JP6353464B2 - Modified polyolefin resin, composition, adhesive, primer, binder and laminate - Google Patents

Description

  The present invention relates to a modified polyolefin resin.

  In general, polyolefin resins such as polypropylene resins and polyethylene resins are inexpensive and have many excellent properties such as moldability, chemical resistance, water resistance, and electrical properties. Widely adopted. However, unlike a polar base material such as a polyurethane resin, a polyamide resin, an acrylic resin, or a polyester resin, a polyolefin resin base material is nonpolar and crystalline, and thus is difficult to paint or bond.

  Chlorinated polyolefin resins are widely used because they have adhesion to non-polar substrates as described above. A chlorinated polyolefin resin has a problem of dehydrochlorination, and is therefore unsuitable for adhesion between a polyolefin resin and a metal. For this reason, a non-aqueous dispersion type acid-modified polyolefin-based resin is generally used for adhesion between the polyolefin resin and the metal (Patent Document 1 and Patent Document 2). However, the adhesive based on the above-mentioned acid-modified polyolefin resin has a problem that roll contamination is likely to occur. In addition, in order to develop adhesive strength, there is a problem related to adhesive strength, such as requiring heat sealing at a temperature exceeding 200 ° C. In order to solve these problems, solution-type acid-modified polyolefin resins have been developed.

JP 2011-256339 A JP 2010-086744 A

  However, although solution-type acid-modified polyolefin-based resins are improved with respect to problems such as roll contamination, further improvements are required in terms of adhesive strength. In addition, the solution of the acid-modified polyolefin resin has a new problem that the stability at low temperature is low.

  Accordingly, an object of the present invention is to provide a modified polyolefin resin that is excellent in adhesion to a resin such as a polyolefin resin and a metal and excellent in stability of a solution at a low temperature.

The present invention provides the following [1] to [11].
[1] Modification in which component (A): polyolefin resin is graft-modified with component (B): α, β-unsaturated carboxylic acid and / or derivative thereof, and component (C): (meth) acrylic acid ester It is a polyolefin resin, the melting point of the modified polyolefin resin by a differential scanning calorimeter is 91 ° C. or more and less than 120 ° C., and the weight average molecular weight of the modified polyolefin resin is 100,000 or more and 200,000 or less, Modified polyolefin resin that is soluble in solvents.
[2] The modified polyolefin resin according to the above [1], wherein the component (C) contains at least a compound represented by the general formula (I).
CH ₂ = CR ₁ COOR ₂ (I)
(In formula (I), R ₁ represents H or CH ₃ , R ₂ represents C _n H _{2n + 1} , and n represents an integer of 8 to 18)
[3] The above [1], wherein the component (A) contains at least one selected from the group consisting of an ethylene-propylene copolymer, a propylene-1-butene copolymer, and an ethylene-propylene-1-butene copolymer. ] Or the modified polyolefin resin according to [2].
[4] The above [1] to [3], wherein at least one of the graft weight of component (B) and the graft weight of component (C) in the modified polyolefin resin is 0.1 wt% or more and 10 wt% or less. The modified polyolefin resin according to any one of the above.
[5] A composition comprising the modified polyolefin resin according to any one of [1] to [4].
[6] The composition according to [5], further including one or more components selected from a solution, a curing agent, and an adhesive component.
[7] An adhesive comprising the modified polyolefin resin according to any one of [1] to [4] or the composition according to [5] or [6].
[8] A primer comprising the modified polyolefin resin according to any one of [1] to [4] above or the composition according to [5] or [6] above.
[9] A coating binder containing the modified polyolefin resin according to any one of [1] to [4] or the composition according to [5] or [6].
[10] An ink binder comprising the modified polyolefin resin according to any one of [1] to [4] above or the composition according to [5] or [6] above.
[11] A laminate comprising a layer comprising the modified polyolefin resin according to any one of [1] to [4] above or the composition according to [5] or [6], a metal layer, and a resin layer. .

