monomer reaches the saturation range.

<< About radical polymerization initiator >>
Examples of the radical polymerization initiator generally include peroxides and azo compounds. Examples of the radical polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide and methyl acetoacetate peroxide; 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis Peroxyketals such as (t-butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane; permethane hydroper Hydroperoxides such as oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide; dicumyl peroxide, 2,5-dimethyl-2,5-di ( t-Butylperoxy) hexane α, α′-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxide) Dialkyl peroxides such as oxy) hexyne-3; diacyl peroxides such as benzoyl peroxide; peroxys such as di (3-methyl-3-methoxybutyl) peroxydicarbonate and di-2-methoxybutylperoxydicarbonate Dicarbonate; t-butyl peroxyoctate, t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy Isopropyl carbonate, 2,5-dimethyl-2,5-di (benzoyl par Carboxymethyl) hexane, t- butyl peroxy acetate, t- butyl peroxybenzoate, one or more organic peroxides such as peroxy esters such as di -t- butyl peroxy isophthalate and the like.

Of these, those having a particularly high hydrogen abstraction ability are preferred. Examples of such radical polymerization initiators include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1. Peroxyketals such as bis (t-butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane; dicumyl Peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di Dialkyl peroxides such as t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; Diacyl peroxides such as nzoyl peroxide; t-butyl peroxyoctate, t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t-butylperoxy-3,5,5-trimethylhexano Ate, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxyiso 1 type, or 2 or more types, such as peroxyesters, such as a phthalate, is mention | raise | lifted.

  The addition amount of the radical polymerization initiator is preferably in the range of 0.01 to 10 parts by weight, and in the range of 0.05 to 5 parts by weight with respect to 100 parts by weight of the polyolefin resin. Further preferred. If the amount is less than 0.01 part by weight, the modification does not proceed sufficiently, and if it exceeds 10 parts by weight, the fluidity may be lowered due to a crosslinking reaction or the mechanical properties may be lowered due to molecular chain breakage.

<< About tackifier >>
(D) As a tackifier, various things can be used without limitation. Specific examples of tackifiers include rosin resins (gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, rosin ester, etc.), terpene phenol resin, terpene resin (α -Polymers such as pinene, β-pinene and limonene), aromatic hydrocarbon modified terpene resins, petroleum resins (aliphatic, alicyclic, aromatic, etc.), coumarone / indene resins, styrene resins, phenols Resins (alkyl phenol, phenol xylene formaldehyde, rosin-modified phenol resin, etc.), xylene resins and the like can be mentioned, and these can be used alone or in combination of two or more. Of these, from the viewpoint of thermal stability, rosin resins, terpene phenol resins, terpene resins, aromatic hydrocarbon-modified terpene resins, petroleum resins, and hydrogenated petroleum resins are preferable, and are compatible with the modified polyolefin resin of the present invention. Of these, rosin resins and terpene phenol resins are particularly preferred because they can contribute to adhesion to polar resins.

  The blending amount of the tackifier is not particularly limited, but is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the modified polyolefin resin. If the amount is less than 1 part by weight, the adhesiveness is not sufficient. If the amount is more than 50 parts by weight, the tackiness of the resin becomes too strong, the handling becomes worse, and the film moldability is lowered.

  Although there is no restriction | limiting in particular as a softening point of a tackifier, It is preferable that a softening point is 180 degrees C or less. A softening point of 180 ° C. or higher is not preferable because, when blended with a modified polyolefin resin and extruded, a poor dispersion occurs and the adhesive performance decreases.

<< About melt graft modification >>
The adhesive resin composition of the present invention can be produced by a general radical graft method such as a melt kneading method, a solution method, or a suspension method. Among them, the melt-kneading method is excellent in that it is economical, simple and rich in productivity. Regarding the addition order and method during melt-kneading, the addition order of melt-kneading the polar group-containing vinyl monomer or aromatic vinyl monomer to the mixture obtained by melt-kneading the polyolefin resin and the radical polymerization initiator is good, By performing in this addition order, the production | generation of the low molecular weight body which does not contribute to a graft | grafting can be suppressed. In addition, the order and method of mixing and melt-kneading the materials added as necessary are not particularly limited. It may be preliminarily mixed with the polyolefin resin by dry blending and simultaneously supplied to an extruder to be modified.

  The heating temperature at the time of melt kneading is preferably 160 to 240 ° C. from the viewpoint that the polyolefin resin is sufficiently melted and excessive thermal decomposition or crosslinking reaction does not occur. The time for melt kneading (the time after mixing the radical polymerization initiator) is usually 30 seconds to 60 minutes.

