JP6970095B2 - Modified polyolefin resin - Google Patents

Description

The present invention relates to a modified polyolefin resin.

Polyolefin-based resins such as polypropylene and polyethylene are thermoplastic general-purpose resins, which are inexpensive and have many excellent properties such as moldability, chemical resistance, light resistance, water resistance, and electrical properties. Therefore, sheets and films have been conventionally used. , Used in a wide range of fields such as molded products. However, the base material made of these polyolefin-based resins (hereinafter, also referred to as "polyolefin-based base material") is different from polar base materials such as polyurethane-based resin, polyamide-based resin, acrylic resin, polyester resin, and metal. Since it has low polarity and is crystalline, it is a difficult-to-adhere base material, and has the disadvantage that it is difficult to bond or paint a substance with low polarity, or to bond or paint a substance with high polarity.

As a method for improving the adhesiveness of a polyolefin-based substrate, surface treatment on the substrate has been conventionally performed. Surface treatments include roughening by polishing and introduction of polar groups by oxidizing agents, corona discharge, plasma treatment, and flame treatment, but these have the drawback of gradually reducing the effect of improving adhesiveness, and are generally popular. Not done.

Therefore, a method has been devised in which a pretreatment agent having adhesiveness to the base material is applied to the surface of the base material in advance. Such pretreatment agents have various names depending on the application, and are called, for example, adhesives, binders, primers and the like. As the pretreatment agent, for example, a resin having a predetermined property is used, and a hot melt type that is melted by heat to be a binder or the like, a solvent type that dissolves the resin in a solvent, or a resin is emulsified using a surfactant or the like. Pretreatment agents such as water-based agents are provided.

Specific examples of the pretreatment agent include a binder resin composition containing a carboxyl group-containing chlorinated polypropylene-based random copolymer described in Japanese Patent Application Laid-Open No. 2003-321588 (Patent Document 1), and this resin composition. As a coating composition for binders and primers, a polyolefin-based substrate, a vinyl chloride substrate, a polypropylene (PC) -based substrate, a polyethylene terephthalate (PET) substrate, and an acrylonitrile-butadiene-styrene resin (ABS) group. A method for improving the affinity with a material, a polyamide (nylon) resin base material, and the like to improve the adhesiveness is disclosed.

Further, a non-chlorine-based modified polyolefin resin grafted with a carboxylic acid or a carboxylic acid anhydride has been developed. For example, Japanese Patent Application Laid-Open No. 2001-279048 (Patent Document 2) discloses a modified polyolefin resin composition graft-modified with an unsaturated carboxylic acid derivative and / or an anhydride thereof, and the modified polyolefin resin composition is coated with a coating composition. A method for increasing the affinity with a polypropylene base material and improving the adhesiveness by using it as a substance is disclosed.

Japanese Unexamined Patent Publication No. 2003-321588 Japanese Unexamined Patent Publication No. 2001-279048

In recent years, in order to apply the pretreatment agent to various uses, it has been required to develop a resin composition that exhibits good adhesiveness to various substrates regardless of the presence or absence of chlorination.
However, Patent Document 1 uses a chlorinated resin, and does not relate to a non-chlorinated resin that is preferable for use in a field where dehalogenation is desired from the viewpoint of recent environmental problems.
Further, in Patent Document 2, the adhesiveness to a polypropylene base material which is a polyolefin-based base material and various polar base materials is improved, but it is still sufficient for a base material made of a polycarbonate-based resin, a polystyrene (PS) -based resin, or the like. No good adhesiveness was obtained.
Therefore, an object of the present invention is a modified polyolefin system having excellent adhesion to a polyolefin-based substrate, which is often used in various industrial applications such as packaging materials, and also having excellent adhesion to a polycarbonate-based substrate and a polystyrene-based substrate. To provide resin.

As a result of diligent studies, the present inventors have found that the above-mentioned problems can be solved by a modified polyolefin resin obtained by modifying a polyolefin resin with a specific modifying component containing a compound having a benzene ring. The present invention has been completed.

That is, the present invention provides the following.
[1] Component (A): Polyolefin resin is modified with a modifying component.
A modified polyolefin-based resin comprising a component (B): one or more selected from α, β-unsaturated carboxylic acid and an acid anhydride thereof, and a component (C): a compound having a benzene ring.
[2] The modified polyolefin resin according to [1], wherein the modified component further contains a component (D): (meth) acrylic acid ester.
[3] The modified polyolefin resin according to [2], wherein the component (D) contains a (meth) acrylic acid ester represented by the formula (I).
CH ₂ = CR ¹ COOR ² ... (I)
(In the formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents a group represented by −C _n H _{2n + 1} , and n is an integer of 8 to 18.)
[4] The modified polyolefin resin according to any one of [1] to [3], wherein the component (C) is a compound having a benzyl group.
[5] The modified polyolefin resin according to any one of [1] to [4], wherein the component (A) is a propylene-ethylene copolymer or a propylene-butene copolymer.
[6] The modified polyolefin resin according to any one of [1] to [5], wherein the weight average molecular weight is 5,000 or more and less than 200,000.
[7] The modified polyolefin according to any one of [1] to [6], wherein the content of the component (C) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the component (A). System resin.
[8] A heat sealant containing the modified polyolefin resin according to any one of [1] to [7].
[9] An adhesive containing the modified polyolefin resin according to any one of [1] to [7].
[10] The primer containing the modified polyolefin resin according to any one of [1] to [7].
[11] A binder for a paint containing the modified polyolefin resin according to any one of [1] to [7].
[12] A binder for ink containing the modified polyolefin resin according to any one of [1] to [7].
[13] Component (A): Includes modifying a polyolefin resin with a modifying component to obtain a modified polyolefin resin.
The denatured component is
Component (B): One or more selected from α, β-unsaturated carboxylic acid and its acid anhydride, and Component (C): A method for producing a modified polyolefin resin, which comprises a compound having a benzene ring.
[14] The method for producing a modified polyolefin resin according to [13], wherein the modification is carried out in the order of modification by the component (B) and modification by the component (C).
[15] The method for producing a modified polyolefin resin according to [13] or [14], wherein the modifying component further contains a component (D): (meth) acrylic acid ester.
[16] The method for producing a modified polyolefin resin according to [15], wherein the modification by the component (B) and the modification by the component (D) are performed at the same time.

