阅读说明：本技术 改性聚烯烃树脂 (Modified polyolefin resin ) 是由 小野勇 近藤圭 木村浩司 竹中天斗 名原悠子 关口俊司 于 2019-11-26 设计创作，主要内容包括：本发明的课题在于,提供无论基础树脂的种类如何,即使使用具有环状结构的α,β-不饱和羧酸衍生物进行接枝改性,也可得到所期望的附着力的改性聚烯烃树脂；所述改性聚烯烃树脂为聚烯烃树脂的改性物,且满足下述条件(A)和(B)。条件(A)：改性成分含有具有环状结构的α,β-不饱和羧酸衍生物。条件(B)：用式(1)表示的开环度为40以上。(1)：开环度=改性度K×开环率R。在式(1)中,改性度K表示α,β-不饱和羧酸衍生物的接枝重量(重量%),开环率R表示α,β-不饱和羧酸衍生物中的环状结构的开环率(%)。(The present invention addresses the problem of providing a modified polyolefin resin that can achieve a desired adhesion force regardless of the type of base resin, even when graft-modified using an α, β -unsaturated carboxylic acid derivative having a cyclic structure; the modified polyolefin resin is a modified product of a polyolefin resin and satisfies the following conditions (A) and (B). Condition (a): the modifying component contains an alpha, beta-unsaturated carboxylic acid derivative having a cyclic structure. Condition (B): the degree of ring opening represented by formula (1) is 40 or more. (1): degree of ring opening = degree of modification K × ring opening ratio R. In formula (1), the modification degree K represents the graft weight (wt%) of the α, β -unsaturated carboxylic acid derivative, and the ring-opening ratio R represents the ring-opening ratio (%) of the cyclic structure in the α, β -unsaturated carboxylic acid derivative.)

1. A modified polyolefin resin which is a modified product of a polyolefin resin and satisfies the following conditions (A) and (B),

condition (a): the modifying component contains an alpha, beta-unsaturated carboxylic acid derivative having a cyclic structure,

condition (B): the degree of ring opening represented by the following formula (1) is 40 or more,

(1): degree of opening = degree of modification K × degree of opening R,

in the formula (1), the modification degree K represents a graft weight (wt%) of the α, β -unsaturated carboxylic acid derivative, and the ring-opening ratio R represents a ring-opening ratio (%) of a cyclic structure in the α, β -unsaturated carboxylic acid derivative.

2. The modified polyolefin resin according to claim 1, having a melting point of 50 ℃ or higher.

3. The modified polyolefin resin according to claim 1 or 2, which has a weight average molecular weight of 10,000 or more.

Technical Field

The present invention relates to a modified polyolefin resin.

Background

Polyolefin resins such as polypropylene and polyethylene are excellent in mechanical properties such as tensile strength, tear strength and impact strength, and in water resistance and chemical resistance. Further, polyolefin resins have various excellent properties such as light weight, low cost, and good moldability. Therefore, polyolefin resins are used for various applications such as sheets, films, and molded articles. However, unlike acrylic resins and polyester resins, they have a disadvantage of being difficult to coat and adhere because they are nonpolar and have good crystallinity.

Chlorinated polyolefin resins are widely used as polyolefin resins having improved adhesion to nonpolar resin substrates. However, chlorinated polyolefin resins have a problem of hydrochloric acid removal, and therefore are considered to be unsuitable for adhesion of polyolefin resins to metals.

Therefore, for the adhesion of a polyolefin resin to a metal, an adhesive based on a nonaqueous dispersion type acid-modified polyolefin resin is generally used.

In addition, in recent years, applications requiring heat resistance have been increasing, and it is known to use a resin having a high melting point in order to solve this problem (for example, see patent document 1). In the technique described in patent document 1, although heat resistance is improved by containing a high-melting-point resin, solution stability may be lowered. Therefore, a modified polyolefin resin having good solution properties and heat resistance has been proposed (for example, see patent document 2).