  The present invention can provide a modified polyolefin resin that is excellent in adhesion between a resin and a metal including a nonpolar resin such as a polyolefin resin and excellent in stability of a solution at a low temperature.

  The modified polyolefin resin of the present invention is a modified polyolefin resin in which component (A) is graft-modified with component (B) and component (C). Components (A) to (C) will be described later. The modified polyolefin resin has a melting point (Tm) of 91 ° C. or more and less than 120 ° C. by a differential scanning calorimeter (DSC), and a weight average molecular weight of 100,000 or more and 200,000 or less.

  The reason why the modified polyolefin resin of the present invention exhibits an excellent effect is presumed as follows. In general, if the weight average molecular weight of the modified polyolefin resin is too large, the solubility in a solvent tends to decrease, and a stable solution tends to be difficult to obtain. On the other hand, if the weight average molecular weight is too small, good adhesion tends to be difficult to obtain. If the melting point of the modified polyolefin-based resin is low, the adhesive force cannot be maintained in the processing step after bonding, and satisfactory adhesion tends to be difficult to obtain. On the other hand, if the melting point is too high, adhesion at low temperatures, good solvent solubility, and stability of the solution at low temperatures tend to be difficult to obtain.

  On the other hand, the modified polyolefin resin of the present invention includes a graft component derived from the components (B) and (C), and exhibits an excellent effect because the melting point and the weight average molecular weight are within a predetermined range. It is considered possible.

  In the present invention, the weight average molecular weight of the modified polyolefin resin is 100,000 or more, preferably 120,000 or more. Thereby, sufficient adhesive force can be expressed. The upper limit is 200,000 or less, preferably 180,000 or less. Thereby, sufficient solvent solubility can be obtained. Therefore, the weight average molecular weight of the modified polyolefin resin is 100,000 or more and 200,000 or less, and preferably 120,000 or more and 180,000 or less. The weight average molecular weight in the present invention including the examples is a value calculated by measuring with gel permeation chromatography (standard substance: polystyrene).

  In this invention, melting | fusing point by the differential scanning calorimeter of a modified polyolefin resin is 91 degreeC or more, and it is preferable that it is 95 degreeC or more. Thereby, sufficient adhesive strength can be obtained. On the other hand, the melting point is less than 120 ° C., preferably 110 ° C. or less, and more preferably 105 ° C. or less. Thereby, adhesiveness at low temperature and solution stability are good, and sufficient storage stability at low temperature can be obtained. Accordingly, the melting point is 91 ° C. or higher and lower than 120 ° C., preferably 91 ° C. or higher and 115 ° C. or lower, and more preferably 95 ° C. or higher and 105 ° C. or lower.

  The measurement of Tm by DSC in the present invention can be performed, for example, under the following conditions. In accordance with JIS K7121-1987 of Japanese Industrial Standards, using a DSC measuring device (manufactured by Seiko Denshi Kogyo), about 5 mg of sample is kept at 150 ° C for 10 minutes by heating and melting, and then cooled at a rate of 10 ° C / minute Then, after stably maintaining at −50 ° C., the melting peak temperature is measured when the temperature is further raised to 150 ° C. at 10 ° C./min to melt, and the temperature is evaluated as Tm. In the examples described later, Tm is measured under the conditions described above.

  Component (A) is a polyolefin resin. The polyolefin resin is not particularly limited as long as it is a polymer of one or more olefin components. Examples of the polyolefin resin include homopolymers of α-olefins having 2 to 6 carbon atoms (such as homopolymers of ethylene or propylene); random copolymers and block copolymers of ethylene or propylene and other comonomers. Illustrated. Examples of other comonomers include 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. Component (A) may be one type of polyolefin resin or two or more types. The component (A) preferably contains at least one selected from the group consisting of an ethylene-propylene copolymer, a propylene-1-butene copolymer, and an ethylene-propylene-1-butene copolymer. More preferably, it contains a 1-butene copolymer. When the polyolefin resin contains a butene component, the molar ratio of the butene component is preferably 5 to 30%, more preferably 10 to 25% of the entire polyolefin resin. When the polyolefin resin contains a propylene component, the molar ratio of the propylene component is preferably 40 to 90%, more preferably 65 to 80% of the entire polyolefin resin. When the polyolefin resin contains an ethylene component, the molar ratio of the ethylene component is preferably 3 to 20%, more preferably 5 to 10% of the entire polyolefin resin. The method for producing the polyolefin resin is not particularly limited.