The present invention also provides the following aspects.
[17] The method for producing a modified polyolefin resin according to [15] or [16], wherein the component (D) contains a (meth) acrylic acid ester represented by the formula (I).
CH ₂ = CR ¹ COOR ² ... (I)
(In the formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents a group represented by −C _n H _{2n + 1} , and n is an integer of 8 to 18.)
[18] The method for producing a modified polyolefin resin according to any one of [13] to [17], wherein the component (C) is a compound having a benzyl group.
[19] The method for producing a modified polyolefin resin according to any one of [13] to [18], wherein the component (A) is a propylene-ethylene copolymer or a propylene-butene copolymer.
[20] The modified polyolefin according to any one of [13] to [19], wherein the content of the component (C) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the component (A). Manufacturing method of based resin.

According to the present invention, it is possible to provide a modified polyolefin-based resin having excellent adhesiveness to a polyolefin-based substrate and having excellent adhesion to a polycarbonate-based substrate and a polystyrene-based substrate.

1. 1. The modified polyolefin-based resin of the present invention The modified polyolefin-based resin of the present invention comprises a component (A): a polyolefin resin modified with a modified component.
The denatured component is
Component (B): One or more selected from α, β-unsaturated carboxylic acid and its acid anhydride, and component (C): a compound having a benzene ring.

<Degeneration>
As used herein, the modification includes graft modification in which the modification component is graft-polymerized on the polyolefin resin, and addition modification in which the modification component is added to the polyolefin resin or the modification component modifying the polyolefin resin. ..
The modified polyolefin resin is a polyolefin resin modified by a modifying component.

<Ingredient (A)>
The polyolefin resin as the component (A) is not particularly limited, and may be a homopolymer of one kind of olefin or a copolymer of two or more kinds of olefins. Examples of the olefin in the monomer unit constituting the polyolefin resin include α-olefins having 2 to 6 carbon atoms (eg, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1). -Octene) is preferred.
Examples of the polyolefin resin include a homopolymer of ethylene or propylene, a copolymer of ethylene and propylene, a copolymer of ethylene and one or more other olefins, and a copolymer of propylene and one or more other olefins. Examples thereof include polymers, preferably a copolymer of ethylene and propylene, a copolymer of ethylene and an α-olefin having 2 to 6 carbon atoms, and a copolymer of propylene and an α-olefin having 2 to 6 carbon atoms. One or more selected from the polymers, more preferably one or more selected from the ethylene-propylene copolymer, the propylene-1-butene copolymer, and the ethylene-propylene-1-butene copolymer. When the polyolefin resin is a copolymer, it may be a random copolymer or a block copolymer.
Further, the component (A) may be a combination of two or more kinds of polyolefin resins.

<Denatured component>
(Component (B))
The component (B) is one or more selected from α, β-unsaturated carboxylic acid and its acid anhydride.
Examples of the α, β-unsaturated carboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, aconitic acid, and (meth) acrylic acid.
Examples of the acid anhydride of α, β-unsaturated carboxylic acid include maleic anhydride, citraconic anhydride, itaconic anhydride, aconitic acid anhydride, hymic anhydride, and (meth) acrylic acid.

The component (B) preferably contains an acid anhydride of α, β-unsaturated carboxylic acid, and more preferably contains maleic anhydride. The component (B) is one or more selected from α, β-unsaturated carboxylic acid and its acid anhydride, and is a combination of one or more α, β-unsaturated carboxylic acid and one or more acid anhydride thereof. , Α, β-unsaturated carboxylic acid 2 or more combinations, α, β-unsaturated carboxylic acid acid anhydride 2 or more combinations may be used.
As used herein, the term "(meth) acrylic acid" means methacrylic acid or acrylic acid.

At the time of denaturation, the blending amount of the component (B) is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, based on the component (A). As a result, the obtained modified polyolefin-based resin has good adhesiveness to polar adherends such as metals, and the reactivity with the component (C) described later is enhanced. The upper limit is preferably 10% by weight or less, more preferably 5% by weight or less, still more preferably 4% by weight or less. As a result, the component (B) can react with the component (A) without waste and can maintain good adhesiveness to the adherend.

The modified weight (graft weight) due to the component (B) in the modified polyolefin resin is preferably 0.1% by weight or more, more preferably 0.5% by weight, when the modified polyolefin resin is 100% by weight. % Or more. The upper limit is preferably 10% by weight or less, more preferably 5% by weight or less, still more preferably 4% by weight or less. The modified weight (graft weight) due to the component (B) in the modified polyolefin resin is preferably 0.1 to 10% by weight, more preferably 0.5, when the modified polyolefin resin is 100% by weight. ~ 4% by weight. When the modified weight (graft weight) is 0.1% by weight or more, the obtained modified polyolefin-based resin has good adhesiveness to a polar adherend such as a metal, and has a good adhesiveness with the component (C) described later. Reactivity can be ensured. When the modified weight (graft weight) is 10% by weight or less, good adhesiveness to the resin adherend can be maintained.

