WO2018128111A1

WO2018128111A1 - Modified polyolefin resin

Info

Publication number: WO2018128111A1
Application number: PCT/JP2017/046355
Authority: WO
Inventors: 勝神埜; 由生 ▲高▼田; 早川　潤一; 実矢田; 高本　直輔
Original assignee: 日本製紙株式会社
Priority date: 2017-01-05
Filing date: 2017-12-25
Publication date: 2018-07-12
Also published as: JPWO2018128111A1; JP6943882B2; TWI762549B; TW201831587A

Abstract

Provided is a modified polyolefin resin having excellent chipping resistance. The modified polyolefin resin is a copolymer in which component (B) is grafted to component (A), wherein the component (A) is a polyolefin resin or a modified product thereof, and the component (B) is a polymer which includes a structural unit (i) derived from (meth)acrylic acid ester and represented by general formula (I) below, and has a glass transition temperature (Tg) of 0°C or lower. (I) CH₂=C(R¹)COOR² (in formula (I), R¹ represents a hydrogen atom or methyl, R² represents a group represented by -C_nH_2n+1, and n represents an integer of 1-18.)

Description

Modified polyolefin resin

The present invention relates to a modified polyolefin resin.

Polyolefin base materials such as polypropylene are widely used for plastic molded parts, various films for food packaging materials and the like because they have excellent performance and are inexpensive. At that time, the surface of the polyolefin substrate is printed or painted for the purpose of surface protection or improvement of aesthetics.
However, since the polyolefin base material is a nonpolar base material and has low surface free energy and further has crystallinity, there is a problem that ink and paint are difficult to adhere. Therefore, a technique for improving the adhesion to a polyolefin base material by adding a chlorinated polyolefin resin to ink or paint during printing or painting is widely used.

Such plastic molded products such as polyolefin base materials are often used as members attached to the outer panel of automobiles and members of household electrical appliances. Usually, in order to improve the adhesion between the top coat film and the molded product, a primer containing a chlorinated polyolefin resin or the like is applied to the plastic molded product in advance before the top coat is applied.
Under such circumstances, in recent years, a method of painting a plastic molded product after integrating the plastic molded product with the automobile outer plate has been proposed (Patent Document 1). In such a coating method, since the coating line can be unified, a reduction in the amount of paint used and, in turn, a reduction in cost is expected.

JP 2012-213692 A

However, in the coating method of Patent Document 1, the primer is applied not only to a plastic molded product but also to an automobile outer plate that is a metal. Therefore, when trying to form a coating film with a certain thickness on the automobile outer plate, the overcoat layer will be reduced by the amount of the primer layer, and the primer layer is resistant to peeling of the coating film by the leapstone. Since the (chipping resistance) is inferior, there is a problem that the chipping resistance of the entire coated portion is lowered.
Accordingly, an object of the present invention is to provide a modified polyolefin resin having excellent chipping resistance.

As a result of diligent research, the present inventors have found that a polyolefin resin or a modified product thereof is a copolymer in which a polymer having a predetermined (meth) acrylic acid ester unit and having a glass transition temperature of 0 ° C. or less is grafted. It has been found that the above-mentioned problems can be solved by a certain modified polyolefin resin. That is, the present invention provides the following.

[1] Component (A): Polyolefin resin or modified product thereof, Component (B): Containing structural unit (i) derived from (meth) acrylic acid ester represented by the following general formula (I), glass transition temperature A modified polyolefin resin, which is a copolymer grafted with a polymer having (Tg) of 0 ° C. or lower.
CH ₂ = C (R ¹ ) COOR ² (I)
(In Formula (I), R ¹ represents a hydrogen atom or methyl, R ² represents a group represented by —C _n H _{2n + 1} , and n represents an integer of 1 to 18)
[2] The modified polyolefin resin according to [1], wherein the structural unit (i) has 4 to 12 carbon atoms.
[3] The modified polyolefin resin according to [2], wherein the content of the structural unit (i) in the component (B) is 40% by weight or more and 100% by weight or less.
[4] The modified polyolefin resin according to any one of [1] to [3], wherein the component (A) is a chlorinated polyolefin resin.
[5] The modified polyolefin resin according to any one of [1] to [4], wherein the component (B) has a weight average molecular weight of 1,000 or more and 100,000 or less.
[6] The modified polyolefin resin according to any one of [1] to [5], wherein the hydroxyl value of the component (B) is from 5 mgKOH / g to 560 mgKOH / g.
[7] Any one of [1] to [6], wherein the weight ratio of component (A) to component (B) (component (A) / component (B)) is 20/80 or more and 80/20 or less. The modified polyolefin resin described in 1.
[8] The modified polyolefin resin according to any one of [1] to [7], which has a weight average molecular weight of 10,000 or more and 200,000 or less.
[9] A dispersion composition comprising the modified polyolefin resin according to any one of [1] to [8] and a dispersion medium.
[10] A primer comprising the modified polyolefin resin according to any one of [1] to [8] or the dispersion composition according to [9].
[11] Component (A): Polyolefin resin or modified product thereof, Component (B): Containing structural unit (i) derived from (meth) acrylic acid ester represented by the following general formula (I), glass transition temperature A method for producing a modified polyolefin resin, comprising a step of graft polymerization of a polymer having (Tg) of 0 ° C. or lower.
CH ₂ = C (R ¹ ) COOR ² (I)
(In Formula (I), R ¹ represents a hydrogen atom or methyl, R ² represents a group represented by —C _n H _{2n + 1} , and n represents an integer of 1 to 18)

According to the present invention, a modified polyolefin resin excellent in chipping resistance can be provided.

In this specification, “(meth) acrylic acid” includes methacrylic acid and acrylic acid, and “(meth) acrylate” includes methacrylate and acrylate.

[1. Modified polyolefin resin]
The modified polyolefin resin of the present invention comprises a component (A): a polyolefin resin or a modified product thereof, a component (B): a structural unit derived from a (meth) acrylic acid ester represented by the general formula (I) (i) ) And a glass transition temperature (Tg) of 0 ° C. or lower is grafted.

