JP5394817B2 - Adhesive resin composition and molded body - Google Patents

Description

  The present invention uses an epoxy group-containing modified polyolefin resin obtained by melt-grafting a polyolefin resin with an epoxy group-containing vinyl monomer, and an α, β-unsaturated carboxylic acid or its anhydride monomer as the polyolefin resin. The present invention relates to an adhesive resin composition comprising an acid-modified polyolefin resin obtained by melt graft modification, and a composition containing the resin. Furthermore, it aims at providing the sheet-like or film-form molded object which has the outstanding adhesiveness with respect to a difficult-to-adhere base material, and its manufacturing method.

Polyolefin resins, such as polypropylene resins, have excellent moldability, rigidity, heat resistance, chemical resistance, electrical insulation, etc., and are inexpensive, so they can be molded into films, fibers, and other various shapes. It is used for a wide range of products. Polypropylene material, on the other hand, is a so-called non-polar and extremely inert polymer substance that does not have a polar group in the molecule, and has high crystallinity and extremely low solubility in solvents. There is a problem that the scratch resistance, oil resistance and the like are low. In order to improve this defect, a method for producing a modified resin by graft polymerization of a polymerizable monomer having a polar functional group to an olefin resin has been proposed, and the following method has been proposed.
(I) A method in which a polyolefin resin particle dispersed in water is impregnated with a vinyl monomer and heated in the presence of a peroxide to produce a modified polyolefin (Patent Document 1).
(Ii) A method for producing a modified polyolefin by melt-kneading a polyolefin resin, maleic anhydride and an organic peroxide (Patent Document 2).

  In the method (i), various vinyl monomers can be grafted onto the polyolefin resin. However, a monomer having a highly polar functional group such as an epoxy group is difficult to impregnate a polyolefin resin having a low polarity, so that the amount capable of copolymerization is limited. In addition, since a dissolution inhibitor of the monomer in water is required, the dissolution inhibitor remains in the modified polyolefin composition after the reaction, and the printability, ink adhesion, and adhesion are impaired.

  In the method (ii), the types of monomers that can be copolymerized with the polyolefin resin are limited. For example, when glycidyl methacrylate is used in place of maleic anhydride, the monomer is volatilized unreacted, the monomers are only polymerized and do not graft onto the polyolefin resin, or excess peroxide causes the main chain of the polyolefin. However, since the molecular weight is reduced by cutting, the mechanical properties are lowered, and it cannot be said that the level has been reached to meet the sufficient requirement for adhesion.

Japanese Patent Laid-Open No. 6-122738 Japanese Patent Laid-Open No. 9-278956

  An object of this invention is to provide the adhesive resin which has the outstanding adhesiveness with respect to a difficult-to-adhere base material, and the composition containing this resin by an easy method using a simple apparatus.

  As a result of intensive studies in view of the above-mentioned present situation, the present inventors have found that excellent adhesion performance is expressed by mixing an epoxy group-containing modified polyolefin resin and an acid-modified polyolefin resin, and complete the present invention. It came to do.

  1) (A) 1 to 99 parts by weight of an epoxy group-containing modified polyolefin resin obtained by melt graft modification of a polyolefin resin with an epoxy group-containing vinyl monomer, and (B) an α, β-unsaturated carboxylic acid Or the adhesive resin composition which consists of 99-1 weight part [however (A) + (B) = 100 weight part] of acid-modified polyolefin resin obtained by melt-grafting modification | denaturation with the anhydride monomer.

  2) (A) Epoxy group-containing modified polyolefin resin is compared with (a-1) polyolefin resin in the presence of a radical polymerization initiator. (A-2) Epoxy group-containing vinyl monomer and (a-3) aroma Obtained by melt-kneading a group vinyl monomer, and the addition amount of the (a-2) epoxy group-containing vinyl monomer is (a-1) a polyolefin resin and (a-2) an epoxy group-containing vinyl monomer The adhesive resin composition according to 1), which is in the range of 0.1 to 50% by weight based on the total weight of the body and (a-3) the aromatic vinyl monomer.