The modified weight% by the component (B) in the modified polyolefin resin can be measured by a known method. For example, it can be obtained by alkaline titration method or Fourier transform infrared spectroscopy.

(Component (C))
The component (C) is a compound having a benzene ring. The component (C) is preferably a compound capable of reacting with the component (A) to introduce a benzene ring into the polyolefin resin. Examples of the compound having a benzene ring include aniline, phenol, benzenethiol, and compounds having a benzyl group (eg, benzylamine, benzyl alcohol, and benzyl mercaptan). Among them, a compound having a benzyl group is preferable because it is easy to handle and has high reactivity, and one or more selected from benzylamine and benzyl alcohol is more preferable.
The component (C) may be one kind of compound having a benzene ring or a combination of two or more kinds.

The modified polyolefin-based resin of the present invention has high adhesiveness not only to the polyolefin-based substrate but also to the polycarbonate-based substrate and the polystyrene-based substrate.
The reason can be inferred as follows. That is, since the benzene ring has a π bond, when the polyolefin resin is modified with a modification component containing a compound having a component (C): benzene ring, the modified polyolefin resin contains a benzene ring in its structure and is intramolecular. A conjugated system is formed in. On the other hand, the polycarbonate-based base material and the polystyrene-based base material have a benzene ring in the structure. Due to the interaction between the conjugated system formed on the modified polyolefin resin and the benzene ring contained in the structure of the substrate, the modified polyolefin resin of the present invention has adhesiveness to the polycarbonate-based substrate and the polystyrene-based substrate. It is presumed that it will increase.

At the time of denaturation, the blending amount (content) of the component (C) is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, based on the component (A). As a result, a sufficient adhesive effect can be exhibited. The upper limit is preferably 20% by weight or less, and more preferably 10% by weight or less. As a result, the component (C) can react with the component (A) without waste and can maintain good adhesiveness to the adherend.

The modified (added) weight of the component (C) in the modified polyolefin resin is preferably 0.1% by weight or more, more preferably 0.5% by weight, when the modified polyolefin resin is 100% by weight. That is all. The upper limit is preferably 20% by weight or less, and more preferably 10% by weight or less. The modified (added) weight of the component (C) in the modified polyolefin resin is preferably 0.1 to 20% by weight, more preferably 0.5, when the modified polyolefin resin is 100% by weight. It is 10% by weight. When the modified weight is 0.1% by weight or more, the modified polyolefin-based resin has good adhesiveness to the adherend. When it is 20% by weight or less, the adhesiveness to the adherend can be well maintained.

The modified weight% by the component (C) in the modified polyolefin resin can be measured by a known method. For example, it can be obtained by Fourier transform infrared spectroscopy.

(Other denatured components)
The denatured component that modifies the component (A) may contain other components in addition to the component (B) and the component (C), depending on the intended use and purpose, as long as the effects of the present invention are not impaired.

(Component (D))
The denatured component that modifies the component (A) preferably contains the component (D): (meth) acrylic acid ester.
Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, and isobornyl (meth) acrylate. Glycidyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, Examples thereof include diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and acetoacetoxyethyl (meth) acrylate.
In addition, in this specification, "(meth) acrylate" means methacrylate or acrylate.
The component (D) may be used alone or in combination of two or more.

The component (D) preferably contains a (meth) acrylic acid ester represented by the formula (I), and more preferably a (meth) acrylic acid ester represented by the formula (I).
CH ₂ = CR ¹ COOR ² ... (I)
(In the formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents a group represented by −C _n H _{2n + 1} , and n is an integer of 8 to 18.)

By including the (meth) acrylic acid ester represented by the formula (I) in the component (D), the molecular weight of the modified polyolefin resin is suppressed from decreasing from the molecular weight of the component (A): the polyolefin resin, and at the same time, it is suppressed. Solvent solubility of modified polyolefin resin, low temperature stability of modified polyolefin resin solution, compatibility between modified polyolefin resin and other resins blended with modified polyolefin resin in adhesives, etc., adhesion of modified polyolefin resin It is possible to improve the sex. When the component (D) contains a (meth) acrylic acid ester represented by the formula (I), the (meth) acrylic acid ester represented by the formula (I) may be used alone or in combination of two or more. Also, two or more kinds of (meth) acrylic acid esters represented by the formula (I) may be mixed and used at an arbitrary ratio.

R ¹ preferably represents a methyl group. n is preferably an integer of 8 to 15, more preferably an integer of 8 to 14, and even more preferably an integer of 8 to 13.
The (meth) acrylic acid ester represented by the formula (I) is preferably one or more selected from stearyl (meth) acrylate, lauryl (meth) acrylate, and octyl (meth) acrylate, and more preferably stearyl methacrylate. , One or more selected from lauryl methacrylate and octyl methacrylate, and more preferably one or more selected from lauryl methacrylate and octyl methacrylate.

At the time of denaturation, the blending amount of the component (D) is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, based on the component (A). As a result, the molecular weight distribution of the modified polyolefin resin can be kept in a sufficiently narrow range. That is, by reducing the high molecular weight portion, solvent solubility, low temperature stability of the solution, and compatibility with other resins can be well maintained. Further, the adhesive strength can be improved by reducing the low molecular weight portion.
The upper limit is preferably 10% by weight or less, and more preferably 4% by weight or less. As a result, the component (D) can be suppressed from remaining as an unreacted substance, and the adhesiveness to the adherend can be well maintained.