Disclosure of Invention

Problems to be solved by the invention

The modified polyolefin resin described in patent document 2 uses polyolefin resins having different melting points, and is graft-modified with an α, β -unsaturated carboxylic acid anhydride such as maleic anhydride.

The modified polyolefin resin of patent document 2 is poor in versatility because it uses a polyolefin resin having a melting point different from that of the base resin. Further, it is known that graft modification using an unsaturated carboxylic acid such as maleic anhydride or an anhydride monomer thereof causes degradation (reduction in molecular weight) of polyolefin (for example, see non-patent document 1), and thus adhesion is sometimes reduced.

The present invention addresses the problem of providing a modified polyolefin resin that can achieve a desired level of adhesion regardless of the type of base resin, even when graft-modified using an α, β -unsaturated carboxylic acid derivative having a cyclic structure.

Means for solving the problems

The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that the above problems can be solved by specifying a numerical value of a ring opening degree represented by a predetermined numerical formula in a modified product of a polyolefin resin, and have completed the present invention.

Namely, the present inventors provide the following [1] to [3 ].

[1] A modified polyolefin resin which is a modified product of a polyolefin resin and satisfies the following conditions (A) and (B),

condition (a): the modifying component contains an alpha, beta-unsaturated carboxylic acid derivative having a cyclic structure,

condition (B): the degree of ring opening represented by the following formula (1) is 40 or more,

(1): degree of opening = degree of modification K × degree of opening R,

in the formula (1), the modification degree K represents a graft weight (wt%) of the α, β -unsaturated carboxylic acid derivative, and the ring-opening ratio R represents a ring-opening ratio (%) of a cyclic structure in the α, β -unsaturated carboxylic acid derivative.

[2] The modified polyolefin resin according to the above [1], which has a melting point of 50 ℃ or higher.

[3] The modified polyolefin resin according to the above [1] or [2], which has a weight average molecular weight of 10,000 or more.

ADVANTAGEOUS EFFECTS OF INVENTION

The modified polyolefin resin of the present invention can obtain a desired adhesive force regardless of the kind of the base resin even when graft-modified with an α, β -unsaturated carboxylic acid derivative having a cyclic structure.

Detailed Description

The present invention will be described in detail below based on preferred embodiments thereof. In the present specification, the expression "AA to BB" means AA or more and BB or less. The "melting point" is a value measured by a differential scanning calorimeter (hereinafter referred to as "DSC"). Further, "weight average molecular weight" is a value measured by Gel Permeation Chromatography (GPC) using polystyrene standards.

[ modified polyolefin resin ]

The modified polyolefin resin of the present invention is a modified product of a polyolefin resin, and satisfies the following conditions (a) and (B).

Condition (a): the modifying component contains an alpha, beta-unsaturated carboxylic acid derivative having a cyclic structure.

Condition (B): the degree of ring opening represented by the following formula (1) is 40 or more.

(1): degree of ring opening = degree of modification K × ring opening ratio R

(in the formula (1), the modification degree K represents the graft weight (wt%) of the α, β -unsaturated carboxylic acid derivative, and the ring-opening ratio R represents the ring-opening ratio (%) of the cyclic structure in the α, β -unsaturated carboxylic acid derivative.)

Since the modified polyolefin resin satisfies the condition (a), a structure in which an α, β -unsaturated carboxylic acid derivative having a cyclic structure is graft-polymerized to a polyolefin resin is obtained.

Since the modified polyolefin resin satisfies the condition (B), a structure in which at least a part of the ring of the α, β -unsaturated carboxylic acid derivative having a cyclic structure is opened, which is incorporated in the polyolefin resin, is obtained. In the present invention, the cyclic structure of the α, β -unsaturated carboxylic acid derivative may be opened by a water molecule. Therefore, the ring-opened structure has a carboxyl group. That is, in the modified polyolefin resin of the present invention, the ring-opening degree may be referred to as a parameter relating to the amount of carboxyl groups present in the modified polyolefin resin.