  Moreover, as said melt-kneading apparatus, a single screw or a multi-screw extruder, a Banbury mixer, a plast mill, a heated roll kneader, etc. can be used. From the viewpoint of productivity, a method using a single-screw or twin-screw extruder equipped with a pressure reducing device is preferable. Moreover, in order to mix each material sufficiently uniformly, the melt kneading may be repeated a plurality of times.

<< About Adhesive Resin Composition >>
The base resin of the adhesive resin composition of the present invention was graft-modified with (B) a polar group-containing vinyl monomer and (C) an aromatic vinyl monomer with respect to (A) 100 parts by weight of a polyolefin-based resin. It is a modified polyolefin resin. The modified polyolefin resin itself contributes to adhesion with a resin having polarity, and also has compatibility when a resin having a polar group such as rosin resin or terpene phenol resin is used as a tackifier. The adhesion can be further improved.

  The content of the polar group-containing vinyl monomer is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyolefin resin. If the amount is less than 0.1 parts by weight, the adhesiveness is insufficient. If the amount is more than 5 parts by weight, it reacts with the tackifier during melt-kneading to cause a crosslinking reaction, which is not preferable.

  As a method of mixing the base resin and the tackifier, any known method may be used, but melt kneading is particularly preferable from the viewpoint that uniform mixing is easy. As an apparatus for melt kneading, a single-screw or multi-screw extruder, a Banbury mixer, a plast mill, a heated roll kneader, or the like can be used. From the viewpoint of productivity, a method using a single-screw or twin-screw extruder equipped with a pressure reducing device is preferable.

  Moreover, in order to mix each material sufficiently uniformly, the melt kneading may be repeated a plurality of times. If necessary, the adhesive resin composition can be used to stabilize antioxidants, metal deactivators, phosphorus processing stabilizers, UV absorbers, UV stabilizers, fluorescent brighteners, metal soaps, antacid adsorbents, etc. Additives or additives such as crosslinking agents, chain transfer agents, nucleating agents, lubricants, plasticizers, fillers, reinforcing materials, pigments, dyes, flame retardants, antistatic agents, etc. within the range that does not impair the effects of the present invention May be.

  When these stabilizers and additives are used, they may be added to the polyolefin resin in advance, or may be added at the time of the melt modification, and the graft modified modification It may be added when melt-kneading each component of polyolefin resin and tackifier, or may be added by an appropriate method after producing an adhesive resin composition Good.

  In addition, a styrenic elastomer may be added to the adhesive resin composition of the present invention for the purpose of improving film moldability and providing tackiness. Although the compounding quantity of a styrene-type elastomer is not specifically limited, As a range which does not become high cost, 1-30 weight part is preferable with respect to 100 weight part of adhesive resin compositions. Styrene elastomers include styrene-butadiene copolymer, styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene diblock copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer. Polymer, styrene-isobutylene diblock copolymer, styrene-butadiene-styrene triblock copolymer, hydrogenated styrene-butadiene-styrene triblock copolymer, styrene-isoprene-styrene triblock copolymer, hydrogenated styrene -Isoprene-styrene triblock copolymer, styrene-isobutylene-styrene triblock copolymer, ethylene-propylene elastomer, styrene-grafted ethylene-propylene elastomer, ethylene ionomer resin, etc. Gerare These may be used alone or in admixture of two or more thereof.

<< About sheet or film-like molded product >>
The adhesive sheet of the present invention is obtained by forming an adhesive resin composition into a sheet-like or film-like molded body having a heat-welding property. In addition, a resin composition obtained by adding the adhesive resin composition of the present invention to a polyolefin resin can also be formed into a sheet-like or film-like molded body having heat-weldability. The heat-weldability referred to in the present invention refers to the property of melting with heat and joining to the adherend. The sheet or film-like molded product of the present invention can be exemplified by a thickness of 3 to 3 mm, preferably 10 to 2 mm, and can be used as a sheet or film.

  Although the manufacturing method of the sheet-like or film-like molding (adhesive sheet) having the heat-welding property of the present invention is not particularly limited, for example, after the adhesive resin composition of the present invention is obtained by melt-kneading. It can be processed into a sheet using various extrusion molding machines, injection molding machines, calendar molding machines, inflation molding machines, roll molding machines, or hot press molding machines.