  Component (B) is an α, β-unsaturated carboxylic acid and / or a derivative thereof. α, β-unsaturated carboxylic acid and its derivatives include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, hymic anhydride Examples thereof include acid and (meth) acrylic acid, and maleic anhydride is preferred. Component (B) may be one or more compounds selected from α, β-unsaturated carboxylic acids and derivatives thereof, a combination of one or more α, β-unsaturated carboxylic acids and one or more derivatives thereof, A combination of two or more α, β-unsaturated carboxylic acids or a combination of two or more derivatives of α, β-unsaturated carboxylic acids may be used.

  In the present specification, “(meth) acrylic acid” means methacrylic acid and / or acrylic acid. “(Meth) acrylate” means methacrylate and / or acrylate.

  The graft weight of the component (B) in the modified polyolefin resin is preferably 0.1% by weight or more, more preferably 0.5% by weight or more when the modified polyolefin resin is 100% by weight. More preferred. Thereby, the adhesiveness with respect to a metal adherend of the modified polyolefin resin obtained can be maintained. The upper limit is preferably 10% by weight or less, and more preferably 4% by weight or less. Thereby, generation | occurrence | production of a graft unreacted substance can be prevented and sufficient adhesiveness with respect to a resin adherend can be acquired. Therefore, the graft weight of the component (B) is preferably 0.1% by weight or more and 10% by weight or less, more preferably 0.5% by weight or more and 4% by weight or less.

  The graft weight (% by weight) of the component (B) can be measured by a known method. For example, it can be determined by alkali titration or Fourier transform infrared spectroscopy.

  Component (C) is a (meth) acrylic acid ester. The (meth) acrylic acid ester is an ester of acrylic acid or methacrylic acid. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meta ) Acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate , Phenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N, N-di Chill aminoethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate.

The component (C) preferably contains a (meth) acrylic acid ester represented by the general formula (I), and more preferably a (meth) acrylic acid ester represented by the general formula (I).
CH ₂ = CR ₁ COOR ₂ (I)
Thereby, it can suppress that the molecular weight of a component (A) falls when synthesize | combining modified polyolefin resin. In addition, the molecular weight distribution of the modified polyolefin resin can be narrowed, and the properties such as solvent solubility of the modified polyolefin resin, low temperature stability of the solution, compatibility with other resins in the adhesive composition, adhesiveness, etc. Can be improved. The component (C) may contain the (meth) acrylic acid ester represented by the general formula (I) alone, or may contain a plurality of types in combination at any ratio.

In the general formula (I), R ₁ represents H or CH ₃ and is preferably CH ₃ . R ₂ represents C _n H _{2n + 1} . n represents an integer of 8 to 18, and n is preferably an integer of 8 to 15, more preferably an integer of 8 to 14, and still more preferably an integer of 8 to 13. As the compound represented by the formula (I), lauryl (meth) acrylate and octyl (meth) acrylate are preferable, and lauryl methacrylate and octyl methacrylate are more preferable.

  The graft weight of component (C) in the modified polyolefin resin is preferably 0.1% by weight or more, more preferably 0.5% by weight or more when the modified polyolefin resin is 100% by weight. It is. Thereby, the molecular weight distribution of the modified polyolefin resin can be kept in a sufficiently narrow range. That is, the adverse effect of the high molecular weight portion can be suppressed, and the solvent solubility, the low temperature stability of the solution, and the compatibility with other resins can be maintained well. Moreover, the adhesive force can be improved by suppressing the adverse effect of the low molecular weight portion. The upper limit is preferably 10% by weight or less, more preferably 4% by weight or less. Thereby, generation | occurrence | production of an unreacted graft can be suppressed and the adhesiveness with respect to adherends, such as resin and a metal, can be hold | maintained favorably. Therefore, the graft weight of the component (C) is preferably 0.1% by weight or more and 10% by weight or less, more preferably 0.5% by weight or more and 4% by weight or less.