  3) (B) Acid-modified polyolefin resin is (b-1) α, β-unsaturated carboxylic acid or acid anhydride monomer thereof in the presence of a radical polymerization initiator with respect to (b-1) polyolefin resin. And (b-3) obtained by melt-kneading an aromatic vinyl monomer, and (b-2) the amount of α, β-unsaturated carboxylic acid or its anhydride monomer added is (b- 1) to 50% by weight based on the total weight of 1) polyolefin resin, (b-2) α, β-unsaturated carboxylic acid or acid anhydride monomer, and (b-3) aromatic vinyl monomer %), The adhesive resin composition according to 1) or 2).

  4) The adhesive resin composition according to any one of 1) to 3), wherein the polyolefin resin is a polypropylene resin in which a propylene unit is a majority amount.

  5) At least one of the (A) epoxy group-containing modified polyolefin resin and the (B) acid-modified polyolefin resin obtained by modifying a polyolefin resin, the polyolefin resin contains 0.01 to 45% by weight of an ethylene component. -Adhesive resin composition in any one of 1) -4) which is a propylene copolymer.

  6) (b-2) The adhesive resin composition according to any one of 3) to 5), wherein the α, β-unsaturated carboxylic acid or its acid anhydride monomer is maleic anhydride.

  7) (A) Epoxy group-containing modified polyolefin resin is melt-kneaded (a-1) polyolefin resin and radical polymerization initiator, then (a-3) epoxy group-containing vinyl monomer, (a-4) The adhesive resin composition according to any one of 2) to 6), which is obtained by adding an aromatic vinyl monomer and melt-kneading.

  8) (B) Acid-modified polyolefin resin was melt-kneaded (b-1) polyolefin resin and radical polymerization initiator, and (b-2) α, β-unsaturated carboxylic acid or its acid anhydride monomer. Then, (b-3) The adhesive resin composition according to any one of 3) to 7), which is obtained by adding an aromatic vinyl monomer and melt-kneading.

  9) Adhesive polyolefin resin composition containing 0.1 to 100 parts by weight of polypropylene resin with a majority of propylene units based on 100 parts by weight of adhesive resin composition according to any one of 1) to 8) object.

  10) A sheet-like or film-like molded article comprising the adhesive resin composition according to any one of 1) to 9) and having heat-weldability.

  11) At least one adhesive resin composition according to 1) to 9) and / or an adhesive body formed by bonding with a sheet-like or film-like molded body according to 10).

  12) A method for producing a sheet-like or film-like molded article, comprising melt-kneading the adhesive resin composition according to any one of 1) to 9) and then molding the sheet into a sheet or film.

  The adhesive resin composition of the present invention can be used not only alone but also mixed with polyolefin resin to ensure excellent adhesion to difficult-to-adhere substrates, such as stationery, miscellaneous goods, food, etc. It is suitably used in a wide range of fields such as packaging materials, automotive parts, electrical and electronic parts such as home appliances, and various industrial materials.

Details of the present invention will be described below.

<< About polyolefin resin >>
Examples of the (a-1) and (b-1) polyolefin resins include polyethylene, polypropylene, poly-1-butene, polyisobutylene, random copolymers in any ratio of propylene and ethylene and / or 1-butene, or Block copolymer, ethylene-propylene-diene terpolymer having a diene component of 50% by weight or less in any ratio of ethylene and propylene, copolymer of polymethylpentene, cyclopentadiene and ethylene and / or propylene And a random copolymer of ethylene or propylene with 50% by weight or less of a vinyl compound, a block copolymer, and the like.

Among these, polypropylene, polyethylene, polyisobutylene, and ethylene-propylene copolymer are preferable. From the viewpoint of adhesiveness and heat resistance, it is particularly preferable to use a combination of polypropylene and ethylene-propylene copolymer.
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.