[1-1. Ingredient (A)]
Component (A) is a polyolefin resin or a modified product of a polyolefin resin.
[1-1-1. Polyolefin resin]
The polyolefin resin as the component (A) is an olefin polymer. The polyolefin resin as the component (A) is preferably a polyolefin resin produced using a Ziegler-Natta catalyst or a metallocene catalyst as a polymerization catalyst, more preferably a Ziegler-Natta catalyst or a metallocene catalyst as a polymerization catalyst. Polypropylene or a polyolefin resin obtained by copolymerization of propylene and α-olefin (eg, ethylene, butene, 3-methyl-1-butene, 3-methyl-1-heptene), which is produced. A polyolefin resin obtained by random copolymerization of propylene and α-olefin is sometimes referred to as a propylene random copolymer. Examples of the propylene random copolymer include an ethylene-propylene copolymer, a propylene-butene copolymer, an ethylene-propylene-diene copolymer, and an ethylene-propylene-butene copolymer. The polyolefin resin is more preferably a polypropylene or propylene random copolymer produced using a metallocene catalyst as a polymerization catalyst, and particularly preferably polypropylene, ethylene produced using a metallocene catalyst as a polymerization catalyst. -Propylene copolymer, propylene-butene copolymer, or ethylene-propylene-butene copolymer. These resins may be used alone or in combination with a plurality of resins.

Known metallocene catalysts can be used. Specific examples of the metallocene catalyst include a catalyst obtained by combining the components (1) and (2) described below, and (3) as necessary, and the components (1) and (2) described below. In addition, a catalyst obtained by combining (3) if necessary is preferable.
Component (1): a metallocene complex that is a transition metal compound of Groups 4 to 6 in the periodic table having at least one conjugated five-membered ring ligand.
-Component (2); ion-exchangeable layered silicate.
-Component (3); organoaluminum compound.

A polyolefin resin synthesized using a metallocene catalyst is preferable as the component (A) because it has a narrow molecular weight distribution, excellent random copolymerizability, a narrow composition distribution, and a wide range of comonomers that can be copolymerized.

The structure of the polyolefin resin as the component (A) is not particularly limited, and may be any of an isotactic structure, an atactic structure, a syndiotactic structure and the like that can be taken by a normal polymer compound. In view of adhesion to a polyolefin substrate, particularly adhesion at low temperature, a polyolefin resin having an isotactic structure polymerized using a metallocene catalyst is preferable as the component (A).

The component composition of the polyolefin resin as the component (A) is not particularly limited, but the propylene component of the component (A) is preferably 60 mol% or more, more preferably 70 mol% or more, and still more preferably. It is preferable that it is 80 mol% or more. When the propylene component of the component (A) is 60 mol% or more, the adhesion (adhesiveness) to the propylene substrate becomes better.

[1-1-2. Modified polyolefin resin]
Component (A) may be a modified polyolefin resin. Examples and preferred examples of the polyolefin resin in the modified polyolefin resin include the above item [1-1-1. As already described in [Polyolefin Resin].
The type of modification is not particularly limited, and examples thereof include known modifications such as chlorination; epoxidation; hydroxylation; anhydrous carboxylic oxidation; carboxylic oxidation; The modified polyolefin resin can be obtained by modifying the polyolefin resin using a known method. The modified product of the polyolefin resin as the component (A) is preferably a chlorinated polyolefin resin. A method for chlorinating a polyolefin resin will be described later.

When the component (A) is a chlorinated polyolefin resin, the chlorine content of the chlorinated polyolefin resin as the component (A) is preferably 15% by weight or more, more preferably 20% by weight or more. When the chlorine content is 15% by weight or more, the modified polyolefin resin is excellent in dispersibility in alcohols such as ethanol and isopropanol. The upper limit of the chlorine content in the chlorinated polyolefin resin as the component (A) is preferably 40% by weight or less, more preferably 35% by weight or less. When the chlorine content is 40% by weight or less, the modified polyolefin resin is excellent in adhesion to a polyolefin substrate.
The chlorine content of the resin can be measured based on JIS-K7229.
In addition, the chlorine content of component (A) in the modified polyolefin resin of the present invention usually coincides with the chlorine content of component (A) as a raw material before grafting with component (B).

The modified product as the component (A) may be an acid-modified product obtained by modifying a polyolefin resin with an acid. The acid for modification is not particularly limited, and examples thereof include α, β-unsaturated carboxylic acids and α, β-unsaturated carboxylic acid derivatives (eg, maleic acid, maleic anhydride, fumaric acid, citraconic acid, Citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, hymic anhydride, (meth) acrylic acid), and acid anhydrides of α, β-unsaturated carboxylic acids are preferred, Maleic anhydride is more preferred.
As a method for modifying the polyolefin resin with an acid, a known method can be used. For example, a method for obtaining an acid-modified polyolefin resin by melting the polyolefin resin and adding an acid and a radical reaction initiator for modification. Is mentioned. The reaction apparatus is not particularly limited, and for example, the modification reaction may be performed using an extruder.

The modified product as the component (A) may be a modified product in which the polyolefin resin is modified with a plurality of modified materials. Therefore, the modified product as component (A) is an acid-modified chlorine obtained by modifying a chlorinated polyolefin resin with an acid (for example, α, β-unsaturated carboxylic acid or a derivative of α, β-unsaturated carboxylic acid). Polyolefin resin may be used.

Component (A) is preferably a chlorinated polyolefin resin or an acid-modified chlorinated polyolefin resin.

[1-1-3. Weight average molecular weight of component (A)]
The weight average molecular weight (Mw) of the component (A) is preferably 5,000 or more. When the weight average molecular weight is 5,000 or more, the cohesive strength of the resin is sufficient and the adhesion to the substrate is excellent. The upper limit of the weight average molecular weight of component (A) is preferably 150,000 or less. When the weight average molecular weight is 150,000 or less, the compatibility with other resins contained in the paint or ink is good, and the adhesion to the substrate is good. The weight average molecular weight can be obtained from a standard polystyrene calibration curve by gel permeation chromatography (GPC).
The weight average molecular weight of component (A) is preferably 5,000 to 150,000.
Here, the weight average molecular weight of the component (A) usually coincides with the weight average molecular weight measured for the component (A) as a raw material before the component (B) is grafted.

[1-2. Ingredient (B)]
The component (B) is a polymer containing the structural unit (i) derived from the (meth) acrylic acid ester represented by the general formula (I) and having a glass transition temperature (Tg) of 0 ° C. or lower.