The graft weight (% by weight) of component (C) can be measured by a known method. For example, it can be determined by Fourier transform infrared spectroscopy or ¹ H-NMR.

  Component (C) may be one or more (meth) acrylic acid esters, and may be a combination of two or more (meth) acrylic acid esters.

  Either of the graft weight of component (B) and the graft weight of component (C) in the modified polyolefin resin is preferably 0.1 wt% or more and 10 wt% or less, and both are 0.1 wt% More preferably, the content is 10% by weight or less.

  Depending on the application and purpose, a graft component (other graft component) other than components (B) and (C) may be used in combination as long as the properties of the present invention are not impaired. For example, (meth) acrylic acid derivatives other than the component (C) (for example, N-methyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, (meth) acryloylmorpholine, etc.) can be mentioned. Other graft components may be used alone or in combination of two or more. The graft weight of the other graft components (the sum of them in the case of a plurality of combinations) is not particularly limited, but preferably does not exceed the sum of the graft weights of components (B) and (C).

  The method for producing the modified polyolefin resin can be obtained by graft polymerization of the component (B) and the component (C) to the component (A). In the production, component (D): radical generator may be used.

  The radical generator may be a known radical generator, and is preferably an organic peroxide compound. Examples of organic peroxide compounds include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide. 1,4-bis [(t-butylperoxy) isopropyl] benzene, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butylper) Oxy) -cyclohexane, cyclohexanone peroxide, t-butylperoxybenzoate, t-butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2- Ethyl hexanoate, t-butyl peroxyisop Pills carbonate, include cumylperoxy octoate, etc., di -t- butyl peroxide, dicumyl peroxide and dilauryl peroxide are preferred, dilauryl peroxide is more preferred. Component (D) may be a single radical generator or a combination of a plurality of radical generators.

  As a method for producing a modified polyolefin resin using component (D), for example, a mixture of components (A), (B) and (C) is heated and dissolved in an organic solvent such as toluene and xylene, and then component (D ) And the components (A), (B), (C) and (D) are added using a kneading machine such as a Banbury mixer, a kneader, or an extruder, and the melt kneading reaction is performed under heating. A method for obtaining a modified polyolefin-based resin is mentioned. In the production of the modified polyolefin resin, the components (A), (B), (C) and (D) may be added to the reaction system all at once or sequentially.

  The addition amount of component (D) in the graft polymerization reaction is preferably 1% by weight, more preferably 10%, based on the total amount (weight) of the addition amount of component (B) and the addition amount of component (C). % By weight. Thereby, sufficient grafting efficiency can be maintained. The upper limit is preferably 100% by weight or less, and more preferably 50% by weight or less. Thereby, the fall of the weight average molecular weight of modified polyolefin resin can be suppressed.

  The modified polyolefin resin of the present invention can exhibit stability (solution stability) when mixed with a solvent to form a solution, particularly solution stability at low temperatures (for example, 25 ° C. or less, 5 ° C. or more). it can. In addition, the modified polyolefin resin of the present invention can exhibit excellent adhesion between a metal and a resin, and since it has solution stability at a low temperature, it also has excellent adhesion at a low temperature. Examples of the metal include aluminum, aluminum alloy, nickel, and stainless steel. Examples of the resin include nonpolar resins such as polyolefin resins, polyurethane resins, polyamide resins, acrylic resins, and polyester resins. Therefore, the modified polyolefin resin of the present invention can be used as an adhesive, a primer, a paint binder and an ink binder or as these components.