  Furthermore, the polyolefin resin (a-1) or (b-1) is preferably an ethylene-propylene copolymer containing 0.01 to 45% by weight of an ethylene component, and 1 to 30% by weight of an ethylene component. Is more preferable.

  There are crystalline and non-crystalline polyolefin resins, but any of them can be used in the present invention without any particular limitation.

  In addition, a polyolefin resin having a polar group introduced may be used by mixing it with a polypropylene or ethylene-propylene copolymer used for modification in that it is easily compatible with a non-aromatic vinyl monomer having a polar group. Good. 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. 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.

<< About epoxy group-containing vinyl monomers >>
The epoxy group-containing vinyl monomer is not particularly limited, but is preferably an epoxy group-containing vinyl monomer having 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms. For example, glycidyl methacrylate, glycidyl acrylate, monoglycidyl maleate, diglycidyl maleate, monoglycidyl itaconate, diglycidyl itaconate, monoglycidyl allyl succinate, diglycidyl allyl succinate, glycidyl p-styrenecarboxylate, allyl glycidyl ether , Glycidyl group-containing vinyl monomers such as methallyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene 1 type, or 2 or more types, such as epoxy olefins, vinyl cyclohexene monoxide, etc. are mentioned.

  Of these, glycidyl methacrylate and glycidyl acrylate are preferable in that they are inexpensive. The amount of the (a-2) epoxy group-containing vinyl monomer added is preferably 0.2 to 100 parts by weight with respect to 100 parts by weight of the (a-1) polyolefin resin, 0.5 to More preferably, it is 50 parts by weight. The proportion of the (a-2) epoxy group-containing vinyl monomer is (a-1) a polyolefin resin, (a-2) an epoxy group-containing vinyl monomer, and (a-3) an aromatic vinyl monomer. It is preferably in the range of 0.1 to 50% by weight of the total amount of the body, more preferably in the range of 0.5 to 40% by weight, and particularly preferably in the range of 1 to 30% by weight. If the addition amount is too small, the adhesiveness tends not to be sufficiently improved, and if the addition amount is too large, the by-product of free polymer that does not contribute to the graft tends to increase.

<< About the aromatic vinyl monomer >>
The aromatic vinyl monomer is not particularly limited, but is preferably an aromatic vinyl monomer having 4 to 20 carbon atoms, more preferably 6 to 15 carbon atoms. 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, p-methylstyrene, divinylbenzene monomer or divinylbenzene isomer mixture is preferable in that it is inexpensive.

  The addition amount of the aromatic vinyl monomers (a-3) and (b-3) is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the polyolefin resin, The amount is more preferably 40 parts by weight, and particularly preferably 1 to 30 parts by weight. If the amount added is too small, the graft ratio of (a-2) epoxy group-containing vinyl monomer and (b-2) α, β unsaturated carboxylic acid or anhydride monomer to polyolefin resin tends to be inferior. . On the other hand, when the addition amount exceeds 50 parts by weight, the graft efficiency of the epoxy group-containing vinyl monomer and the α, β unsaturated carboxylic acid or its anhydride monomer reaches the saturation range.

<< α, β-unsaturated carboxylic acid or acid anhydride monomer thereof >>
The α, β-unsaturated carboxylic acid or anhydride monomer thereof is an unsaturated mono- or dicarboxylic acid having an ethylenic double bond and a carboxylic acid group or carboxylic anhydride group in the same molecule and These acid anhydrides are 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, maleic anhydride, endic acid anhydride, citraconic anhydride, itaconic anhydride, nadic acid anhydride and the like can be exemplified. Among these monomers, acrylic acid, methacrylic acid and maleic anhydride are preferable, and maleic anhydride is more preferable. These may be used individually by 1 type, and may be used in combination of 2 or more types. Among these, maleic anhydride is preferable in terms of adhesion at a low temperature when adhering to a dissimilar material, particularly when adhering to a metal material.