Modified polyolefin resins obtained by modifying polyolefin resins with α, β -unsaturated carboxylic acid derivatives having cyclic structures such as maleic anhydride are conventionally known. However, modified polyolefin resins known so far can exhibit various effects by utilizing the cyclic structure of an α, β -unsaturated carboxylic acid derivative introduced into a polyolefin resin in a chemical reaction. Therefore, the cyclic structure of the α, β -unsaturated carboxylic acid derivative introduced into the polyolefin resin is desired to be not ring-opened, that is, the ring-opening degree is desired to be low.

On the other hand, in the modified polyolefin resin of the present invention, the ring opening degree of the cyclic structure of the α, β -unsaturated carboxylic acid derivative introduced into the polyolefin resin is set to a predetermined value or more, that is, the ring opening degree is increased.

The modified polyolefin resin of the present invention has a ring opening degree of 40 or more, preferably 50 or more. When the ring opening degree is 40 or more, a desired adhesive force can be obtained even when graft polymerization is performed using an α, β -unsaturated carboxylic acid derivative having a cyclic structure, regardless of the type of the base resin. The upper limit is preferably 750 or less, more preferably 700 or less.

The ring-opening degree is defined as the product of the modification degree K and the ring-opening ratio R. Details of the modification degree K and the ring-opening ratio R are shown below.

The modification degree K is the graft weight (wt%) of the α, β -unsaturated carboxylic acid derivative. That is, the modification degree K represents the proportion of the α, β -unsaturated carboxylic acid derivative having a cyclic structure introduced into the polyolefin resin. The degree of modification K can be set according to the degree of ring opening of the modified polyolefin resin. The degree of modification K is preferably 0.1 to 20.0% by weight, more preferably 0.2 to 10.0% by weight.

The degree of modification K can be adjusted by the amount of the modifying component and the radical initiator used when the polyolefin resin is modified with the modifying component, the reaction temperature, the reaction time, and the like.

The degree of modification K can be calculated as described below in accordance with JIS K-0070 (1992). That is, about 0.5g of the modified polyolefin resin and about 100g of toluene were precisely weighed and put into a 300ml separable flask equipped with a cooling tube and a thermometer, and the mixture was dissolved with stirring while heating the mixture on a heating stirrer so that the internal temperature became 80 ℃. After the resin was dissolved, 15ml of methanol was added and held for 5 minutes. Then, 5 to 6 drops of an indicator (1% phenolphthalein-methanol solution) was added, and the mixture was titrated with 0.1mol/L potassium hydroxide-ethanol solution. In this case, the degree of modification K of the modified polyolefin resin can be calculated from the following formula based on the amount of titration required for neutralization.

K={B×f×F/(S×1000)}×100

Here, K represents the degree of modification (wt%), B represents the titration amount (ml) of the potassium hydroxide-ethanol solution, F represents a factor of 0.1mol/L of the potassium hydroxide-ethanol solution, F is the formula weight of the α, β -unsaturated carboxylic acid derivative X1/10, and S represents the weight (g) of the modified polyolefin resin.

The ring-opening ratio R is the ring-opening ratio (%) of the cyclic structure in the α, β -unsaturated carboxylic acid derivative. That is, the ring-opening ratio R represents the ring-opening ratio of an α, β -unsaturated carboxylic acid derivative having a cyclic structure incorporated in a polyolefin resin. The ring opening ratio R can be set according to the ring opening degree of the modified polyolefin resin. The ring-opening ratio R is preferably 10 to 80%, more preferably 15 to 75%.

The open loop ratio R can be adjusted by, for example: the modified polyolefin resin is immersed in water while the temperature and time are variously changed, and the modified polyolefin resin is left under a constant humidity condition.

The details of the measurement of the ring opening ratio R are as follows.

First, a modified polyolefin resin is dissolved in an organic solvent to obtain a solution. Then, the solution was applied to a KBr plate and dried,thus, a thin film is formed, and the film is observed with FT-IR (for example, "FT/IR-4100", manufactured by Japan spectral Co., Ltd.) at 400 to 4000cm^-1Infrared absorption spectrum of (1). The analysis was carried out by software (for example, "Spectro Manager", Japan Spectroscopy).