  The adhesive resin composition according to the present invention may be a laminate in which a metal layer is sandwiched, and various metals such as gold, silver, copper, iron, tin, lead, aluminum, silicon, and alloys containing these metals. These foils or plates can be sandwiched between film-like adhesive resin compositions and laminated by hot roll molding, press molding, hot air oven, vapor deposition or the like. The metal layer thickness is 1 to 200 μm, and it is easy to tear at 1 μm or less, and handling is bad, and at 200 μm or more, the heat at the time of lamination is taken away by the metal layer, and the adhesion between the hot melt layer and the metal layer is reduced, It is mentioned that productivity falls remarkably. By using the adhesive resin composition according to the present invention, it is possible to bond different kinds of materials as well as the same kind of materials. Materials for the adherend used in the present invention include cellulosic polymer materials such as paper, cotton, hemp and cloth, various woven or non-woven fabrics such as polyester and nylon, wood board, gold, silver, copper, iron and tin. Various metals such as lead, aluminum, and alloys or foils containing these metals, polypropylene, polystyrene, polyethylene, polyester, nylon, polycarbonate resin, (meth) acrylic resin, phenol resin, polyurethane, styrene-butadiene block Polymer (SBS resin), styrene-acrylonitrile copolymer (AS resin), acrylonitrile-ethylene / propylene-styrene copolymer (AES resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), epoxy resin, etc. Plates molded from various synthetic polymer materials, molding , Mention may be made of a film or foam, glass, glass fiber, various inorganic substances such as ceramics and the like. Two or more different materials may be mixed and combined as the material of the adherend. When the laminate is formed by adhering two different adherends via the adhesive film of the present invention, the materials constituting the two adherends may be the same type of material but different types. Any of the materials may be used. If necessary, the adherend may be subjected to a surface treatment such as a release agent, a coating such as plating, a coating with a paint, surface modification with plasma or laser, surface oxidation, etching, or the like.

Although it does not specifically limit as a specific example of the use of the composite molding of this invention, It can use suitably as interior / exterior components, such as a motor vehicle, household appliance components, and housing materials. Examples of these materials include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl chloride, polyester, nylon, polycarbonate resin, polystyrene, impact polystyrene, polyvinylidene chloride, ( (Meth) acrylic resin, AES resin, ABS resin and the like can be mentioned, and the adhesive resin composition of the present invention can be suitably used. In producing these composite molded bodies, various molding methods such as electromagnetic induction heating (IH), insert molding, in-mold molding, vacuum molding, vacuum / pressure air molding, and hot press can be employed. For example, when bonding injection-molded products, an adhesive three-layer laminate with a metal layer sandwiched between the welded parts is placed, covered with the other injection-molded product, and an IH coil (electromagnetic induction coil) is energized from above. There is a method (electromagnetic induction heating) in which the layers are heated to be welded. The energization time to the coil varies depending on the size of the molded body, but is about 0.1 to 5 seconds. In the case of this method, when the adhesive three-layer laminate is placed on the welded portion and transported to the welding process, an adhesive force that prevents the adhesive three-layer laminate from dropping due to vibration or shaking is required.
The electromagnetic induction heating is characterized in that only the metal layer is heated to melt and bond the adhesive film, so that the damage to the adherend is extremely small and the design is not impaired. In vibration welding, ultrasonic welding, and hot plate welding, where the adherend itself is melted and bonded, the damage to the adherend is large and the design is easy to lose, and the bonding mechanism is also different from electromagnetic induction heating. is there.

  Specific examples are shown below, but the present invention is not limited to the following examples.

(Production Example 1)
(A) 100 parts by weight of an ethylene-propylene copolymer (Vistamax 6202 manufactured by ExxonMobil), (b) 1,3-di (t-butylperoxyisopropyl) benzene (manufactured by NOF Corporation: Perbutyl P, 1 0.5 parts by weight (minute half-life 175 ° C.) is supplied to a twin-screw extruder (30 mmφ, L / D = 28, manufactured by Nippon Steel Works, product name LABOTEX 30) set at a cylinder temperature of 200 ° C. and a rotation speed of 250 rpm. After melt-kneading to obtain a pellet obtained by melt-kneading, 5 parts by weight of glycidyl methacrylate and 5 parts by weight of styrene were added and melt-kneaded from the middle of the cylinder to obtain a modified polyolefin resin (A-1). The resulting modified polyolefin resin had a glycidyl methacrylate content of 1.2 parts by weight.