[1-2-1. Structural unit (i)]
A component (B) contains the structural unit (i) derived from the (meth) acrylic acid ester represented by general formula (I).
CH ₂ = C (R ¹ ) COOR ² (I)

In general formula (I), R ¹ represents a hydrogen atom or methyl, R ² represents a group represented by —C _n H _{2n + 1} , and n represents an integer of 1 to 18.
The group represented by —C _n H _{2n + 1} may be a linear alkyl group or a branched alkyl group.

Here, the structural unit derived from a certain monomer is a structural unit obtained when a certain monomer is used for the polymerization reaction.

The structural unit (i) preferably has 4 or more carbon atoms, preferably 12 or less. The structural unit (i) preferably has 4 to 12 carbon atoms. Thereby, the chipping resistance of the modified polyolefin resin can be further improved. Here, the number of carbon atoms of the structural unit (i) is usually the same as the number of carbon atoms of the (meth) acrylic acid ester represented by the general formula (I), which is derived from the structural unit (i).

In the case where the component (B) includes the structural unit (i) having 4 to 12 carbon atoms (hereinafter also referred to as the structural unit (i _4-12 )), the structural unit (i _4- The content of ₁₂ ) is preferably 40% by weight or more, more preferably 60% by weight or more, and preferably 100% by weight or less. Thereby, when the modified polyolefin resin is combined with other components to form a composition (for example, a coating composition), the compatibility with the other components is improved.

The content (%) of the structural unit (i _4-12 ) in the component (B) is represented by the general formula (I) with respect to the total monomer weight used in producing the polymer of the component (B). This usually corresponds to the weight percentage of the (meth) acrylic acid ester having 4 to 12 carbon atoms.

The structural unit (i) contained in the component (B) may be a single type or two or more types.

Component (B) may contain a structural unit other than the structural unit (i). Examples of the structural unit other than the structural unit (i) that may be contained in the component (B) include a structural unit derived from α, β-unsaturated carboxylic acid (eg, a structure derived from (meth) acrylic acid). Units) and structural units derived from α, β-unsaturated carboxylic acid esters other than the structural unit (i) (eg, (meth) acrylic acid alkyl esters, (meth) acrylic acid hydroxyalkyl esters).

[1-2-2. Glass transition temperature of component (B)]
Component (B) has a glass transition temperature (Tg) of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −25 ° C. or lower, and further preferably −30 ° C. or lower. When Tg exceeds 0 ° C., the flexibility of the modified polyolefin-based resin is lowered, so that the chipping resistance is inferior. Tg is usually −70 ° C. or higher, preferably −65 ° C. or higher, more preferably −60 ° C. or higher.

The glass transition temperature (Tg) is obtained by using the value of each glass transition temperature when each monomer unit constituting the component (B) is a homopolymer and the weight ratio of each monomer unit in the component (B). It can be calculated by the following FOX equation. The Tg of each homopolymer may be Tg listed in the Polymer Handbook (Wiley-Interscience Publication, 4th Edition, 1999) and product data.
The weight ratio of each monomer unit in component (B) is usually the same as the weight ratio (blending ratio) of each monomer with respect to the total monomer weight used in producing the polymer of component (B). To do.

<FOX _{_{_{_{formula> 1 / Tg = W 1 /}}}} Tg 1 + W 2 / Tg 2 + W 3 / Tg 3 + ··· W n / Tg n

In the above formula, component (B) and composed of n kinds of monomer units _U 1 ~ _{U n,} monomer units _{_U} 1 ~ _U _Tg 1 ~ each glass transition temperature of the homopolymer of the _n Tg _n and then, each of the weight fraction of monomer units _U 1 ~ _{U n} and _{_W} 1 ~ _W _n. However, the 1 the sum of proportions by weight of monomer units _U 1 ~ _{U n.}

As the glass transition temperature of component (B), the glass transition temperature measured for the polymer of component (B) as a raw material before grafting to component (A) may be used. The glass transition temperature of the component (B) as a raw material can be measured using, for example, a differential scanning calorimeter (eg, “DSC6200R thermal analysis system”, supplied from Seiko Instruments Inc.).
Preferably, the glass transition temperature of the component (B) according to the present invention is the value of each glass transition temperature when each monomer unit constituting the component (B) is a homopolymer and each unit in the component (B). It is a value calculated by the FOX equation using the weight ratio of the monomer unit.

[1-2-3. Weight average molecular weight of component (B)]
Although there is no limitation in particular in the weight average molecular weight (Mw) of a component (B), Preferably it is 1,000 or more, More preferably, it is 3,000 or more, Preferably it is 100,000 or less, More preferably 20,000 or less.
The weight average molecular weight of component (B) is preferably 1,000 to 100,000, more preferably 3,000 to 20,000.
Here, the weight average molecular weight of the component (B) usually coincides with the weight average molecular weight measured for the polymer of the component (B) as a raw material before being grafted to the component (A).

[1-2-4. Hydroxyl value of component (B)]
The hydroxyl value of component (B) is not particularly limited, but is preferably 5 mgKOH / g or more, preferably 560 mgKOH / g or less, more preferably 280 mgKOH / g or less, and even more preferably 168 mgKOH / g or less. It is.
When the component (B) has a hydroxyl value of 5 mgKOH / g or more, when the modified polyolefin resin is combined with other components to form a composition (for example, a coating composition), the compatibility with the other components is good. It becomes. When the hydroxyl value of the component (B) is 560 mgKOH / g or less, the modified polyolefin resin has an appropriate polarity, so when the modified polyolefin resin is combined with other components to form a composition, The compatibility with the component is improved.
The hydroxyl value of component (B) is preferably 5 to 560 mgKOH / g, more preferably 5 to 280 mgKOH / g, and still more preferably 5 to 168 mgKOH / g.

Hydroxyl value _{X B} component (B), component (B) n type (n is an integer of 1 or more) is composed of monomer units _U 1 ~ _{U n} of the monomer unit _U 1 ~ _{U n} hydroxyl value of a homopolymer of each set to _{_{X 1 ~ X n (mgKOH /}} g), the weight ratio of the monomer units _U 1 ~ _{U n} in component (B), respectively and _{_Y} 1 ~ _Y _n (where monomer The sum of the weight ratios of the body units U ₁ to U _n is 1.) and the following formula.
X _B = X ₁ Y ₁ + X ₂ Y ₂ +... X _n Y _n
The hydroxyl value of component (B) in the examples is also a value calculated by the above method.