Will be 1700-1750 cm^-1The peak appearing at the wave number is ascribed to the peak derived from the carbonyl group of the ring-opened α -unsaturated carboxylic acid derivative, and the peak height is A. 1750 to 1820cm^-1The peak appearing at the wave number is assigned as a peak derived from the carbonyl group of the α -unsaturated carboxylic acid derivative not ring-opened, and the peak height is counted as B.then, the ring-opening ratio R (%) can be calculated from the formula of (A/(A + B) × 100. the ring-opening ratio in the following examples is a value calculated by this method.

The melting point of the modified polyolefin resin is preferably 50 to 120 ℃, and more preferably 60 to 110 ℃. When the melting point is 50 ℃ or higher, sufficient adhesiveness can be exhibited. On the other hand, when the melting point is 120 ℃ or lower, the adhesiveness and solution stability at low temperatures are good, and sufficient storage stability at low temperatures can be exhibited.

The melting point can be adjusted by, for example, the kind of the base resin of the polyolefin resin.

The details of the measurement of the melting point by DSC are as follows. About 5mg of the sample was kept in a heat-melted state at 150 ℃ for 10 minutes in accordance with JIS K7121(1987) using a DSC measuring apparatus (for example, "DISCOVERY DSC 2500", manufactured by TA Instruments Japan Inc.). The temperature is reduced at the speed of 10 ℃/min and is stably kept at the temperature of minus 50 ℃ for 5 minutes. Then, the melting peak temperature at the time of melting by heating to 150 ℃ again at 10 ℃/min was measured, and this temperature was defined as the melting point. The melting points in the following examples are values calculated by this method.

The modified polyolefin resin of the present invention preferably has a weight average molecular weight of 10,000 to 200,000, more preferably 20,000 to 180,000.

The weight average molecular weight can be adjusted by, for example, the weight average molecular weight of the base resin of the polyolefin resin, the amount of the modifying component used, or the like.

The details of the measurement conditions of GPC are as follows. The weight average molecular weight of the modified polyolefin resins in the following examples is a value measured under the conditions.

Measurement equipment: HLC-8320GPC (TOSOH CORPORATION)

Eluent: tetrahydrofuran (THF)

Column: TSKgel (TOSOH CORPORATION)

Standard substance: polystyrene (manufactured by TOSOH CORPORATION, GL Sciences Inc.)

A detector: differential refractometer (manufactured by TOSOH CORPORATION).

(polyolefin resin)

The polyolefin resin is not particularly limited. As the olefin constituting the polyolefin resin, an α -olefin is preferably used. Examples of the α -olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene.

The polyolefin resin may be 1 olefin polymer alone, or a copolymer of 2 or more olefin polymers. In the case where the polyolefin resin is a copolymer, the polyolefin resin may be a random copolymer or a block copolymer.

The polyolefin resin is more preferably polypropylene (propylene homopolymer), ethylene-propylene copolymer, propylene-1-butene copolymer, or ethylene-propylene-1-butene copolymer, from the viewpoint of exhibiting sufficient adhesion to a nonpolar resin substrate such as a polypropylene substrate.

Here, "polypropylene" means a polymer whose basic unit is a structural unit derived from propylene. "ethylene-propylene copolymer" means a copolymer whose basic units are structural units derived from ethylene and propylene. "propylene-1-butene copolymer" means a copolymer whose basic units are structural units derived from propylene and butene. "ethylene-propylene-1-butene copolymer" means a copolymer whose basic units are structural units derived from ethylene, propylene and butene. These (co) polymers may also contain a small amount of structural units derived from other olefins than the basic units. The content thereof may be in such an amount that the original properties of the resin are not significantly impaired.

The polyolefin resin preferably contains 50 mol% or more of a structural unit derived from propylene in 100 mol% of the structural unit. When the structural unit derived from propylene is contained within the above range, adhesion to a nonpolar resin substrate such as a propylene resin can be maintained.