(Production Example 2)
(A) 90 parts by weight of an ethylene-propylene copolymer (Vistamax 6202 manufactured by ExxonMobil), (b) 10 parts by weight of a homopropylene polymer (S119 manufactured by Prime Polymer), (c) 1,3-di (t-butyl) Peroxyisopropyl) benzene (Nippon Yushi Co., Ltd .: Perbutyl P, 1 minute half-life 175 ° C.) 0.5 parts by weight of a twin screw extruder (30 mmφ, L / D) set at a cylinder temperature of 200 ° C. and a rotation speed of 250 rpm = 28, manufactured by Nippon Steel Works, product name LABOTEX30), melt-kneaded to obtain pellets, melt-kneaded to obtain pellets, and then melt-kneaded by adding 5 parts by weight of glycidyl methacrylate and 5 parts by weight of styrene from the middle of the cylinder. Thus, a modified polyolefin resin (A-2) was obtained. The resulting modified polyolefin resin had a glycidyl methacrylate content of 1.3 parts by weight.

(Production Example 3)
(A) 70 parts by weight of an ethylene-propylene copolymer (Vistamax 6202 manufactured by ExxonMobil), (b) 30 parts by weight of a homopropylene polymer (S119 manufactured by Prime Polymer), (c) 1,3-di (t-butyl) Peroxyisopropyl) benzene (Nippon Yushi Co., Ltd .: Perbutyl P, 1 minute half-life 175 ° C.) 0.5 parts by weight of a twin screw extruder (30 mmφ, L / D) set at a cylinder temperature of 200 ° C. and a rotation speed of 250 rpm = 28, manufactured by Nippon Steel Works, product name LABOTEX30), melt-kneaded to obtain pellets, melt-kneaded to obtain pellets, and then melt-kneaded by adding 5 parts by weight of glycidyl methacrylate and 5 parts by weight of styrene from the middle of the cylinder. Thus, a modified polyolefin resin (A-3) was obtained. The resulting modified resin had a glycidyl methacrylate content of 1.3 parts by weight.

(Production Example 4)
(A) Homopropylene polymer (Prime Polymer S119) 100 parts by weight, (b) 1,3-di (t-butylperoxyisopropyl) benzene (Nippon Yushi Co., Ltd .: Perbutyl P, 1 minute half-life 175 ° C) 0.5 parts by weight was supplied to a twin screw extruder (30 mmφ, L / D = 28, manufactured by Nippon Steel Co., Ltd., product name LABOTEX30) set at a cylinder temperature of 200 ° C. and a rotation speed of 250 rpm. Next, after melt-kneading to obtain pellets, 5 parts by weight of glycidyl methacrylate and 5 parts by weight of styrene were added and melt-kneaded from the middle of the cylinder to obtain a modified polyolefin resin (A-4). The resulting modified resin had a glycidyl methacrylate content of 1.2 parts by weight.

Example 1
100 parts by weight of modified polyolefin resin (A-1) obtained in Production Example 1 above, 10 parts by weight of terpene phenol resin (YS Polystar T100, manufactured by Yasuhara Chemical Co., Ltd., softening point 100 ° C.), cylinder temperature 180 ° C., screw rotation It was supplied to a twin screw extruder (30 mmφ, L / D = 28, manufactured by Nippon Steel Works, product name LABOTEX30) set at several 150 rpm, and melt-kneaded to obtain adhesive resin pellets. The obtained adhesive resin pellets were a single-screw extruder (20 mmφ, L / D = 20, manufactured by Toyo Seiki Co., Ltd., product name Laboplast Mill) set at a cylinder and die temperature of 180 ° C. and a screw rotation speed of 100 rpm. An adhesive sheet having a width of about 13 cm and a thickness of 600 μm was formed from a T-shaped die placed in a hopper and attached to the tip of the die.

(Example 2)
100 parts by weight of modified polyolefin resin (A-1) obtained in Production Example 1 above, 10 parts by weight of terpene phenol resin (YS Polystar T160 manufactured by Yasuhara Chemical Co., Ltd., softening point 160 ° C.), cylinder temperature 180 ° C., screw rotation It was supplied to a twin screw extruder (30 mmφ, L / D = 28, manufactured by Nippon Steel Works, product name LABOTEX30) set at several 150 rpm, and melt-kneaded to obtain adhesive resin pellets. The obtained adhesive resin pellets were a single-screw extruder (20 mmφ, L / D = 20, manufactured by Toyo Seiki Co., Ltd., product name Laboplast Mill) set at a cylinder and die temperature of 180 ° C. and a screw rotation speed of 100 rpm. An adhesive sheet having a width of about 13 cm and a thickness of 600 μm was formed from a T-shaped die placed in a hopper and attached to the tip of the die.