[1-3. Modified polyolefin resin]
The modified polyolefin resin of the present invention is a copolymer in which the component (B) is grafted to the component (A): polyolefin resin or a modified product thereof.
The modified polyolefin resin of the present invention may be a copolymer in which the component (B) is grafted to the component (A), and after the graft polymerization reaction for grafting the component (B) to the component (A). Further, it may be a copolymer modified with a modifying agent (for example, with chlorine and / or acid), or a copolymer not modified with a modifying agent after the graft polymerization reaction.
In the modified polyolefin resin of the present invention, the polymer of component (B) is grafted to component (A). The modified polyolefin resin of the present invention may be a resin produced by grafting a polymer of the component (B) as a raw material to the component (A) as a raw material by a graft polymerization reaction. A resin produced by grafting a monomer for constituting the polymer (block) of the component (B) to the component (A) sequentially or simultaneously by a graft polymerization reaction may be used.
The modified polyolefin resin of the present invention may be a chlorinated graft modified polyolefin resin, an acid modified graft modified polyolefin resin, or an acid modified and chlorinated graft modified polyolefin resin.

The modified polyolefin resin of the present invention is preferably a chlorinated resin. “Chlorinated resins” include resins in which component (A) is chlorinated, resins in which component (B) is chlorinated, and resins in which components (A) and (B) are chlorinated. The The modified polyolefin resin of the present invention is more preferably a chlorinated resin in which the component (A) is chlorinated.

When the modified polyolefin resin is a chlorinated resin, the chlorine content of the modified polyolefin resin is preferably 10% by weight or more, more preferably 15% by weight or more. The upper limit of the chlorine content in the modified polyolefin resin is preferably 35% by weight or less, more preferably 30% by weight or less.
It is estimated that the chlorine content of the modified polyolefin resin is within this range, the polarity of the modified polyolefin resin increases, and the modified polyolefin resin is likely to exhibit a linear structure due to steric repulsion between chlorine atoms, Therefore, it is estimated that it is excellent in dispersibility in highly polar solvents (eg, alcohols).

[1-3-1. Weight average molecular weight of modified polyolefin resin]
The weight average molecular weight of the modified polyolefin resin of the present invention is not particularly limited, but is preferably 10,000 or more, more preferably 30,000 or more, preferably 200,000 or less, more preferably 150,000 or less.
Adhesion is improved when the weight average molecular weight of the modified polyolefin resin is 10,000 or more. Further, when the weight average molecular weight of the modified polyolefin resin is 200,000 or less, when the modified polyolefin resin is combined with other components to form a composition, the compatibility with the other components becomes good.
The weight average molecular weight of the modified polyolefin resin of the present invention is preferably 10,000 to 200,000, and more preferably 30,000 to 150,000.

[1-3-2. Content of component (B)]
Although there is no limitation in particular in the content rate of the component (B) in the modified polyolefin resin of this invention, Preferably it is 20 weight% or more, More preferably, it is 30 weight% or more, More preferably, it is 50 weight% or more. is there. The upper limit is preferably 80% by weight or less.
The content of the component (B) in the modified polyolefin resin means the weight ratio of the component (B) grafted to the component (A) to the modified polyolefin resin.
The weight ratio (%) of the component (B) part to the modified polyolefin resin usually coincides with the blending ratio (%) of the component (B) graft-polymerized to the component (A) when producing the modified polyolefin resin ( However, the total of the blending weight of component (A) and the blending weight of component (B) is 100%.)

[1-3-3. Ingredient (A) / Ingredient (B)]
The weight ratio of component (A) to component (B) in the modified polyolefin resin of the present invention is not particularly limited, but is preferably 20/80 or more, more preferably 30/70 or more, and still more preferably. It is 50/50 or more, preferably 80/20 or less.
The weight ratio of component (A) to component (B) in the modified polyolefin resin of the present invention is preferably 20/80 or more and 80/20 or less.

[2. Method for producing modified polyolefin resin]
The production method of the modified polyolefin resin of the present invention is derived, for example, from component (A): polyolefin resin or a modified product thereof, component (B): (meth) acrylic acid ester represented by the above general formula (I) And a step of graft polymerizing a polymer containing the structural unit (i) and having a glass transition temperature (Tg) of 0 ° C. or lower. In formula (I), R ¹ represents a hydrogen atom or methyl, R ² represents a group represented by —C _n H _{2n + 1} , and n represents an integer of 1 to 18.
Component (A) and Component (B) are the items [1. The same as the component (A) and the component (B) respectively described in the modified polyolefin resin].
As a method of introducing the component (B) into the component (A) by graft copolymerization, for example, the component (A) as a raw material, the component (B) as a raw material: represented by the general formula (I) ( A method of graft copolymerizing a polymer containing a structural unit (i) derived from a (meth) acrylic acid ester and having a glass transition temperature (Tg) of 0 ° C. or lower, and component (A) as a raw material, component (B) And a method of graft copolymerizing a (meth) acrylic acid ester represented by the above general formula (I), which is a raw material for constituting the polymer.
When the (meth) acrylic acid ester represented by the above general formula (I) is graft copolymerized with the component (A) as a raw material, the (meth) acrylic acid ester represented by the above general formula (I) You may add sequentially to the component (A) as a raw material, or may be added at once. Moreover, you may add monomers other than the (meth) acrylic acid ester represented by the said general formula (I) to the component (A) as a raw material.

The conditions for graft polymerization are not particularly limited, and may be a known method such as a melting method or a solution method. The melting method is advantageous in that the operation is simple and the reaction can be performed in a short time. When the solution method is used, a uniform graft polymer can be obtained with few side reactions.

In the case of the melting method, the component (A) is heated and melted (heated and melted) in the presence of a radical reaction initiator to react with the component (B). Component (B) may be in the form of a monomer before polymerization or in the form of a polymer after polymerization. The temperature for heating and melting may be not lower than the melting point of component (A), and preferably not lower than the melting point of component (A) and not higher than 300 ° C. In the case of heating and melting, equipment such as a Banbury mixer, a kneader, and an extruder can be used.