The polyolefin resin is preferably a polyolefin resin obtained by using a metallocene catalyst as a polymerization catalyst.

As the metallocene catalyst, a known one can be used. The metallocene catalyst is preferably a combination of the following components (1) and (2) and, if necessary, a component (3).

Component (1): metallocene complexes as transition metal compounds of groups 4 to 6 of the periodic Table of the elements with at least one conjugated five-membered ring ligand;

component (2): an ion-exchange layered silicate;

component (3): an organoaluminum compound.

When the metallocene catalyst is used, the polyolefin resin has the following characteristics. The molecular weight distribution of the polyolefin resin becomes narrow. In addition, when the polyolefin resin is a copolymer, the random copolymerization property is excellent, the composition distribution is narrow, and the range of copolymerizable comonomers is wide.

When the ethylene-propylene copolymer or the propylene-1-butene copolymer is a random copolymer, it is preferable that the ethylene-derived structural unit or the butene-derived structural unit is 5 to 50 mol% and the propylene-derived structural unit is 50 to 95 mol% of 100 mol% of the structural units.

The weight average molecular weight of the polyolefin resin may be appropriately set according to the weight average molecular weight of the modified polyolefin resin. For example, when the weight average molecular weight of the modified polyolefin resin is preferably 10,000 to 200,000, more preferably 20,000 to 180,000, the weight average molecular weight of the polyolefin resin is preferably adjusted so that the weight average molecular weight of the obtained modified polyolefin resin falls within this range. More specifically, it is preferable to adjust the weight average molecular weight of the polyolefin resin to an appropriate range, for example, 200,000 or less, by degrading the polyolefin resin under heat or in the presence of radicals.

The weight average molecular weight of the polyolefin resin is a value measured by gel permeation chromatography (GPC, standard substance: polystyrene) in the same manner as described above. The measurement conditions were the same as described above.

The lower limit of the melting point of the polyolefin resin is preferably 50 ℃ or higher, more preferably 60 ℃ or higher. When the melting point of the polyolefin resin is 50 ℃ or higher, sufficient coating film strength can be exhibited when the modified polyolefin resin is used for ink, paint, or the like. Therefore, the adhesion to the substrate can be sufficiently exhibited. In addition, when used as an ink, blocking during printing can be suppressed. The upper limit is preferably 120 ℃ or lower, more preferably 110 ℃ or lower. When the melting point of the polyolefin resin is 120 ℃ or lower, excessive hardening of the coating film can be suppressed when the modified polyolefin resin is used for ink, paint, or the like. Therefore, the coating film can exhibit appropriate flexibility.

One embodiment of the melting point of the polyolefin resin is preferably 50 to 120 ℃, more preferably 60 to 110 ℃.

The melting point of the polyolefin resin can be measured using a DSC measuring apparatus (for example, "DISCOVERY DSC 2500", manufactured by TAInstructions Japan Inc.). More specifically, about 5mg of the sample was melted at 150 ℃ for 10 minutes, and cooled to-50 ℃ at a rate of 10 ℃/min to crystallize. Then, the temperature was raised to 150 ℃ at 10 ℃/min to melt. The melting point was determined as the melting peak temperature at the time of melting.

(modifying Components)

The modifying component contains an alpha, beta-unsaturated carboxylic acid derivative having a cyclic structure. Examples of the α, β -unsaturated carboxylic acid derivative having a cyclic structure include α, β -unsaturated carboxylic acid anhydrides having a cyclic structure such as maleic anhydride, citraconic anhydride, itaconic anhydride, and aconitic anhydride. Among them, maleic anhydride is preferable.

The modifying component may contain a component other than the α, β -unsaturated carboxylic acid derivative having a cyclic structure. Examples thereof include α, β -unsaturated carboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and aconitic acid, methyl (meth) acrylate, ethyl (meth) acrylate, N-butyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, octadecyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, and mixtures thereof, (meth) acrylic acid esters such as acetoacetoxyethyl (meth) acrylate, monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, monobutyl fumarate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, monomethyl maleate, monoethyl maleate, monopropyl maleate, monobutyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, maleimide and N-phenylmaleimide.