(Example 3)
100 parts by weight of modified polyolefin resin (A-2) obtained in Production Example 2 above, 10 parts by weight of terpene phenol resin (YS Polystar T100 manufactured by Yasuhara Chemical Co., Ltd., softening point 100 ° C.), cylinder temperature 180 ° C., screw rotation It was supplied to a twin screw extruder (30 mmφ, L / D = 28, manufactured by Nippon Steel Works, product name LABOTEX30) set at several 150 rpm, and melt-kneaded to obtain adhesive resin pellets. The obtained adhesive resin pellets were a single-screw extruder (20 mmφ, L / D = 20, manufactured by Toyo Seiki Co., Ltd., product name Laboplast Mill) set at a cylinder and die temperature of 180 ° C. and a screw rotation speed of 100 rpm. An adhesive sheet having a width of about 13 cm and a thickness of 600 μm was formed from a T-shaped die placed in a hopper and attached to the tip of the die.

Example 4
100 parts by weight of modified polyolefin resin (A-1) obtained in Production Example 1 above, 20 parts by weight of terpene phenol resin (YS Polystar T100 manufactured by Yasuhara Chemical Co., Ltd., softening point 100 ° C.), cylinder temperature 180 ° C., screw rotation It was supplied to a twin screw extruder (30 mmφ, L / D = 28, manufactured by Nippon Steel Works, product name LABOTEX30) set at several 150 rpm, and melt-kneaded to obtain adhesive resin pellets. The obtained adhesive resin pellets were a single-screw extruder (20 mmφ, L / D = 20, manufactured by Toyo Seiki Co., Ltd., product name Laboplast Mill) set at a cylinder and die temperature of 180 ° C. and a screw rotation speed of 100 rpm. An adhesive sheet having a width of about 13 cm and a thickness of 600 μm was formed from a T-shaped die placed in a hopper and attached to the tip of the die.

(Example 5)
100 parts by weight of modified polyolefin resin (A-1) obtained in Production Example 1 above, 20 parts by weight of terpene phenol resin (YS Polystar T160 manufactured by Yasuhara Chemical Co., Ltd., softening point 160 ° C), cylinder temperature 180 ° C, screw rotation It was supplied to a twin screw extruder (30 mmφ, L / D = 28, manufactured by Nippon Steel Works, product name LABOTEX30) set at several 150 rpm, and melt-kneaded to obtain adhesive resin pellets. The obtained adhesive resin pellets were a single-screw extruder (20 mmφ, L / D = 20, manufactured by Toyo Seiki Co., Ltd., product name Laboplast Mill) set at a cylinder and die temperature of 180 ° C. and a screw rotation speed of 100 rpm. An adhesive sheet having a width of about 13 cm and a thickness of 600 μm was formed from a T-shaped die placed in a hopper and attached to the tip of the die.

(Example 6)
An adhesive sheet having a width of about 13 cm and a thickness of 600 μm was obtained under the same conditions as in Example 2 except that 20 parts by weight of terpene phenol resin (YS Polystar T160 manufactured by Yasuhara Chemical Co., Ltd., softening point: 160 ° C.) was used.

(Comparative Example 1)
A single-screw extruder (20 mmφ, L / D = 20, manufactured by Toyo Seiki Co., Ltd.) in which 100 parts by weight of the modified polyolefin resin obtained in Production Example 1 was set to a cylinder and a die temperature of 180 ° C. and a screw rotation speed of 100 rpm. A film having a width of about 13 cm and a thickness of 600 μm was introduced from a T-shaped die attached to the tip of the die.

(Comparative Example 2)
100 parts by weight of the modified polyolefin resin and 10 parts by weight of terpene phenol resin (YS Polystar T100 manufactured by Yasuhara Chemical Co., Ltd., softening point 100 ° C.) obtained in Production Example 3 were set to a cylinder temperature of 180 ° C. and a screw rotation speed of 150 rpm. The mixture was supplied to a twin screw extruder (30 mmφ, L / D = 28, manufactured by Nippon Steel Works, product name LABOTEX30) and melt kneaded to obtain adhesive resin pellets. The obtained adhesive resin pellet was a single-screw extruder (20 mmφ, L / D = 20, manufactured by Toyo Seiki Co., Ltd., product name: Laboplast Mill) set at a cylinder and die temperature of 200 ° C. and a screw rotation speed of 100 rpm. A T-type die placed in the hopper and attached to the tip of the die was used as a film having a width of about 13 cm and a thickness of 600 μm.