The weight of the modified (grafted) due to the component (D) in the modified polyolefin resin is preferably 0.1% by weight or more, more preferably 0.5% by weight, when the modified polyolefin resin is 100% by weight. That is all. The upper limit is preferably 10% by weight or less, and more preferably 4% by weight or less. Therefore, the modified (graft) weight of the component (D) in the modified polyolefin resin is preferably 0.1 to 10% by weight, more preferably 0, when the modified polyolefin resin is 100% by weight. .5-4% by weight. When the modified weight (graft weight) is 0.1% by weight or more, the molecular weight distribution of the modified polyolefin resin can be kept in a sufficiently narrow range. That is, by reducing the high molecular weight portion, solvent solubility, low temperature stability of the solution, and compatibility with other resins can be well maintained. Further, the adhesive strength can be improved by reducing the low molecular weight portion. When the modified weight (graft weight) is 10% by weight or less, the adhesiveness to the resin adherend can be well maintained.

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

(Any other denatured ingredient)
The denatured component may contain a denatured component other than the component (B), the component (C), and the component (D) alone or in combination of two or more.
Examples of the denatured component other than the component (B), the component (C), and the component (D) include derivatives of α, β-unsaturated carboxylic acid other than the component (B) and the component (D). Examples of the derivative of the α, β-unsaturated carboxylic acid include α, β-unsaturated carboxamide. Examples of α, β-unsaturated carboxamide include amides of (meth) acrylic acid (eg, N-methyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, (meth) acryloylmorpholine).
As used herein, (meth) acrylamide means methacrylamide or acrylamide, and (meth) acryloyl means methacryloyl or acryloyl.

The denatured component may contain component (E): chlorine, but the denatured component preferably does not contain the component (E). Thereby, the modified polyolefin resin of the present invention can be suitably used for adhering a substance in which the residual component derived from chlorine is not preferable.
When the denatured component contains a denatured component other than the component (B), the component (C), and the component (D), each modified weight due to the denatured component other than the component (B), the component (C), and the component (D). It is preferable that the total of the modified weights of the components (B) does not exceed the total of the modified weights of the component (B), the modified weight of the component (C), and the modified weight of the component (D).

The modified polyolefin-based resin of the present invention is obtained by modifying the component (A) with the modified component, and is a polymer or modified component containing only the modified component as a constituent unit as long as the object (objective) and the effect of the present invention are not impaired. It may be in a form containing a substance other than the modified polyolefin resin such as a monomer and an unmodified polyolefin resin.

<Manufacturing method of modified polyolefin resin>
The modified polyolefin resin of the present invention can be produced by a known method.
In the production of the modified polyolefin resin of the present invention, the component (F): radical generator may be used.

The radical generator as the component (F) is not particularly limited, and may be appropriately selected from known radical generators. As the component (F), an organic peroxide compound is preferable. Examples of the organic peroxide compound include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, and t-butyl hydroper. Oxide, 1,4-bis [(t-butylperoxy) isopropyl] benzene, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butyl) Peroxy) -cyclohexane, cyclohexanone peroxide, t-butylperoxybenzoate, t-butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2 -Ethylhexanoate, t-butylperoxyisopropyl carbonate, cumylperoxyoctate and the like, and one or more selected from di-t-butyl peroxide, dicumyl peroxide, and dilauryl peroxide are preferable. .. The component (F) may be used alone or in combination of two or more.

The blending amount of the component (F) in the production of the modified polyolefin resin of the present invention is preferably the total (weight) of the blending amounts of the component (B), the component (C), and optionally the component (D). It is 1 to 100% by weight, more preferably 10 to 50% by weight. When it is 1% by weight or more, sufficient graft efficiency can be maintained. When it is 100% by weight or less, it is possible to suppress a decrease in the weight average molecular weight of the modified polyolefin resin.

As a method for obtaining a modified polyolefin resin, for example, a mixture of the component (A) and the modified component (eg, component (B), component (C), and component (D)) is used as a solvent (eg, organic such as toluene). Using a solution method in which the component (F) is added by heating and dissolving in (solvent), and a kneader such as a Banbury mixer, kneader, or extruder, the component (A), the denaturing component (eg, the component (B), Examples thereof include a melt-kneading method in which the component (C), the component (D)), and the component (F) are melt-kneaded and reacted under heating.

When the component (A) is denatured by the denatured component, the order of denatured by each component contained in the denatured component is not particularly limited, and all the denatured components may be denatured at the same time. , Before or after the denaturation with the remaining denaturing components, or the denaturation with each denaturing component may be performed sequentially.
The modification of the component (A) by the modifying component is preferably carried out in the order of the modification by the component (B) and the modification by the component (C).
When the denaturing component contains the component (D), the denaturation by the component (B) and the denaturation by the component (D) are preferably performed at the same time.

When the denaturing component contains the component (D), a method is preferable in which the component (A) is graft-modified with the component (B) and the component (D) using the component (F) and then modified with the component (C). In this method, it is presumed that the component (C) is introduced into the modified portion of the component (A) by an addition reaction.

It is preferable that any one of the modified weight due to the component (B), the modified weight due to the component (D), and the modified weight due to the component (C) in the modified polyolefin resin is 0.1 to 10% by weight, and the component. It is more preferable that the modified weight according to (B), the modified weight due to the component (D), and the modified weight according to the component (C) are all 0.1 to 10% by weight.