  The addition amount of the (b-2) α, β-unsaturated carboxylic acid or acid anhydride monomer is 0.05 to 100 parts by weight with respect to 100 parts by weight of the (b-1) polyolefin resin. It is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 20 parts by weight. Moreover, the ratio of (b-2) unsaturated carboxylic acid or its anhydride monomer is (b-1) polyolefin resin, (b-2) unsaturated carboxylic acid or its anhydride monomer, and (b- 3) It is preferably in the range of 0.01 to 50% by weight of the total amount of the aromatic vinyl monomer, more preferably 0.1 to 40% by weight, and 0.5 to 20% by weight. More preferably. If the addition amount is too small, there is a tendency that the adhesiveness is not sufficiently improved. On the other hand, if the addition amount is too large, an excessive amount of monomer remains in the modified resin, and the cost for removing them is high, and preferable. There arises a problem that it cannot be obtained as a resin composition having a simple shape and appearance.

<< About radical initiators >>
Examples of radical polymerization initiators 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 more preferably in the range of 0.05 to 5 parts by weight with respect to 100 parts by weight of the polyolefin resin. preferable. If it is less than 0.01 part by weight, the modification does not proceed sufficiently, and if it exceeds 10 parts by weight, fluidity and mechanical properties may be lowered.

<< About modified polyolefin >>
For the production of the modified polyolefin, an impregnation method, a solution method, a melting method and the like are used. In the present invention, a simpler melting method can be used. In the melt method, (a-2) an epoxy group-containing vinyl monomer or (b-2) an α, β unsaturated carboxylic acid or its anhydride monomer as compared with the case of reacting by a method such as impregnation polymerization Can be used. Furthermore, by using a radical initiator and an aromatic vinyl monomer in combination, (a-2) an epoxy group-containing vinyl monomer or (b-2) an α, β unsaturated carboxylic acid or its anhydride The effect of the present invention can be obtained by improving the grafting efficiency of the monomer.

Regarding the order and method of addition at the time of melt kneading, (a-2) epoxy group-containing vinyl monomer or (b-2) α, β unsaturated carboxylic acid is added to a mixture obtained by melt kneading a polyolefin resin and a radical polymerization initiator. Alternatively, the addition order in which the anhydride monomer and aromatic vinyl monomer are added and melt-kneaded is good, and the formation of a low molecular weight substance that does not contribute to grafting can be suppressed by performing this addition order. When the unsaturated carboxylic acid or its anhydride is solid and does not cause homopolymerization like maleic anhydride, it may be mixed with the polyolefin resin by dry blending and melt kneaded with a radical polymerization initiator.
The adhesive resin composition of the present invention comprises (A) an epoxy group-containing modified polyolefin resin, after (a-1) melt-kneading (a-1) a polyolefin resin and a radical polymerization initiator, and then (a-3) an epoxy group-containing vinyl. Monomer, (a-4) A method in which an aromatic vinyl monomer is added and melt-kneaded for production.

  In the adhesive resin composition of the present invention, (B) the acid-modified polyolefin resin comprises (b-1) a polyolefin resin and a radical polymerization initiator, and (b-2) an α, β-unsaturated carboxylic acid or an acid thereof. After melt-kneading the anhydride monomer, (b-3) a method in which an aromatic vinyl monomer is added and melt-kneaded for production.

  The heating temperature at the time of melt kneading is preferably 130 to 300 ° C. from the viewpoint that the polyolefin resin is sufficiently melted and is not thermally decomposed. 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 >>
In the adhesive resin composition of the present invention, the blending ratio of (A) epoxy group-containing modified polyolefin and (B) acid-modified polyolefin is (A) 1 to 99 parts by weight of epoxy group-containing modified polyolefin, and (B) acid-modified polyolefin. 99 to 1 part by weight (where [(A) + (B) is a total of 100 parts by weight). In order to sufficiently improve the adhesive performance, the component (A) is larger than the component (B). Specifically, it is preferably within the range of 60 to 95 parts by weight of component (A) and 40 to 5 parts by weight of component (B), and 70 to 85 parts by weight of component (A) and 30 to 30 parts of component (B). More preferably, it is 15 parts by weight (however, (A) + (B) is 100 parts by weight in total).