  The modified polyolefin resin of the present invention may be used as a composition in combination with other components. The composition of the present invention only needs to contain a modified polyolefin resin, and other components are not particularly limited. Examples of other components include a curing agent, an adhesive component, and a solvent.

  Examples of the curing agent include polyisocyanate compounds, epoxy compounds, polyamine compounds such as isophorone diamine, polyol compounds, and crosslinking agents in which their functional groups are blocked with protecting groups. A hardening | curing agent may be individual and may be a combination of multiple types. The compounding quantity of a hardening | curing agent can be suitably selected with content of the component (B) in the modified polyolefin resin of this invention. When the composition of the present invention contains a curing agent, it may contain a catalyst. Examples of the catalyst include organotin compounds and tertiary amine compounds, which may be appropriately selected from these according to the purpose.

  Examples of the adhesive component include known adhesives such as polyester adhesives, polyurethane adhesives, and acrylic adhesives.

  Solvents include aromatic solvents (toluene, xylene, etc.); alicyclic hydrocarbon solvents (cyclohexane, methylcyclohexane, etc.); aliphatic hydrocarbon solvents (hexane, heptane, octane, etc.); ketone solvents (acetone, methyl ethyl ketone, Ester solvents (such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate) glycol solvents (such as ethylene glycol, ethyl cellosolve, and butyl cellosolve); alcohol solvents (methanol, Ethanol, n-butanol, t-butanol, etc.); and mixed solvents thereof are exemplified. The solvent is preferably an aromatic solvent (preferably toluene), an alicyclic hydrocarbon solvent (preferably cyclohexane), or a mixed solvent thereof. The weight ratio of each solvent in the mixed solvent is not particularly limited, but is preferably 6/4 in the case of the aromatic solvent / alicyclic hydrocarbon solvent.

  The composition of this invention should just contain the modified polyolefin resin of this invention, and content ratio with the other component which may be contained as needed is not specifically limited. For example, the content (weight ratio) of the modified polyolefin resin of the present invention relative to the total amount of the composition is preferably 5% by weight or more, more preferably 10% by weight or more, and more preferably 20% by weight or more. Even more preferred. An upper limit is not specifically limited, What is necessary is just to be less than 100 weight%, and it is preferable that it is 95 weight% or less.

  Since the composition of this invention is excellent in adhesiveness with resin and a metal, and solution stability, it can be used as an adhesive agent for metal and / or resin, a primer, a binder for coating materials, and a binder for ink. For example, it is useful as an adhesive in a laminate film such as an aluminum laminate film.

  The modified polyolefin resin or composition of the present invention may be one material of the layers constituting the laminate. The laminate of the present invention has a layer containing the modified polyolefin resin or composition of the present invention, a metal layer, and a resin layer. The arrangement of the layers in the laminate is not particularly limited, but the mode in which the metal layer and the resin layer are positioned with the layer containing the modified polyolefin resin or composition interposed therebetween, the first resin layer and the second resin with the metal layer interposed therebetween A mode in which a layer exists and a layer containing a modified polyolefin resin or composition is sandwiched between the metal layer and each resin layer is exemplified. The laminate of the present invention may be used as an exterior material for lithium ion secondary batteries, capacitors, electric double layer capacitors and the like, and is preferably used.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these.

Example 1
2. Propylene-1-butene copolymer (propylene component 80 mol%, butene component 20 mol%, weight average molecular weight 250,000, Tm = 100 ° C.) 100 parts by weight, maleic anhydride 3.5 parts by weight, octyl methacrylate 5 parts by weight and 2 parts by weight of dilauryl peroxide were subjected to a kneading reaction using a twin screw extruder set at 170 ° C. In the extruder, vacuum degassing was performed to remove the remaining unreacted materials. The weight average molecular weight was 180,000, Tm = 100 ° C., the graft weight of maleic anhydride was 3.1% by weight, and the graft weight of octyl methacrylate. Of 3.0% by weight was obtained.