The weight average molecular weight of the modified polyolefin resin of the present invention is preferably 5,000 to 300,000, more preferably 8,000 to 200,000, or more preferably 5,000 or more and less than 200,000. More preferably, it is 10,000 to 150,000. When the weight average molecular weight is 5,000 or more, sufficient adhesive strength can be obtained.
When it is 300,000 or less, it can be dissolved in a solvent well and relatively good fluidity can be obtained. The weight average molecular weight in the present invention including the examples is a value measured and calculated by gel permeation chromatography (GPC) (standard substance: polystyrene).
For example, GPC can be performed under the following conditions.
Measuring equipment: HLC-8320GPC (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Column: TSKgel (manufactured by Tosoh Corporation)

The melting point (hereinafter, also referred to as Tm) of the modified polyolefin resin of the present invention by a differential scanning calorimeter (hereinafter, DSC) is preferably 50 ° C to 120 ° C, although it depends on the conditions of use. When the melting point is 50 ° C. or higher, sufficient adhesive strength can be obtained. On the other hand, when the melting point is 120 ° C. or lower, the adhesiveness at a relatively low temperature that does not cause deformation of the shape of the base material is good, the solution stability is good, and sufficient storage stability at a low temperature is obtained. Obtainable.

The measurement of Tm by DSC in the present invention can be performed under the following conditions, for example. In accordance with JIS K7121-1987, using a DSC measuring device (manufactured by Seiko Electronics Co., Ltd.), a sample of about 5 mg is heated at 150 ° C. for 10 minutes to maintain a molten state, and then the temperature is lowered at a rate of 10 ° C./min. After stable holding at 50 ° C., the temperature is further raised to 150 ° C. at 10 ° C./min, the melting peak temperature at the time of melting is measured, and the temperature is evaluated as Tm. It should be noted that Tm in the examples described later was measured under the above-mentioned conditions.

The modified polyolefin-based resin of the present invention can be combined with other components as necessary to form a modified polyolefin-based resin composition. The modified polyolefin-based resin or the modified polyolefin-based resin composition can be used as a heat sealant, an adhesive, a primer, a binder (eg, a binder for paints, a binder for inks).
Other components include, for example, curing agents, solvents or dispersion media, antioxidants, light stabilizers, UV absorbers, pigments, dyes, and inorganic fillers.

Examples of the curing agent include polyisocyanate compounds, epoxy compounds, polyamine compounds, polyol compounds, and curing agents in which the functional groups of these compounds are protected by protecting groups.
The curing agent may be blended alone in the resin composition, or may be blended as a combination of two or more kinds.
The amount of the curing agent to be blended in the resin composition is not particularly limited, but is appropriately selected depending on, for example, the amount of α, β-unsaturated carboxylic acid in the modified polyolefin resin of the present invention or the amount of modification with an acid anhydride thereof. good. When a curing agent is blended, a catalyst such as an organotin compound or a tertiary amine compound may be used in combination depending on the purpose.

The solvent or dispersion medium is not particularly limited, and is, for example, an aromatic hydrocarbon (eg, toluene, xylene), an ester (eg, ethyl acetate, butyl acetate, propyl acetate), an aliphatic or alicyclic hydrocarbon (eg,). , Cyclohexane, methylcyclohexane, ethylcyclohexane, nonane, decane), alcohols (eg methanol, ethanol, propanol, isopropanol, butanol), glycol ethers (eg propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol-t-butyl ether). ), Water. The solvent or dispersion medium contained in the modified polyolefin resin composition may be one kind alone or a combination of two or more kinds.
The modified polyolefin resin composition may be an aqueous resin composition containing a solvent containing water or a dispersion medium.

The resin composition containing the modified polyolefin resin of the present invention contains other components (eg, polyester adhesive, polyurethane adhesive, acrylic adhesive, etc.) used in the adhesive as long as the desired effect is not impaired. A known adhesive), other components used in a heat sealant, other components used in a primer, and other components used in a binder may be blended.

The modified polyolefin resin of the present invention has excellent adhesiveness not only to polyolefin-based substrates but also to polycarbonate-based substrates and polystyrene-based substrates with few polar groups, and is therefore useful as an adhesive or heat sealant for adhering them. Is. The modified polyolefin resin of the present invention can be used, for example, for adhering a cover tape of an embossed carrier tape for electronic parts.

2. 2. Method for Producing Modified Polyolefin Resin of the Present Invention The method for producing the modified polyolefin resin of the present invention is as follows.
Component (A): Includes modifying a polyolefin resin with a modifying component to obtain a modified polyolefin resin.
The denatured component is
Component (B): One or more selected from α, β-unsaturated carboxylic acid and its acid anhydride, and component (C): a compound having a benzene ring.

Regarding the component (A) and the components (B) and (C) which are denatured components, the above item 1. As already explained in.

The modified component preferably further contains the component (D): (meth) acrylic acid ester.
Regarding the component (D), the above item 1. As already explained in.
The method for denaturing the component (A) with the denaturing component is not particularly limited. For example, a mixture of the component (A) and the denaturing component is heated and dissolved in a solvent (eg, an organic solvent such as toluene), and the above component (F) is used. ), And a melt-kneading method in which the component (A), the modified component, and the component (F) are melt-kneaded and reacted under heating.
Examples of the component (F) and preferable examples are described in the above item 1. As already explained in.
The device for carrying out these methods is not particularly limited, and a known device may be used. For example, in the melt kneading method, a kneader such as a Banbury mixer, a kneader, or an extruder may be used.

The order of denaturation of the component (A) by each component contained in the denaturing component is not particularly limited, and all denaturation by each denaturing component may be performed at the same time. It may be performed before or after the above, and the modification by each modification component may be sequentially performed.
The modification of the component (A) by the modifying component is preferably carried out in the order of the modification by the component (B) and the modification by the component (C).
When the denaturing component contains the component (D), the denaturation by the component (B) and the denaturation by the component (D) are preferably performed at the same time.