  Any known method may be used as the method for mixing the (A) epoxy group-containing modified polyolefin and the (B) acid-modified polyolefin. Alchemy is preferred. 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 in advance to the polyolefin resin of (a-1) and / or (b-1), and (a-1) and / or ( It may be added when the polyolefin resin of b-1) is melt-modified, and is added when (A) the epoxy group-containing modified polyolefin and (B) the acid-modified polyolefin are melt-kneaded. It may also be added after the adhesive resin composition is produced by an appropriate method.

  Moreover, even if it adds to the polyolefin resin as an additive, the adhesive resin composition of this invention can improve adhesiveness.

  Examples of the polyolefin resin mixed with the modified polyolefin resin of the present invention include polypropylene homopolymer, high density polyethylene, low density polyethylene, linear low density polyethylene, poly-1-butene, polyisobutylene, polymethylpentene, and cyclopentadiene. Random of cyclic polyolefin such as a copolymer of ethylene and / or propylene, ethylene or propylene and 50% by weight or less of vinyl compound such as vinyl acetate, alkyl methacrylate, alkyl acrylate, aromatic vinyl A copolymer etc. are mentioned, These can be used individually or in mixture of 2 or more types. A polypropylene homopolymer is preferable from the viewpoint of high rigidity and low cost, and a block copolymer of propylene and another monomer is preferable from the viewpoint of high rigidity and impact resistance.

  When the adhesive resin composition of the present invention and the polyolefin resin are mixed, the mixing amount is not particularly limited, but is 0.1 to 100 parts by weight, more preferably 0.1 to 70 parts by weight with respect to 100 parts by weight of the polyolefin resin. It is preferable to include parts by weight. More preferably, it is 0.1-50 weight part, More preferably, it is 0.1-20 weight part. If the amount is too large, the inherent mechanical properties of the polyolefin resin may be degraded, and economic problems may occur.

<< About sheet or film-like molded article >>
The adhesive resin composition of the present invention can be formed into a sheet-like or film-like molded product having heat-weldability. 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 article 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 article of the present invention can be exemplified by a thickness of the molded article of 3 to 3 mm, preferably 10 to 2 mm, and can be used as a sheet or film.

  The method for producing the sheet-like or film-like molded article having the heat-weldability of the present invention is not particularly limited. For example, after dry blending or melt-kneading the polyolefin resin of the present invention and the adhesive resin composition. It is possible to form into a sheet-like molded body using various extrusion molding machines, injection molding machines, calendar molding machines, inflation molding machines, roll molding machines, or hot press molding machines.

  The material of the adherend used in the present invention is, for example, a material that can adhere to the adhesive resin layer of the adhesive film of the present invention. Specifically, for example, metals such as gold, silver, copper, iron, tin, lead and aluminum, inorganic materials such as glass and ceramics; cellulosic polymer materials such as paper and cloth, melamine resins, acrylic and urethane Examples thereof include synthetic polymer materials such as epoxy resins, urethane resins, (meth) acrylic resins, styrene / acrylonitrile copolymers, ABS resins, polycarbonate resins, phenol resins, alkyd resins, and epoxy resins.

  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. The property of the adherend is not particularly limited, and examples thereof include a film shape, a sheet shape, a plate shape, and a fiber shape. In addition, 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, etc., if necessary. Good.

  Specific examples of the use of adherends include automotive parts such as trims (door trims, interior trims, etc.), molded ceilings, sheet materials (interior sheets, instrument panel skins, decorative sheets, etc.), indoor doors, partitions, interior walls. Examples include, but are not limited to, decorative films used in housing materials such as boards, furniture, and system kitchens.