In the case of the solution method, the component (A) is dissolved in an organic solvent and then reacted with the component (B) by heating and stirring in the presence of a radical reaction initiator. Component (B) may be in the form of a monomer before polymerization or in the form of a polymer after polymerization.
As the organic solvent, an aromatic hydrocarbon solvent such as toluene or xylene is preferably used. The temperature during the reaction is preferably 100 to 180 ° C.

Although it does not specifically limit as a radical reaction initiator used in the case of a melting method and a solution method, For example, an organic peroxide type compound or an azonitrile is mentioned. Examples of the organic peroxide compounds include di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, 2,5-dimethyl-2,5- Di (tert-butylperoxy) hexane, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1-bis (tert-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (tert -Butylperoxy) -cyclohexane, cyclohexanone peroxide, tert-butylperoxybenzoate, tert-butylperoxyisobutyrate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butyl 2-ethyl hexanoate, tert- butylperoxy isopropyl carbonate, cumylperoxy octoate, and the like, may be selected to have an appropriate half-life temperature in accordance with temperature at which the radical polymerization.

In the method for producing a modified polyolefin resin of the present invention, the component (A) may be graft-polymerized as a composition containing an optional stabilizer in addition to the component (A).
As optional stabilizers, for example, epoxy compounds; metal soaps such as calcium stearate and lead stearate, which are used as stabilizers for polyvinyl chloride resins; organometallic compounds such as dibutyltin dilaurate and dibutylmalate Hydrotalcite compounds. The epoxy compound is not particularly limited, but an epoxy compound that is compatible with a resin that has been modified such as chlorination is preferable. Examples of the epoxy compound include compounds having an epoxy equivalent of about 100 to 500 and having one or more epoxy groups per molecule. Examples of such epoxy compounds include vegetable oils having natural unsaturated groups. Epoxidized vegetable oil obtained by epoxidizing with peracid such as peracetic acid (epoxidized soybean oil, epoxidized linseed oil, etc.); epoxidized unsaturated fatty acid such as oleic acid, tall oil fatty acid, soybean oil fatty acid, etc. Epoxidized fatty acid esters; Epoxidized alicyclic compounds such as epoxidized tetrahydrophthalate; obtained by condensing bisphenol A or polyhydric alcohol and epichlorohydrin, for example, bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl Ether, glyce Ethers such as allyl polyglycidyl ether and sorbitol polyglycidyl ether; and butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butylphenyl glycidyl ether, and monoepoxy compounds represented by tert-butylphenyl glycidyl ether, phenol polyethylene oxide glycidyl ether and the like. One type of stabilizer may be used alone, or a combination of two or more types may be used. When the component (A) is graft-polymerized in the form of a composition containing a stabilizer, the weight ratio of the stabilizer to the component (A) is preferably 1 to 20% by weight (in terms of solid content).

The method for producing the modified polyolefin resin of the present invention may include an optional step in addition to the above-described steps.
Examples of the optional step include a step of graft-polymerizing the component (B) to the component (A) to obtain a graft-modified polyolefin-based resin, and further modifying the graft-modified polyolefin-based resin. The type of modification is not particularly limited, and examples thereof include known modifications such as chlorination; epoxidation; hydroxylation; anhydrous carboxylic oxidation; carboxylic oxidation;
These modifications can be performed by known methods.
For example, when the modified polyolefin resin is a chlorinated resin, the production method of the present invention may include a step of chlorinating the resin at any stage of the production. For example, the polyolefin resin is chlorinated. And a step of chlorinating the graft-modified polyolefin resin obtained after graft polymerization of the component (B) onto the polyolefin resin.
Therefore, as a production method for obtaining a modified polyolefin resin which is a chlorinated resin, for example, a method of grafting component (B) onto component (A) and then chlorinating, a method of chlorinating polyolefin resin and component (A) And a method of grafting component (B) onto component (A) after obtaining chlorinated polyolefin resin as.

The chlorination method may be a known method and is not particularly limited. Examples thereof include a method in which chlorine is blown after the resin is dissolved in a chlorination solvent such as chloroform and chlorine is introduced. More specifically, the chlorination is carried out by dispersing or dissolving the resin in a medium such as water, carbon tetrachloride, or chloroform, and applying pressure or atmospheric pressure in the presence of a catalyst or under irradiation with ultraviolet light at 50 to 140 ° C. This can be done by blowing chlorine gas in the temperature range.

When a chlorinated solvent is used in the production of the chlorinated resin, the chlorinated solvent used can be usually distilled off under reduced pressure or replaced with another organic solvent.

When the chlorinated polyolefin resin as the component (A) is obtained by chlorinating the polyolefin resin, the chlorine content of the chlorinated polyolefin resin as the component (A) is preferably 15% by weight or more, more preferably 20% by weight. That's it. When the chlorine content is 15% by weight or more, the resulting modified polyolefin resin is excellent in dispersibility in alcohols such as ethanol and isopropanol. The upper limit of the chlorine content in the chlorinated polyolefin resin as the component (A) is preferably 40% by weight or less, more preferably 35% by weight or less. When the chlorine content is 40% by weight or less, the resulting modified polyolefin resin is excellent in adhesion to a polyolefin substrate.

[3. Modified polyolefin resin composition]
The modified polyolefin resin of the present invention may constitute a modified polyolefin resin composition together with other optional components. Examples of the optional component include a stabilizer for suppressing the release of chlorine. Stabilizers are not particularly limited. For example, epoxy compounds; metal soaps such as calcium stearate and lead stearate used as stabilizers for polyvinyl chloride resins; organic metals such as dibutyltin dilaurate and dibutylmalate Compounds: Hydrotalcite compounds are exemplified, and an epoxy compound is preferable. Although an epoxy compound is not specifically limited, For example, said [2. In the method for producing a modified polyolefin resin], an epoxy compound exemplified as an optional stabilizer that the composition of component (A) can contain is exemplified, and an epoxy compound compatible with a modified polyolefin resin modified with chlorine is used. preferable. As a stabilizer, only 1 type may be used among these and 2 or more types may be used together.
In addition, for example, the modified polyolefin resin composition may be in the form of a dispersion composition containing a modified polyolefin resin and a dispersion medium. In the present specification, the “dispersion medium” includes a solvent capable of dissolving the modified polyolefin resin, and the “dispersion composition” may be a solution of the modified polyolefin resin composition.