  In addition, including the following Examples and Comparative Examples, the graft weight of α, β-unsaturated carboxylic acid and its derivatives was measured by alkali titration method, and the graft weight of (meth) acrylic acid ester was determined by 1H-NMR. It was measured.

(Example 2)
100 parts by weight of propylene-1-butene copolymer (propylene component 75 mol%, butene component 25 mol%, weight average molecular weight 180,000, Tm = 108 ° C.) is dissolved in xylene, and maleic anhydride is 4.5 wt. Then, 4.2 parts by weight of octyl methacrylate was added and stirred to be uniform, and then 2 parts by weight of dilauryl peroxide was added successively over 30 minutes to react. After completion of the reaction, vacuum deaeration is performed in an explosion-proof extruder to remove the remaining unreacted material, the weight average molecular weight is 185,000, Tm = 108 ° C., and the graft weight of maleic anhydride is 3.0% by weight. Then, a modified polyolefin resin having an octyl methacrylate graft weight of 3.0% by weight was obtained.

(Example 3)
100 parts by weight of propylene-1-butene copolymer (83 mol% of propylene component, 17 mol% of butene component, weight average molecular weight 170,000, Tm = 93 ° C.) is placed in a four-necked flask and placed in a 120 ° C. oil bath. After dissolution, 3.7 parts by weight of maleic anhydride and 3.7 parts by weight of octyl methacrylate were added and stirred to be uniform, and then 2 parts by weight of dilauryl peroxide were added over 30 minutes and reacted. After completion of the reaction, vacuum deaeration is performed using a vacuum pump to remove the remaining unreacted substances, the weight average molecular weight is 186,000, Tm = 93 ° C., the graft weight of maleic anhydride is 3.2% by weight, A modified polyolefin resin having a graft weight of octyl methacrylate of 2.9% by weight was obtained.

Example 4
100 parts by weight of propylene-1-butene copolymer (propylene component 75 mol%, butene component 25 mol%, weight average molecular weight 110,000, Tm = 108 ° C.) is dissolved in xylene, and maleic anhydride is 4.5 wt. Then, 4.2 parts by weight of octyl methacrylate was added and stirred to be uniform, and then 2 parts by weight of dilauryl peroxide was added successively over 30 minutes to react. After completion of the reaction, vacuum deaeration is performed in an explosion-proof extruder to remove the remaining unreacted material, the weight average molecular weight is 121,000, Tm = 108 ° C., and the graft weight of maleic anhydride is 3.2% by weight. A modified polyolefin resin having an octyl methacrylate graft weight of 3.2% by weight was obtained.

(Example 5)
100 parts by weight of propylene-1-butene copolymer (83 mol% of propylene component, 17 mol% of butene component, weight average molecular weight 100,000, Tm = 93 ° C.) is placed in a four-necked flask and placed in a 120 ° C. oil bath. After dissolution, 3.7 parts by weight of maleic anhydride and 3.7 parts by weight of octyl methacrylate were added and stirred to be uniform, and then 2 parts by weight of dilauryl peroxide were added over 30 minutes and reacted. After completion of the reaction, vacuum deaeration is performed using a vacuum pump to remove the remaining unreacted materials, the weight average molecular weight is 119,000, Tm = 93 ° C., the graft weight of maleic anhydride is 3.0% by weight, A modified polyolefin resin having an octyl methacrylate graft weight of 2.8% by weight was obtained.

(Example 6)
100 parts by weight of propylene-1-butene copolymer (70 mol% of propylene component, 30 mol% of butene component, weight average molecular weight 100,000, Tm = 118 ° C) is put into a four-necked flask and placed in an oil bath at 120 ° C. After dissolution, 3.7 parts by weight of maleic anhydride and 3.4 parts by weight of lauryl methacrylate were added, and the mixture was stirred so as to be uniform, and then 2 parts by weight of dilauryl peroxide was added successively over 30 minutes for reaction. After completion of the reaction, vacuum deaeration is performed using a vacuum pump to remove the remaining unreacted material, the weight average molecular weight is 118,000, Tm = 117 ° C., the graft weight of maleic anhydride is 3.0% by weight, A modified polyolefin resin having a lauryl methacrylate graft weight of 2.8% by weight was obtained.