The denatured component may contain a denatured component other than the component (B), the component (C), and the component (D) alone or in combination of two or more. For any other denatured components other than the component (B), the component (C), and the component (D), refer to the above item 1. As already explained in.

The preferred modified weight, preferred weight average molecular weight, and preferred melting point of the modified polyolefin resin obtained by the production method of the present invention are described in the above item 1. As already explained in.

The modified polyolefin resin obtained by the production method of the present invention is described in the above item 1. As described above, a modified polyolefin-based resin composition can be obtained by combining with other components as necessary, and the modified polyolefin-based resin or the modified polyolefin-based resin composition can be a heat sealant, an adhesive, or a primer. , Can be used as a binder (eg, paint binder, ink binder).

In addition, in this specification, "agent" includes "composition".

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

(Example 1)
Kneading using a twin-screw extruder in which 100 parts by weight of the propylene-ethylene copolymer, 1 part by weight of maleic anhydride, 0.75 parts by weight of lauryl methacrylate, and 3 parts by weight of dit-butyl peroxide was set at 180 ° C. Reacted. Decompression was performed in the extruder to remove the residual unreacted product to obtain a modified product. 75 parts by weight of the obtained modified product and 45 parts by weight of xylene were dissolved at 135 ° C., 1 part by weight of benzylamine was added under stirring, and the mixture was held at 135 ° C. for 2 hours, and then xylene was removed by distillation under reduced pressure. , A modified polyolefin resin was obtained. When the obtained modified polyolefin resin was dissolved in a mixed solvent of methylcyclohexane / propyl acetate = 70/30 (V / V) so as to have a solid content of 20%, the properties of the modified polyolefin resin solution showed no solidification. It was in a fluid state and was in good condition.
The weight average molecular weight of the obtained modified polyolefin resin was 70,000.

(Example 2)
Using a twin-screw extruder in which 100 parts by weight of the propylene-ethylene copolymer, 1 part by weight of maleic anhydride, 0.75 parts by weight of lauryl methacrylate, and 1.5 parts by weight of dit-butyl peroxide were set at 170 ° C. Kneaded reaction. Decompression was performed in the extruder to remove the residual unreacted product to obtain a modified product. 75 parts by weight of the obtained modified product and 45 parts by weight of xylene were dissolved at 135 ° C., 5 parts by weight of benzylamine was added under stirring, the mixture was held at 135 ° C. for 2 hours, and then xylene was removed by distillation under reduced pressure. Then, a modified polyolefin resin was obtained. When the obtained modified polyolefin resin was dissolved in a mixed solvent of methylcyclohexane / propyl acetate = 70/30 (V / V) so as to have a solid content of 20%, the properties of the modified polyolefin resin solution showed no solidification. It was in a fluid state and was in good condition.
The weight average molecular weight of the obtained modified polyolefin resin was 68,000.

(Example 3)
A kneading reaction was carried out using a twin-screw extruder in which 100 parts by weight of the propylene-ethylene copolymer, 3 parts by weight of itaconic anhydride, and 3 parts by weight of dit-butyl peroxide were set at 170 ° C. Decompression was performed in the extruder to remove the residual unreacted product to obtain a modified product. 75 parts by weight of the obtained modified product and 45 parts by weight of xylene were dissolved at 135 ° C., 5 parts by weight of benzyl mercaptan was added under stirring, and the mixture was held at 135 ° C. for 2 hours, and then xylene was removed by distillation under reduced pressure. Then, a modified polyolefin resin was obtained. When the obtained modified polyolefin resin was dissolved in a mixed solvent of methylcyclohexane / propyl acetate = 70/30 (V / V) so as to have a solid content of 20%, the properties of the modified polyolefin resin solution showed no solidification. It was in a fluid state and was in good condition.
The weight average molecular weight of the obtained modified polyolefin resin was 71,000.

(Example 4)
Kneading using a twin-screw extruder in which 100 parts by weight of the propylene-ethylene copolymer, 3 parts by weight of maleic anhydride, 0.25 parts by weight of octyl methacrylate, and 4 parts by weight of dit-butyl peroxide was set at 160 ° C. Reacted. Decompression was performed in the extruder to remove the residual unreacted product to obtain a modified product. 75 parts by weight of the obtained modified product and 45 parts by weight of xylene were dissolved at 135 ° C., 1 part by weight of benzylamine was added under stirring, the mixture was held at 135 ° C. for 2 hours, and then xylene was removed by distillation under reduced pressure. Then, a modified polyolefin resin was obtained. When the obtained modified polyolefin resin was dissolved in a mixed solvent of methylcyclohexane / propyl acetate = 70/30 (V / V) so as to have a solid content of 20%, the properties of the modified polyolefin resin solution showed no solidification. It was in a fluid state and was in good condition.
The weight average molecular weight of the obtained modified polyolefin resin was 72,000.

(Example 5)
Kneading using a twin-screw extruder in which 100 parts by weight of the propylene-ethylene copolymer, 3 parts by weight of maleic anhydride, 0.25 parts by weight of octyl methacrylate, and 3 parts by weight of dit-butyl peroxide was set at 160 ° C. Reacted. Decompression was performed in the extruder to remove the residual unreacted product to obtain a modified product. 75 parts by weight of the obtained modified product and 45 parts by weight of xylene were dissolved at 135 ° C., 5 parts by weight of benzylamine was added under stirring, the mixture was held at 135 ° C. for 2 hours, and then xylene was removed by distillation under reduced pressure. Then, a modified polyolefin resin was obtained. When the obtained modified polyolefin resin was dissolved in a mixed solvent of methylcyclohexane / propyl acetate = 70/30 (V / V) so as to have a solid content of 20%, the properties of the modified polyolefin resin solution showed no solidification. It was in a fluid state and was in good condition.
The weight average molecular weight of the obtained modified polyolefin resin was 71,000.