Examples of the dispersion medium include aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aliphatic hydrocarbons such as hexane, heptane, and octane; acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketones; esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol; ethylene glycol, Examples include glycols such as ethyl cellosolve and butyl cellosolve; water and the like.
The dispersion medium may be a single type or a combination of two or more types.

[4. Use of modified polyolefin resin]
The modified polyolefin resin of the present invention can be used as a metal and / or resin adhesive, primer, paint binder and ink binder. In particular, the modified polyolefin resin of the present invention has good adhesion and excellent chipping resistance, and is therefore useful as a binder for automobile paint and a primer for automobile painting.

Next, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited thereto. “Part” and “%” mean “part by weight” and “% by weight”, respectively, unless otherwise specified. The following operations were performed in a normal temperature and normal pressure atmosphere unless otherwise specified.

<Production Example A1> Polyolefin resin Twin-screw extrusion in which a propylene-based random copolymer (propylene unit content: 80% by weight, ethylene unit content 20% by weight) produced using a metallocene catalyst as a polymerization catalyst is set at a barrel temperature of 350 ° C. It was supplied to a machine for thermal degradation to obtain a polypropylene resin (A1) having a weight average molecular weight of 5,000.

<Production Example A2> Polyolefin Resin Same as Production Example A1 except that a propylene random copolymer (propylene unit content: 90% by weight, ethylene unit content 10% by weight) produced using a metallocene catalyst as a polymerization catalyst was used. Thus, a polypropylene resin (A2) having a weight average molecular weight of 111,000 was obtained.

<Production Example A3> Polyolefin Resin Similar to Production Example A1 except that a propylene random copolymer (propylene unit content: 94% by weight, ethylene unit content 6% by weight) produced using a metallocene catalyst as a polymerization catalyst was used. Thus, a polypropylene resin (A3) having a weight average molecular weight of 100,000 was obtained.

<Production Example A4> Polyolefin resin A propylene random copolymer produced using a metallocene catalyst as a polymerization catalyst (propylene unit content: 90 wt%, ethylene unit content 5 wt%, butene unit content 5 wt%) was used. Except for the above, a polypropylene resin (A4) having a weight average molecular weight of 45,000 was obtained in the same manner as in Production Example A1.

<Production Example A5> Polyolefin Resin A biaxial extrusion in which a propylene random copolymer (propylene unit content: 80% by weight, ethylene unit content 20% by weight) produced using a metallocene catalyst as a polymerization catalyst is set at a barrel temperature of 400 ° C. It was supplied to a machine for thermal degradation to obtain a polypropylene resin (A5) having a weight average molecular weight of 2,000.

<Production Example CL1> Chlorinated Polyolefin Resin 100 parts by weight of the polypropylene resin (A1) obtained in Production Example A1 was charged into a glass-lined reaction kettle. Chloroform was added thereto, and chlorine gas and oxygen gas were blown in while irradiating ultraviolet rays under a pressure of ² kg / cm ² , and chlorinated until the chlorine content became 32 wt%. After completion of the reaction, 6 parts by weight of an epoxy compound (Eposizer W-100EL, manufactured by Dainippon Ink & Chemicals, Inc.) is added as a stabilizer and supplied to a vented extruder equipped with a solvent removal suction part on the screw shaft part. Then, the solvent was removed and solidified to obtain a chlorinated polypropylene resin (A1CL1) having a weight average molecular weight of 5000, which is a chlorinated polyolefin resin.

<Production Example CL2> Chlorinated Polyolefin Resin Chlorinated polypropylene resin (A5CL2) having a weight average molecular weight of 2,000 as in Production Example CL1, except that the polypropylene resin (A5) obtained in Production Example A5 was used. Got.

<Production Example CL3> Chlorinated Polyolefin Resin Chlorinated polypropylene resin (A4CL3) having a weight average molecular weight of 50,000 in the same manner as in Production Example CL1 except that the polypropylene resin (A4) obtained in Production Example A4 was used. Got.

<Production Example M1> Acid-Modified Polyolefin Resin 100 parts by weight of the polypropylene resin (A3) obtained in Production Example A3 is placed in a three-necked flask equipped with a stirrer, a dropping funnel, and a monomer reflux condenser tube, and 180 ° C. Completely dissolved in an oil bath. After replacing the flask with nitrogen for about 10 minutes, 4 parts by weight of maleic anhydride was added over about 5 minutes while stirring, and then 0.4 parts by weight of di-tert-butyl peroxide was added to 1 part of heptane. It melt | dissolved in the part and it injected | thrown-in over about 30 minutes from the dropping funnel. Thereafter, the inside of the system was kept at 180 ° C., and the reaction was further continued for 1 hour. Then, the unreacted maleic anhydride was removed over about 1 hour while reducing the pressure in the flask with an aspirator, and the acid modification with a weight average molecular weight of 105,000 was performed. A polyolefin resin (A3M1) was obtained.

<Production Example MCL1> Acid-modified chlorinated polyolefin resin (acid-modified)
100 parts by weight of the polypropylene resin (A2) obtained in Production Example A2, 4 parts by weight of maleic anhydride and 2 parts by weight of di-t-butyl peroxide were uniformly mixed, and a twin-screw extruder (L / D = 60, φ = 15 mm, 1st barrel to 14th barrel). Residence time 10 minutes, rotation speed 200 rpm, barrel temperature 100 ° C (first and second barrels), 200 ° C (third to eighth barrels, 90 ° C (9th and 10th barrels), 110 ° C (11th to 14th barrels) The reaction was carried out under the conditions of), and unreacted maleic anhydride was removed by performing a reduced pressure treatment to obtain a maleic anhydride-modified polypropylene resin (A2M2).

(Chlorination)
100 parts by weight of the obtained maleic anhydride-modified polypropylene resin (A2M2) was put into a glass-lined reaction kettle. Chloroform was added thereto, and chlorine gas and oxygen gas were blown in while irradiating ultraviolet rays under a pressure of ² kg / cm ² , and chlorinated until the chlorine content became 32 wt%. After completion of the reaction, 6 parts by weight of an epoxy compound (Eposizer W-100EL, manufactured by Dainippon Ink & Chemicals, Inc.) is added as a stabilizer and supplied to a vented extruder equipped with a solvent removal suction part on the screw shaft part. Then, the solvent was removed and solidified to obtain an acid-modified chlorinated polypropylene resin (A2M2CL1) having a weight average molecular weight of 143,000, which is a chlorinated polyolefin resin.