As a method for modifying a polyolefin resin with a modifying component, a known method can be used. Examples of such a method include a method in which a polyolefin resin is melted or dissolved in a solvent, and a modifying component and a radical initiator are added to modify the resin.

As the reaction apparatus, for example, an extruder such as a twin screw extruder can be used.

The reaction may be carried out batchwise or continuously.

A graft polymer having a polyolefin as a main chain and a side chain containing a structural unit derived from a modifying component is usually obtained by modifying a polyolefin resin with the modifying component.

[ production method ]

The method for producing the modified polyolefin resin of the present invention is not particularly limited. An example is shown below.

First, a polyolefin resin is prepared. The polyolefin resin can be produced by polymerizing an α -olefin such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, or the like in the presence of a catalyst such as a ziegler-natta catalyst or a metallocene catalyst. The polyolefin resin may be a commercially available one.

Subsequently, the polyolefin resin is modified with a modifying component. The modification method can be carried out by a known method, for example, a graft polymerization method. In the case of graft polymerization, free-radical initiators may also be used. Examples of the method for obtaining the modified polyolefin resin include: a solution method in which a modifying component is dissolved in a solvent such as toluene by heating and a radical initiator is added; a melt kneading method in which a modifying component and a radical initiator are added to a Banbury mixer, a kneader, an extruder, or the like and kneaded. Here, the modifying component may be added at once or successively.

In the graft polymerization reaction, the modifying component is preferably used in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the polyolefin resin from the viewpoint of grafting in a preferred amount.

The radical initiator may be suitably selected from known ones. Among them, organic peroxide compounds are preferable. Examples of the organic peroxide-based compound include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, 1-bis (t-butylperoxy) -3,5, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) -cyclohexane, cyclohexanone peroxide, t-butyl peroxybenzoate, t-butyl peroxyisobutyrate, t-butyl peroxy-3, 5, 5-trimethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisopropylcarbonate, cumyl peroxyoctoate, and 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane. Among them, di-tert-butyl peroxide, dilauryl peroxide, and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane are preferable.

The preferable range of the addition amount of the radical initiator with respect to 100% by mass of the modifying component is as follows. The lower limit of the amount of addition is preferably 1% by mass or more, and more preferably 10% by mass or more. If the amount of the radical initiator added is 1 mass% or more, the grafting efficiency can be ensured. On the other hand, the upper limit of the amount added is preferably 200 mass% or less, more preferably 100 mass% or less. It is economical if the amount of the radical initiator added is 200 mass% or less.

The unreacted material as the modifying component not graft-polymerized with the polyolefin resin can be removed by, for example, extraction with a poor solvent. By doing so, a graft polymer can be obtained.

The modified polyolefin resin of the present invention can be produced by reacting the resulting graft polymer with water molecules in such a manner as to satisfy the condition (B). More specifically, the modified polyolefin resin can be produced by subjecting a modified polyolefin resin to a ring-opening treatment of immersing the resin in water and leaving the resin under a constant humidity condition. In this case, the ring-opening ratio (%) and the ring-opening degree can be adjusted by changing the water temperature or the temperature/humidity of the treatment conditions, the immersion time, or the time during which the sheet is left under constant humidity conditions.

The modified polyolefin resin of the present invention is useful as an intermediate medium for substrates having low adhesion (adhesiveness) and difficult to apply a coating material or the like, and is useful as an adhesive for polyolefin substrates such as polypropylene and polyethylene having insufficient adhesion (adhesiveness). In this case, the substrate may be used regardless of whether it is surface-treated by plasma, corona, or the like. Further, by laminating the modified polyolefin resin of the present invention on the surface of a polyolefin-based substrate by hot-melt method and further applying a coating material or the like thereon, adhesion stability of the coating material or the like can be improved.