(Example 6)
A kneading reaction was carried out using a twin-screw extruder in which 100 parts by weight of the propylene-ethylene copolymer, 5 parts by weight of citraconic anhydride and 5 parts by weight of dit-butyl peroxide were set at 170 ° C. Decompression was performed in the extruder to remove the residual unreacted product to obtain a modified product. 75 parts by weight of the obtained modified product and 45 parts by weight of xylene were dissolved at 135 ° C., 5 parts by weight of benzyl alcohol was added under stirring, the mixture was held at 135 ° C. for 2 hours, and then xylene was removed by distillation under reduced pressure. Then, a modified polyolefin resin was obtained. When the obtained modified polyolefin resin was dissolved in a mixed solvent of methylcyclohexane / propyl acetate = 70/30 (V / V) so as to have a solid content of 20%, the properties of the modified polyolefin resin solution showed no solidification. It was in a fluid state and was in good condition.
The weight average molecular weight of the obtained modified polyolefin resin was 73,000.

(Example 7)
Kneading using a twin-screw extruder in which 100 parts by weight of the propylene-ethylene copolymer, 5 parts by weight of maleic anhydride, 3.75 parts by weight of stearyl methacrylate, and 2 parts by weight of dit-butyl peroxide were set at 170 ° C. Reacted. Decompression was performed in the extruder to remove the residual unreacted product to obtain a modified product. 75 parts by weight of the obtained modified product and 45 parts by weight of xylene were dissolved at 135 ° C., 1 part by weight of benzylamine was added under stirring, the mixture was held at 135 ° C. for 2 hours, and then xylene was removed by distillation under reduced pressure. Then, a modified polyolefin resin was obtained. When the obtained modified polyolefin resin was dissolved in a mixed solvent of methylcyclohexane / propyl acetate = 70/30 (V / V) so as to have a solid content of 20%, the properties of the modified polyolefin resin solution showed no solidification. It was in a fluid state and was in good condition.
The weight average molecular weight of the obtained modified polyolefin resin was 75,000.

(Example 8)
Using a twin-screw extruder in which 100 parts by weight of the propylene-ethylene copolymer, 5 parts by weight of maleic anhydride, 3.75 parts by weight of stearyl methacrylate, and 1.5 parts by weight of dit-butyl peroxide were set at 170 ° C. Kneaded reaction. Decompression was performed in the extruder to remove the residual unreacted product to obtain a modified product. 75 parts by weight of the obtained modified product and 45 parts by weight of xylene were dissolved at 135 ° C., 5 parts by weight of benzylamine was added under stirring, the mixture was held at 135 ° C. for 2 hours, and then xylene was removed by distillation under reduced pressure. Then, a modified polyolefin resin was obtained. When the obtained modified polyolefin resin was dissolved in a mixed solvent of methylcyclohexane / propyl acetate = 70/30 (V / V) so as to have a solid content of 20%, the properties of the modified polyolefin resin solution showed no solidification. It was in a fluid state and was in good condition.
The weight average molecular weight of the obtained modified polyolefin resin was 72,000.

(Example 9)
Kneading using a twin-screw extruder in which 100 parts by weight of the propylene-ethylene copolymer, 10 parts by weight of itaconic anhydride, 7.5 parts by weight of stearyl methacrylate, and 2 parts by weight of dit-butyl peroxide were set at 180 ° C. It reacted. Decompression was performed in the extruder to remove the residual unreacted product to obtain a modified product. 75 parts by weight of the obtained modified product and 45 parts by weight of xylene were dissolved at 135 ° C., 5 parts by weight of benzyl alcohol was added under stirring, and the mixture was held at 135 ° C. for 2 hours to obtain a modified polyolefin resin. .. When the obtained modified polyolefin resin was dissolved in a mixed solvent of methylcyclohexane / propyl acetate = 70/30 (V / V) so as to have a solid content of 20%, the properties of the modified polyolefin resin solution showed no solidification. It was in a fluid state and was in good condition.
The weight average molecular weight of the obtained modified polyolefin resin was 78,000.

(Example 10)
Kneading using a twin-screw extruder in which 100 parts by weight of the propylene-ethylene copolymer, 10 parts by weight of itaconic anhydride, 7.5 parts by weight of stearyl methacrylate, and 3 parts by weight of dit-butyl peroxide were set at 170 ° C. It reacted. Decompression was performed in the extruder to remove the residual unreacted product to obtain a modified product. 75 parts by weight of the obtained modified product and 45 parts by weight of xylene were dissolved at 135 ° C., 10 parts by weight of benzyl alcohol was added under stirring, and the mixture was held at 135 ° C. for 2 hours to obtain a modified polyolefin resin. .. When the obtained modified polyolefin resin was dissolved in a mixed solvent of methylcyclohexane / propyl acetate = 70/30 (V / V) so as to have a solid content of 20%, the properties of the modified polyolefin resin solution showed no solidification. It was in a fluid state and was in good condition.
The weight average molecular weight of the obtained modified polyolefin resin was 78,000.