(Example 7)
100 parts by weight of an ethylene-propylene copolymer (ethylene component 10 mol%, propylene component 90 mol%, weight average molecular weight 100,000, Tm = 115 ° C.) was placed in a four-necked flask and dissolved in an oil bath at 120 ° C. Thereafter, 3.9 parts by weight of maleic anhydride and 3.5 parts by weight of lauryl methacrylate were added and stirred to be uniform, and then 2 parts by weight of dilauryl peroxide were successively added over 30 minutes to cause reaction. After completion of the reaction, vacuum deaeration is performed using a vacuum pump to remove the remaining unreacted substances, the weight average molecular weight is 120,000, Tm = 113 ° C., the graft weight of maleic anhydride is 3.2% by weight, A modified polyolefin resin having a lauryl methacrylate graft weight of 2.8% by weight was obtained.

(Example 8)
100 parts by weight of ethylene-propylene-1-butene copolymer (ethylene component 5%, propylene component 75 mol%, butene component 20 mol%, weight average molecular weight 175,000, Tm = 105 ° C.) is dissolved in xylene, After adding 4.5 parts by weight of maleic anhydride and 4.2 parts by weight of octyl methacrylate and stirring the mixture uniformly, 2 parts by weight of dilauryl peroxide was added and reacted over 30 minutes. After completion of the reaction, vacuum deaeration is performed in an explosion-proof extruder to remove the remaining unreacted material, the weight average molecular weight is 195,000, Tm = 105 ° C., and the graft weight of maleic anhydride is 3.0% by weight. Then, a modified polyolefin resin having an octyl methacrylate graft weight of 3.0% by weight was obtained.

(Comparative Example 1)
Instead of the propylene-1-butene copolymer of Example 1, the same propylene-1-butene copolymer was used except that the weight average molecular weight was 80,000. This copolymer was modified in the same manner as in Example 1. The resulting modified polyolefin resin had a weight average molecular weight of 45,000, Tm = 80 ° C., a graft weight of maleic anhydride of 1.3% by weight, and a graft weight of octyl methacrylate of 1.5% by weight.

(Comparative Example 2)
A propylene-ethylene copolymer (propylene component 92 mol%, ethylene component 8 mol%; weight average molecular weight 220,000, Tm = 120 ° C.) was used in place of the propylene-1-butene copolymer of Example 1. Was modified in the same manner as in Example 1. The resulting modified polyolefin resin had a weight average molecular weight of 165,000, Tm = 120 ° C., a maleic anhydride graft weight of 1.1% by weight, and a lauryl methacrylate graft weight of 1.3% by weight.

(Comparative Example 3)
In Example 2, it modified | denatured by the method similar to Example 2 except not having added octyl methacrylate (it was set as 0 weight part). The resulting modified polyolefin resin had a weight average molecular weight of 88,000, Tm = 99 ° C., and a graft weight of maleic anhydride of 2.9% by weight.

(Evaluation test)
For the modified polyolefin resins obtained in Examples 1 to 8 and Comparative Examples 1 to 3, toluene / cyclohexane = 6/4 (W / W) solution samples were prepared so as to be 15% by weight, respectively. The mixture was uniformly mixed so that the molar equivalent ratio [amino group / carboxyl group] = 1.5. Table 1 shows the results of performance evaluation of the obtained solution samples according to the following procedure.

<Test 1: Solution stability test>
The solution sample was put in a sealed glass bottle and stored at 5 ° C. for 7 days, and then visually evaluated for appearance.