<Production Example MCL2> Acid-Modified Chlorinated Polyolefin Resin An acid-modified chlorinated polypropylene resin having a weight average molecular weight of 5,000 in the same manner as in Production Example MCL1, except that the polypropylene resin A1 obtained in Production Example A1 was used. (A1M2CL2) was obtained.

<Production Example MCL3> Acid-Modified Chlorinated Polyolefin Resin An acid-modified chlorinated polypropylene resin having a weight average molecular weight of 110,000 in the same manner as in Production Example MCL1 except that the polypropylene resin A3 obtained in Production Example A3 was used. (A3M2CL3) was obtained.

<Production Example MCL4> Acid-Modified Chlorinated Polyolefin Resin An acid-modified polyolefin resin (A4M1) was obtained in the same manner as in Production Example M1, except that the polypropylene resin A4 obtained in Production Example A4 was used. Next, chlorination was carried out in the same manner as in Production Example CL1 except that the obtained acid-modified polyolefin resin (A4M1) was used to obtain an acid-modified chlorinated polypropylene resin (A4M1CL4) having a weight average molecular weight of 75,000. It was.

<Example 1>
(Production of acrylic polymer (B1))
After adding 2.8 parts by weight of a peroxyester peroxide (Nyper BMT-K40, manufactured by NOF Corporation) to 233 parts of toluene heated to 85 ° C. in a nitrogen atmosphere, the examples in Table 2 100 parts by weight of each acrylic monomer was added at the blending ratio described in 1 and reacted at 85 ° C. for 6 hours or longer, then cooled and cooled with an acrylic polymer having a glass transition temperature of −66 ° C. A coalescence (B1) was obtained.

(Manufacture of modified polyolefin resin)
80 parts of chlorinated polypropylene resin (A1CL1) as component (A) obtained in Production Example CL1 and 20 parts of acrylic polymer (B1) as component (B) were heated to 70 ° C. in a nitrogen atmosphere. After being added to 233 parts of toluene, reacted at 70 ° C. for 4 hours, cooled, and then added 1 part by weight of an epoxy compound (Eposizer W-100EL, manufactured by Dainippon Ink & Chemicals, Inc.) as a stabilizer. Then, a toluene dispersion containing the modified polyolefin resin (C1) was obtained.

<Example 2>
An acrylic polymer having a glass transition temperature of −33 ° C. was prepared in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added in the mixing ratio described in Example 2 in Table 2. Combined (B2) was obtained.
Instead of 80 parts of chlorinated polypropylene resin (A1CL1), 50 parts of acid-modified chlorinated polypropylene resin (A2M2CL1) obtained in Production Example MCL1 was used, and acrylic polymer (B1) was used in place of 20 parts. A toluene dispersion containing the modified polyolefin resin (C2) was obtained in the same manner as in Example 1 except that 50 parts of the coalescence (B2) was used.

<Example 3>
Acrylic polymer having a glass transition temperature of −1 ° C. was prepared in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added in the mixing ratio described in Example 3 in Table 2. Combined (B3) was obtained.
Instead of 80 parts of chlorinated polypropylene resin (A1CL1), 20 parts of acid-modified chlorinated polypropylene resin (A1M2CL2) obtained in Production Example MCL2 was used, and acrylic polymer (B1) instead of 20 parts. A toluene dispersion containing the modified polyolefin resin (C3) was obtained in the same manner as in Example 1 except that 80 parts of the combined (B3) was used.

<Example 4>
An acrylic polymer having a glass transition temperature of −55 ° C. was prepared in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the blending ratio described in Example 4 in Table 2. Combined (B4) was obtained.
Instead of 80 parts of chlorinated polypropylene resin (A1CL1), 70 parts of acid-modified chlorinated polypropylene resin (A3M2CL3) obtained in Production Example MCL3 was used, and acrylic polymer (B1) was used in place of 20 parts. A toluene dispersion containing the modified polyolefin resin (C4) was obtained in the same manner as in Example 1 except that 30 parts of the coalescence (B4) was used.

<Example 5>
Acrylic polymer having a glass transition temperature of −46 ° C. was prepared in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the blending ratio described in Example 5 in Table 2. Combined (B5) was obtained.
Instead of 80 parts of chlorinated polypropylene resin (A1CL1), 60 parts of acid-modified chlorinated polypropylene resin (A4M1CL4) obtained in Production Example MCL4 was used, and acrylic polymer (B1) instead of 20 parts. A toluene dispersion containing the modified polyolefin resin (C5) was obtained in the same manner as in Example 1 except that 40 parts of the coalesced (B5) was used.

<Example 6>
An acrylic polymer having a glass transition temperature of -43 ° C. was prepared in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the blending ratio described in Example 6 in Table 2. Combined (B6) was obtained.
The chlorinated polypropylene resin (A4CL3) obtained in Production Example CL3 was used instead of the chlorinated polypropylene resin (A1CL1), and the acrylic polymer (B6) was used instead of the acrylic polymer (B1). In the same manner as in Example 1, a toluene dispersion containing a modified polyolefin resin (C6) was obtained.

<Example 7>
An acrylic polymer having a glass transition temperature of −60 ° C. was prepared in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the blending ratio described in Example 7 in Table 2. Combined (B7) was obtained.
Modified polyolefin resin in the same manner as in Example 1 except that 60 parts of chlorinated polypropylene resin (A1CL1) was used and 40 parts of acrylic polymer (B7) was used instead of 20 parts of acrylic polymer (B1). A toluene dispersion containing (C7) was obtained.

<Example 8>
An acrylic polymer having a glass transition temperature of −66 ° C. was prepared in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the blending ratio described in Example 8 in Table 2. Combined (B8) was obtained.
Instead of 80 parts of the chlorinated polypropylene resin (A1CL1), 70 parts of the chlorinated polypropylene resin (A5CL2) obtained in Production Example CL2 was used, and an acrylic polymer (B1) instead of 20 parts. B8) A toluene dispersion containing the modified polyolefin resin (C8) was obtained in the same manner as in Example 1 except that 30 parts were used.