(Comparative Example 1)
Kneading reaction using a twin-screw extruder in which 100 parts by weight of propylene-ethylene copolymer, 3 parts by weight of maleic acid, 2.25 parts by weight of octyl methacrylate, and 3 parts by weight of dit-butyl peroxide are set at 170 ° C. bottom. Decompression was performed in the extruder to remove the residual unreacted product to obtain a modified product. 75 parts by weight of the obtained modified product and 45 parts by weight of xylene were dissolved at 135 ° C. and held for 2 hours to obtain a modified polyolefin resin. When the obtained modified polyolefin resin was dissolved in a mixed solvent of methylcyclohexane / propyl acetate = 70/30 (V / V) so as to have a solid content of 20%, the properties of the modified polyolefin resin solution were good. ..
The weight average molecular weight of the obtained modified polyolefin resin was 72,000.

(Comparative Example 2)
The kneading reaction was carried out using a twin-screw extruder in which 100 parts by weight of the propylene-ethylene copolymer, 2.25 parts by weight of lauryl methacrylate, and 2 parts by weight of the dit-butyl peroxide were set at 160 ° C. Decompression was performed in the extruder to remove the residual unreacted product to obtain a modified product. 75 parts by weight of the obtained modified product and 45 parts by weight of xylene were dissolved at 135 ° C., 5 parts by weight of benzyl alcohol was added under stirring, and the mixture was held at 135 ° C. for 2 hours to obtain a modified polyolefin resin. .. When the obtained modified polyolefin resin was dissolved in a mixed solvent of methylcyclohexane / propyl acetate = 70/30 (V / V) so as to have a solid content of 20%, the properties of the modified polyolefin resin solution showed no solidification. It was in a fluid state and was in good condition.
The weight average molecular weight of the obtained modified polyolefin resin was 65,000.

(Evaluation method)
Each of the resins obtained in Examples 1 to 10 and Comparative Examples 1 and 2 was evaluated according to the following method.
(Heat seal strength)
Each resin is dissolved in a mixed solvent of methylcyclohexane / propyl acetate = 70/30 (V / V) so as to have a solid content of 20%, and stretched polypropylene (oriented polypropylene: OPP) film (Futamura chemistry) is used in Meyerbar # 10. It was applied to the corona-treated surface of (manufactured by), dried with a hair dryer for 30 seconds, and then allowed to stand overnight to obtain a resin-coated film.
Resin-coated film The film and each base material (PS plate, PC plate, or PET plate) were superposed, and No. Heat seal was performed using a 276 heat seal tester (manufactured by Yasuda Seiki Seisakusho). The heat seal was performed by heating only the film side to 140 ° C. and pressurizing at 2 kgf for 6 seconds. After heat-sealing, the mixture was allowed to stand for 3 hours, and a peeling test in the 180 ° direction was performed with a Tencilon universal testing machine (RTG-1210 manufactured by A & D Co., Ltd.). The peeling speed was 100 mm / min.

From the results of Tables 1 and 2, the modified polyolefin resin of Examples 1 to 10 is the modified polyolefin resin of Comparative Example 1 not modified by the component (C) and Comparative Example 2 not modified by the component (B). It can be seen that when the OPP film and each base material (PS plate, PC plate, or PET plate) are heat-sealed, the heat-sealing strength is significantly improved.
This result shows that the modified polyolefin resin of the present invention has excellent adhesiveness to polyester-based substrates such as polyolefin-based substrates, polystyrene-based substrates, polycarbonate-based substrates, and PET.

Claims (14)

Component (A): Polyolefin resin is modified with a modifying component,
The denaturing component is one or more selected from the component (B): α, β-unsaturated carboxylic acid and its acid anhydride .
Component (C): aniline, phenol, benzenethiol, benzylamine, it is benzyl alcohol, and one or more members selected from the group consisting of benzyl mercaptan, a compound having a benzene ring, and
Component (D): A modified polyolefin-based resin containing a (meth) acrylic acid ester. The modified polyolefin-based resin according to claim 1 , wherein the component (D) contains a (meth) acrylic acid ester represented by the formula (I).
CH ₂ = CR ¹ COOR ² ... (I)
(In the formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents a group represented by −C _n H _{2n + 1} , and n is an integer of 8 to 18.) The modified polyolefin resin according to claim 1 or 2 , wherein the component (A) is a propylene-ethylene copolymer or a propylene-butene copolymer. The modified polyolefin resin according to any one of claims 1 to 3, wherein the component (C) is a compound having a benzyl group. The modified polyolefin resin according to any one of claims 1 to 4 , wherein the weight average molecular weight is 5,000 or more and less than 200,000. The modified polyolefin resin according to any one of claims 1 to 5 , wherein the content of the component (C) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the component (A). A heat sealant containing the modified polyolefin resin according to any one of claims 1 to 6. An adhesive containing the modified polyolefin resin according to any one of claims 1 to 6. A primer containing the modified polyolefin resin according to any one of claims 1 to 6. A binder for a paint containing the modified polyolefin resin according to any one of claims 1 to 6. A binder for ink containing the modified polyolefin resin according to any one of claims 1 to 6. Component (A): Includes modifying a polyolefin resin with a modifying component to obtain a modified polyolefin resin.
The denatured component is
Component (B): One or more selected from α, β-unsaturated carboxylic acid and its acid anhydride ,
Component (C): aniline, phenol, benzenethiol, benzylamine, it is benzyl alcohol, and one or more members selected from the group consisting of benzyl mercaptan, a compound having a benzene ring, and
Ingredient (D): Containing (meth) acrylic acid ester,
A method for producing a modified polyolefin resin. The method for producing a modified polyolefin resin according to claim 12 , wherein the modification is performed in the order of modification by the component (B) and modification by the component (C). The method for producing a modified polyolefin resin according to claim 13 , wherein the modification with the component (B) and the modification with the component (D) are performed at the same time.