<Test 2: Adhesive strength test>
The solution sample was applied as an adhesive with a # 16 Meyer bar on a 1.0 mm thick SUS304-2B plate and an aluminum foil so that the resin dry film thickness was 2 μm, and dried at 180 ° C. for 10 seconds. The coated aluminum foil was bonded to an unstretched polypropylene (CPP) sheet and thermocompression bonded under conditions of 200 kPa at 120 ° C. for 3 seconds to prepare a test piece cut out to a width of 15 mm. After the test piece was stored at 23 ° C. and 50% relative humidity for 24 hours at constant temperature and humidity, the laminate adhesive strength was measured under the conditions of 180-degree direction peeling and peeling speed of 100 mm / min.

  As is clear from Table 1, the modified polyolefin resins of Examples 1 to 8 are excellent in adhesiveness between the aluminum foil and the polypropylene sheet, and simultaneously have low-temperature storage stability of the solution. On the other hand, the modified polyolefin resin of Comparative Example 1 whose weight average molecular weight and melting point are not within the scope of the present invention was inferior in adhesive strength as compared with Examples 1-8. The modified polyolefin resin of Comparative Example 2 whose melting point is not within the scope of the present invention, and the modified polyolefin resin of Comparative Example 3 having a low molecular weight that is not modified with the component (C) are compared with those of Examples 1-8. Both stability and adhesive strength were inferior.

  These results indicate that the modified polyolefin resin of the present invention has excellent adhesion to both the resin and the metal, and excellent solution stability at low temperatures.

Claims (12)

Component (A): polyolefin resin, component (B): maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, hymic anhydride A modified polyolefin resin graft-modified with an α, β-unsaturated carboxylic acid, which is one or more compounds selected from acids and (meth) acrylic acid, and component (C) :( meth) acrylic acid ester Yes,
According to JIS K7121-1987, the melting point of the modified polyolefin resin measured at a heating rate of 10 ° C./min by a differential scanning calorimeter is 91 ° C. or more and less than 120 ° C.,
The weight average molecular weight of the modified polyolefin resin is from 100,000 to 200,000, and
The graft weight of the component (B) in the modified polyolefin resin is 0.5% by weight or more and 4% by weight or less.
Modified polyolefin resin for application and / or lamination to aluminum members. The modified polyolefin resin according to claim 1, wherein the component (C) contains at least a compound represented by the general formula (I).
CH ₂ = CR ₁ COOR ₂ (I)
(In formula (I), R ₁ represents H or CH ₃ , R ₂ represents C _n H _{2n + 1} , and n represents an integer of 8 to 18) The component (A) contains at least one selected from the group consisting of an ethylene-propylene copolymer, a propylene-1-butene copolymer, and an ethylene-propylene-1-butene copolymer. The modified polyolefin resin as described. Modified polyolefin resin of Ingredient (C) of the graft heavy weight modified polyolefin resin according to any one of claims 1 to 3 is 10 wt% or less than 0.1 wt%. The composition for application | coating to the aluminum member containing the modified polyolefin resin of any one of Claims 1-4, and / or a lamination | stacking. The composition according to claim 5, further comprising one or more curing agents selected from a polyisocyanate compound, an epoxy compound, a polyamine compound, a polyol compound, and a crosslinking agent whose functional group is blocked with a protective group. Further comprising one or more components selected from solvent Eki及 Beauty adhesive component composition of claim 6. The adhesive for aluminum members containing the modified polyolefin resin of any one of Claims 1-4, or the composition of any one of Claims 5-7 . The primer for aluminum members containing the modified polyolefin resin of any one of Claims 1-4, or the composition of any one of Claims 5-7. A binder for paint for aluminum members comprising the modified polyolefin resin according to any one of claims 1 to 4 or the composition according to any one of claims 5 to 7 . The binder for ink for aluminum members containing the modified polyolefin resin of any one of Claims 1-4, or the composition of any one of Claims 5-7. It has a layer containing the modified polyolefin resin according to any one of claims 1 to 4 or the composition according to any one of claims 5 to 7 , a metal layer and a resin layer, wherein the metal is aluminum. A laminate in which the layer containing the modified polyolefin resin or composition and the metal layer are in direct contact.