  Specific examples are shown below, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

(Production Example 1)
(A) Homopolypropylene (manufactured by Prime Polymer Co., Ltd., J105G, MFR = 9) 100 parts, (b) 1,3-di (t-butylperoxyisopropyl) benzene (manufactured by NOF Corporation: Perbutyl P, 1 A twin screw extruder (44 mmφ, L / D = 38.5, manufactured by Nippon Steel Works, product name TEX44XCT) in which 0.5 part was set at a cylinder temperature of 200 ° C. and a screw rotation speed of 150 rpm. Then, 5 parts of glycidyl methacrylate and 5 parts of styrene were added and melt-kneaded from the middle of the cylinder to obtain modified polyolefin resin pellets (A-1).

(Production Example 2)
(A) 100 parts of homopolypropylene (Prime Polymer S119, MFR = 60), (b) 1,3-di (t-butylperoxyisopropyl) benzene (Nippon Yushi Co., Ltd .: Perbutyl P, 1 A twin screw extruder (44 mmφ, L / D = 38.5, manufactured by Nippon Steel Works, product name TEX44XCT) in which 0.5 part was set at a cylinder temperature of 200 ° C. and a screw rotation speed of 150 rpm. Then, 5 parts of glycidyl methacrylate and 5 parts of styrene were added from the middle of the cylinder and melt-kneaded to obtain modified polyolefin resin pellets (A-2).

(Production Example 3)
(A) Homopolypropylene (manufactured by Prime Polymer Co., Ltd., J105G, MFR = 9) 100 parts, (b) 1,3-di (t-butylperoxyisopropyl) benzene (manufactured by NOF Corporation: Perbutyl P, 1 0.1 part of a half-life of 175 ° C. (min), (c) 1 part of maleic anhydride (Wako Pure Chemical Industries, Ltd.) is set to a cylinder temperature of 200 ° C. and a screw rotation speed of 250 rpm (30 mmφ, L / L D = 28, manufactured by Nippon Steel Co., Ltd., product name LABOTEX30, vent pressure 60 cmHg), melt-kneaded, then added 1 part of styrene from the middle of the cylinder, melt-kneaded, and modified polyolefin resin pellets (A- 3) was obtained.

(Production Example 4)
100 parts of ethylene-propylene copolymer (Varphi 3401 manufactured by Dow Co., Ltd., ethylene content 15% by weight, MFR = 8), (b) 1,3-di (t-butylperoxyisopropyl) benzene (Nippon Yushi Co., Ltd.) ): Perbutyl P, half-life 175 ° C for 1 minute) twin screw extruder (44mmφ, L / D = 38.5, Nippon Steel Corporation) with 0.5 parts set to cylinder temperature 200 ° C and screw rotation speed 150rpm Then, the product was melt-kneaded and supplied with 5 parts of glycidyl methacrylate and 5 parts of styrene from the middle of the cylinder to obtain a modified polyolefin resin pellet (B-1).

(Production Example 5)
(A) Ethylene-propylene copolymer (Versify 3401 manufactured by Dow Co., Ltd., ethylene content 15% by weight, MFR = 8) 100 parts, (b) 1,3-di (t-butylperoxyisopropyl) benzene (Japan) Oil and fat Co., Ltd .: Perbutyl P, 0.1 part of half-life 175 ° C. 0.1 part, (c) Maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) 5 parts was set at a cylinder temperature of 200 ° C. and a screw speed of 250 rpm After being supplied to a shaft extruder (30 mmφ, L / D = 28, manufactured by Nippon Steel Co., Ltd., product name LABOTEX30) and melt-kneaded, 5 parts of styrene was added from the middle of the cylinder and melt-kneaded to obtain a modified polyolefin resin. A pellet (B-2) was obtained.

Example 1
A twin-screw extruder (30 mmφ, L / L) in which the modified polyolefin resin pellets obtained in the above production example, 85 parts of (A-1) and 15 parts of (B-2) were set at a cylinder temperature of 200 ° C. and a screw rotation speed of 200 rpm. 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 film (A1) having a width of about 13 cm and a thickness of 30 μm was formed from a T-type die placed in a hopper and attached to the tip of the die.