In addition, the modified polyolefin resin of the present invention can exhibit excellent adhesion between a metal and a resin. 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 binder for coating materials and a binder for inks, or can be used as a component thereof.

[ composition ]

The modified polyolefin resin of the present invention is usually used as a composition containing the modified polyolefin resin. The composition preferably further contains at least 1 component selected from the group consisting of a solution, a curing agent and an adhesive component in addition to the modified polyolefin resin.

(solution)

One embodiment of the above composition is a resin composition containing a modified polyolefin resin and a solution. The solution may be an organic solvent. Examples of the organic solvent include aromatic solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as methyl ethyl ketone, methyl butyl ketone and ethyl cyclohexanone, and aliphatic or alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, nonane and decane. From the viewpoint of environmental problems, organic solvents other than aromatic solvents are preferred, and mixed solvents of alicyclic hydrocarbon solvents and ester solvents or ketone solvents are more preferred.

The organic solvent may be used alone in 1 kind, or as a mixed solvent of 2 or more kinds.

In order to improve the storage stability of the solution of the resin composition containing the modified polyolefin resin and the solution, 1 kind of alcohol (for example, methanol, ethanol, propanol, isopropanol, butanol) or 2 or more kinds of propylene glycol ethers (for example, propylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol t-butyl ether) may be used alone or in combination. In this case, it is preferable to add 1 to 20% by mass of the organic solvent.

(curing agent)

Another embodiment of the above composition is a composition comprising a modified polyolefin resin and a curing agent. Examples of the curing agent include polyisocyanate compounds, epoxy compounds, polyamine compounds, polyol compounds, and crosslinking agents obtained by blocking functional groups thereof with protecting groups.

The curing agent may be a combination of 1 or more kinds alone.

The blending amount of the curing agent can be appropriately selected depending on the degree of modification K in the modified polyolefin resin. When the curing agent is blended, a catalyst such as an organotin compound or a tertiary amine compound may be used in combination according to the purpose.

(bonding component)

Another embodiment of the above composition is a composition containing a modified polyolefin resin and an adhesive component. As the adhesive component, a known adhesive component such as a polyester adhesive, a polyurethane adhesive, or an acrylic adhesive can be used within a range not to impair the desired effect.

The composition is excellent in adhesion between nonpolar resins such as polyolefin-based substrates and between a nonpolar resin and a metal, and therefore, is useful as an adhesive, a primer, a coating adhesive, and an ink adhesive, and is useful as an adhesive in a laminated film such as an aluminum laminated film.

[ primer, Binder ]

The modified polyolefin resin of the present invention or the above-mentioned composition can be used as a primer, a binder for coating or a binder for ink. The modified polyolefin resin of the present invention or a composition containing the same is excellent in adhesion, solution stability and heat resistance, and therefore can be suitably used as a primer in the case of applying a top coat to a polyolefin substrate such as an automobile bumper or as a coating adhesive excellent in adhesion to a top coat paint or a clear coat.

The primer, the binder for coating or the binder for ink may be used in the form of a solution, powder, sheet or the like according to the application. In addition, additives such as antioxidants, light stabilizers, ultraviolet absorbers, pigments, dyes, and inorganic fillers may be added as necessary.

[ laminate ]

The modified polyolefin resin of the present invention or the composition containing the same can also be used as a laminate. The laminate usually has a layer containing a modified polyolefin resin or the above composition, a metal layer and a resin layer. The arrangement of the layers in the laminate is not particularly limited, and examples thereof include a mode in which the metal layer and the resin layer are positioned with the layer containing the modified polyolefin resin or the composition interposed therebetween, and a mode in which the 1 st resin layer and the 2 nd resin layer are present with the metal layer interposed therebetween and the layer containing the modified polyolefin resin or the composition is interposed between the metal layer and each resin layer. The laminate is useful as an exterior material for lithium ion secondary batteries, capacitors, electric double layer capacitors, and the like.