(Comparative Example 3)
100 parts by weight of modified polyolefin resin and 10 parts by weight of terpene phenol resin (YS Polystar T100 manufactured by Yashara Chemical Co., Ltd., softening point 100 ° C.) obtained in Production Example 4 were set to a cylinder temperature of 180 ° C. and a screw rotation speed of 150 rpm. The mixture was supplied to a twin screw extruder (30 mmφ, L / D = 28, manufactured by Nippon Steel Works, product name LABOTEX30) and melt kneaded to obtain adhesive resin pellets. The obtained adhesive resin pellet was a single-screw extruder (20 mmφ, L / D = 20, manufactured by Toyo Seiki Co., Ltd., product name: Laboplast Mill) set at a cylinder and die temperature of 200 ° C. and a screw rotation speed of 100 rpm. A T-type die placed in the hopper and attached to the tip of the die was used as a film having a width of about 13 cm and a thickness of 600 μm.

(Initial adhesion evaluation)
PC / ABS (manufactured by Teijin Chemicals Ltd .: Multilon T-7000F) and GFR / PP (Nippon Polypro Co., Ltd.) prepared by injection molding were cut into 1 cm × 10 cm for the films prepared in Examples 1-5 and Comparative Examples 1-3. The product was placed on a flat plate (120 mm × 120 mm × t2 mm) made by Funkster LR24A), and the plate was turned upside down in a state where it was lightly stroked and adhered by hand. When the film did not fall, it was peeled off by hand and evaluated for adhesion. The evaluation was made into a three-step evaluation: x: the film fell before the flat plate was inverted, Δ: the film fell within 5 seconds when the flat plate was inverted, and ○: the film did not fall even when the flat plate was inverted. .
The results are shown in Table 1.

(Ball tack evaluation)
The films created in Examples 1 to 5 and Comparative Examples 1 to 3 were attached to a jig having an inclination angle of 5 ° according to JIS Z 0237: 2000, and 1/32 to 32/32 inch size iron balls were rolled. The maximum size that stopped for more than 5 seconds on the film surface was recorded. The results are shown in Table 1.

  In Examples 1 to 5, the initial adhesion evaluation was a pass judgment in all cases, and the ball tack evaluation also showed good results that cleared Claim 1. In Comparative Examples 1 to 3, the initial adhesion and ball tack evaluation were poor.

Claims (8)

An adhesive resin composition processed into a film, wherein the film has a tackiness of 3/32 inches or more in a ball tack test according to JIS Z0237 (with or without an inclination angle of 5 °), and the film An adhesive sheet, wherein the film does not fall when the molded product is turned upside down when attached to a thermoplastic molded product. The adhesive resin composition comprises (B) a polar group-containing vinyl monomer and (C) an aromatic vinyl monomer in the presence of a radical polymerization initiator with respect to (A) 100 parts by weight of a polyolefin resin. 2. The adhesive according to claim 1, wherein 1 to 50 parts by weight of a tackifier having a softening point of 180 ° C. or less is blended with 100 parts by weight of the modified polyolefin resin modified by the melt-kneading step. Sex sheet.
The adhesive sheet according to claim 1 or 2, wherein the polyolefin resin of (A) is a polypropylene resin having a majority of propylene units of 100 to 80 parts by weight and a polypropylene of 0 to 20 parts by weight.
The adhesive sheet according to claim 1, wherein the (C) polar group-containing vinyl monomer is glycidyl methacrylate or maleic anhydride.
The adhesive composition contains (D) a tackifier, and the tackifier is at least selected from a rosin resin, a terpene phenol resin, a terpene resin, an aromatic hydrocarbon-modified terpene resin, a petroleum resin, and a hydrogenated petroleum resin. It is 1 type of tackifier, The adhesive sheet of Claims 1-4 characterized by the above-mentioned. An adhesive resin composition comprising a laminate having a three-layer structure in which a metal foil or a plate having a thickness of 1 to 200 µm is sandwiched and laminated on the adhesive sheet according to any one of claims 1 to 5. Laminated body. 7. The adhesive resin composition according to claim 6, wherein the metal foil or plate is a metal such as gold, silver, copper, iron, tin, lead, aluminum, or silicon and / or an alloy containing these metals. Laminated body. A method for using an adhesive resin composition laminate, wherein electromagnetic induction heating is used to fuse the laminate according to any one of claims 6 to 7 and an adherend.