(Example 2)
The modified polyolefin resin pellets obtained in the above production example, (A-2) 85 parts and (B-2) 15 parts, a twin-screw extruder (30 mmφ, L / L) set to a cylinder temperature of 200 ° C. and a screw rotation speed of 200 rpm. 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 film (A2) having a width of about 13 cm and a thickness of 30 μm was formed from a T-type die that was put into a hopper and attached to the tip of the die.

(Example 3)
The modified polyolefin resin pellets obtained in the above production example, (A-3) 15 parts and (B-1) 85 parts were subjected to 5 times at a temperature of 200 ° C. using a lab plast mill (manufactured by Toyo Seiki Co., Ltd., LABOPLASTOMILL). The mixture was melt-kneaded at 100 rpm for 1 minute 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 film (A3) having a width of about 13 cm and a thickness of 50 μm was formed from a T-type die placed in the hopper and attached to the tip of the die.

(Comparative Example 1)
A single screw extruder (20 mmφ, L / D = 20, Toyo Seiki Co., Ltd.) in which the modified polyolefin resin (A-1) obtained in Production Example 1 was set to a cylinder and a die temperature of 200 ° C. and a screw rotation speed of 100 rpm. A film (A4) having a width of about 13 cm and a thickness of 30 μm was introduced from a T-shaped die attached to the tip of the die.

(Comparative Example 2)
A single-screw extruder (20 mmφ, L / D = 20, Toyo Seiki Co., Ltd.) in which the modified polyolefin resin (A-2) obtained in Production Example 2 was set to a cylinder and a die temperature of 200 ° C. and a screw rotation speed of 100 rpm. A film (A5) having a width of about 13 cm and a thickness of 30 μm was introduced from a T-shaped die attached to a hopper of the product, product name Lab Plast Mill).

(Comparative Example 3)
A single-screw extruder (20 mmφ, L / D = 20, Toyo Seiki Co., Ltd.) in which the modified polyolefin resin (A-3) obtained in Production Example 3 was set to a cylinder and die temperature of 200 ° C. and a screw rotation speed of 100 rpm. A film (A6) having a width of about 13 cm and a thickness of 30 μm was introduced from a T-shaped die attached to a hopper of the product, product name Lab Plast Mill).

(Comparative Example 4)
A single-screw extruder (20 mmφ, L / D = 20, Toyo Seiki Co., Ltd.) in which the modified polyolefin resin (A-4) obtained in Production Example 4 was set to a cylinder and die temperature of 200 ° C. and a screw rotation speed of 100 rpm. A film (A7) having a width of about 13 cm and a thickness of 50 μm was introduced from a T-shaped die attached to the tip of the die.

(Comparative Example 5)
A single-screw extruder (20 mmφ, L / D = 20, Toyo Seiki Co., Ltd.) in which the modified polyolefin resin (A-5) obtained in Production Example 5 was set to a cylinder and die temperature of 200 ° C. and a screw rotation speed of 100 rpm. A film (A8) having a width of about 13 cm and a thickness of 50 μm was introduced from a T-shaped die attached to the tip of the die.

  Using the adhesive sheets or films (A1 to A8) prepared in Examples 1 to 3 and Comparative Examples 1 to 5, adhesion test samples of steel plate were prepared, and T-shaped peeling evaluation was performed. The test sample was obtained by sandwiching an adhesive film or sheet between two steel plate plates (25 mm × 150 mm, thickness 0.15 mm), and a press machine (Kanto Metal Industries, Model NSF-50, press temperature 200 ° C., no pressure) (Preheating 4 minutes, 2 MPa, press 30 seconds, no pressure, cooling press 3 min) T-peel evaluation was performed using AG-2000A manufactured by Shimadzu Corporation at 23 ° C. and a tensile test speed of 200 mm / min. Table 1 summarizes the modified formulations of the modified polyolefin resins used in the examples, and Table 2 summarizes the T-shaped peel strengths of the examples and comparative examples together with the recipe.

  Examples 1 to 3 use the adhesive resin composition of the present invention, and in each case glycidyl methacrylate-modified polyolefin resin and maleic anhydride-modified polyolefin resin are used alone as an adhesive resin (Comparative Examples 1 to 5). It showed stronger adhesive strength.

Claims (11)

(A) 1 to 99 parts by weight of an epoxy group-containing modified polyolefin resin obtained by melt graft modification of a polyolefin resin with an epoxy group-containing vinyl monomer, and (B) an α, β-unsaturated carboxylic acid or its An adhesive resin composition comprising 99 to 1 part by weight of an acid-modified polyolefin resin obtained by melt graft modification with an anhydride monomer (where (A) + (B) = 100 parts by weight) ,
An adhesive resin composition, wherein the polyolefin resin is a polypropylene resin having a majority of propylene units . (A) Epoxy group-containing modified polyolefin resin is (a-1) polyolefin resin, in the presence of a radical polymerization initiator, (a-2) epoxy group-containing vinyl monomer and (a-3) aromatic vinyl It is obtained by melt-kneading the monomer, and the amount of the (a-2) epoxy group-containing vinyl monomer added is (a-1) a polyolefin resin and (a-2) an epoxy group-containing vinyl monomer. (A-3) The adhesive resin composition according to claim 1, which is in the range of 0.1 to 50% by weight based on the total weight of the aromatic vinyl monomer. (B) Acid-modified polyolefin resin is (b-2) α, β-unsaturated carboxylic acid or acid anhydride monomer thereof and (b-1) polyolefin resin in the presence of a radical polymerization initiator and ( b-3) obtained by melt-kneading an aromatic vinyl monomer, and (b-2) the amount of α, β-unsaturated carboxylic acid or acid anhydride monomer added is (b-1) 0.01 to 50% by weight based on the total weight of the polyolefin resin, (b-2) α, β-unsaturated carboxylic acid or acid anhydride monomer and (b-3) aromatic vinyl monomer The adhesive resin composition according to claim 1 or 2, which is in a range. In at least one of the (A) epoxy group-containing modified polyolefin resin and the (B) acid-modified polyolefin resin obtained by modifying a polyolefin resin, the polyolefin resin contains 0.01 to 45% by weight of an ethylene component. The adhesive resin composition according to any one of claims 1 to 3 , which is a copolymer. (B-2) The adhesive resin composition according to claim 3 or 4 , wherein the α, β-unsaturated carboxylic acid or acid anhydride monomer thereof is maleic anhydride. (A) After the epoxy group-containing modified polyolefin resin is melt-kneaded (a-1) a polyolefin resin and a radical polymerization initiator, then (a-3) an epoxy group-containing vinyl monomer, (a-4) aroma The adhesive resin composition according to any one of claims 2 to 5 , wherein the adhesive resin composition is obtained by adding a group vinyl monomer and melt-kneading. (B) After the acid-modified polyolefin resin is melt-kneaded (b-1) a polyolefin resin and a radical polymerization initiator, and (b-2) an α, β-unsaturated carboxylic acid or an acid anhydride monomer thereof, The adhesive resin composition according to any one of claims 3 to 6 , which is obtained by adding (b-3) an aromatic vinyl monomer and then melt-kneading. Against adhesive resin composition 100 parts by weight of any one of claim 1 to 7 adhesive polyolefin-based resin composition containing a polypropylene resin 0.1 parts by weight of propylene units is a major amount object. A sheet-like or film-like molded article comprising the adhesive resin composition according to any one of claims 1 to 8 and having heat-weldability. The adhesive body formed by adhering with the at least 1 adhesive resin composition of Claims 1-8 , and / or the sheet-like or film-shaped molded object of Claim 9 . A method for producing a sheet-like or film-like molded product, comprising melt-kneading the adhesive resin composition according to any one of claims 1 to 8 and then molding the sheet-like or film-like product.