<Example 9>
Acrylic polymer having a glass transition temperature of −24 ° C. was prepared in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the blending ratio described in Example 9 in Table 2. Combined (B9) was obtained.
A modified polyolefin resin (Example 1) except that 50 parts of chlorinated polypropylene resin (A1CL1) was used and 50 parts of acrylic polymer (B9) was used instead of 20 parts of acrylic polymer (B1). A toluene dispersion containing C8) was obtained.

<Example 10>
An acrylic polymer having a glass transition temperature of −66 ° C. was prepared in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the blending ratio described in Example 10 in Table 2. Combined (B10) was obtained.
Instead of 80 parts of chlorinated polypropylene resin (A1CL1), 60 parts of acid-modified polypropylene resin (A3M1) obtained in Production Example M1 was used, and acrylic polymer (B10) instead of 20 parts of acrylic polymer (B1). ) A toluene dispersion containing the modified polyolefin resin (C10) was obtained in the same manner as in Example 1 except that 40 parts were used.

<Comparative Example 1>
An acrylic polymer having a glass transition temperature of 27 ° C., in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the blending ratio described in Comparative Example 1 in Table 2. (B11) was obtained.
Instead of 80 parts of chlorinated polypropylene resin (A1CL1), 50 parts of acid-modified chlorinated polypropylene resin (A3M2CL3) obtained in Production Example MCL3 was used, and acrylic polymer (B1) instead of 20 parts. (B11) A toluene dispersion containing a modified polyolefin resin (C10) was obtained in the same manner as in Example 1 except that 50 parts were used.

<Evaluation>
The modified polyolefin resins obtained in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Table 3.

<Weight average molecular weight (Mw)>
It measured by GPC according to the following conditions.
Equipment: HLC-8320GPC (supplied by Tosoh Corporation)
Column: TSK-gel G-6000 H × L, G-5000 H × L, G-4000 H × L, G-3000 H × L, G-2000 H × L (supplied by Tosoh Corporation)
Eluent: THF
Flow rate: 1 mL / min
Temperature: Pump oven, column oven 40 ° C
Injection volume: 100 μL
Reference material: Polystyrene EasiCal PS-1 (supplied by Agilent Technology)

<Glass transition temperature (Tg)>
Each glass transition temperature when each monomer used in producing the polymer of component (B) that has been identified is a homopolymer, and the blend of each monomer used in producing component (B) Using the ratio, the above-mentioned FOX equation was used for calculation.

<Hydroxyl value of component (B) (acrylic polymer) (mgKOH / g)>
The hydroxyl value in the case where each monomer used in producing the polymer of the component (B) that has been identified is a homopolymer, and the blending ratio of each monomer used in producing the component (B) And calculated by the method described above.

<Stability of resin dispersion>
About the toluene dispersion liquid containing the modified polyolefin resin obtained in Examples and Comparative Examples, the properties immediately after production and after one week from immediately after production were visually evaluated according to the following criteria. If it is good, it can be used.
Best: No separation of the dispersion was observed immediately after production and after 1 week, and the solution properties were good.
Good: After one week, the separation of the dispersion can be confirmed visually, or the dispersion is turbid, but no separation is observed in the dispersion immediately after production.
Defect: Separation of the dispersion is observed immediately after production and after one week.

<Paint stability>
The toluene dispersions of the modified polypropylene resins obtained in Examples and Comparative Examples were blended with toluene to prepare a toluene dispersion having a solid content of 20%. 15 parts by weight of the prepared toluene dispersion (solid content 20 wt%) is added to 90 parts by weight of urethane resin (manufactured by Hitachi Chemical Co., Ltd., solid content 30 wt%), and the mixture is stirred for 10 minutes with a shaker and allowed to stand at room temperature for 1 day. The solution properties after placement were observed, and the paint stability (compatibility of the compounded resin) was visually judged from the separated state of the solution.
A: Thickening and separation of the solution are not observed, and the solution property is good.
B: Although the solution is slightly thickened, no separation or the like is observed.
C: Although there is no separation of components, fine particles are confirmed in the solution.
D: Separation of components can be visually confirmed.

<Preparation of test piece>
The dispersions obtained in the examples and comparative examples were adjusted to a solid content concentration of 30% by weight, coated on a polypropylene base material, dried at 80 ° C. for 5 minutes, and then coated with a two-component urethane paint, and 30 at 80 ° C. Each test was performed after partial drying and preparing a test piece (painted plate).

<Adhesion test>
Line coatings that reach the substrate at 1 mm intervals are placed vertically and horizontally on the paint film on the painted plate to create 100 sections (cross-cut), and cellophane adhesive tape is adhered onto it and peeled off in the 180 ° direction. . The operation of bringing the cellophane adhesive tape into close contact and peeling off was performed 10 times for the same 100 sections, and the adhesion (adhesiveness) was evaluated according to the following criteria. If there are 50 or less sections of the peeled coating film, there is no practical problem.
(Adhesion evaluation criteria)
A: There is no peeling of the coating film.
B: There are 1 or more and 10 or less sections of the peeled coating film.
C: The division of the peeled coating film is more than 10 and 50 or less.
D: There are more than 50 sections of the peeled coating film.

<Gasohole resistance test>
The coated plate was immersed in regular gasoline / ethanol = 9/1 (v / v) for 120 minutes, the state of the coating film was observed, and the gasohol resistance was evaluated according to the following criteria. If peeling does not occur on the coating film surface, there is no practical problem.
(Evaluation criteria for gasohol resistance)
A: There is no change in the coating film surface.
B: A slight change is observed on the surface of the coating film, but no peeling is observed.
C: A change is observed on the surface of the coating film, but no peeling occurs.
D: Peeling has occurred on the coating film surface.

<Chip resistance test>
The painted plate is cooled in a low-temperature room cooled to -20 ° C, and the test plate is fixed vertically to the test plate mounting part of the stepping stone testing machine (Suga Test Instruments Co., Ltd., JA-400 type) at an angle of 90 ° from the horizontal. Then, 100 g of No. 7 crushed stone was sprayed for 5 seconds at an air pressure of 5 kgf / cm ² to scratch the test plate. After that, the painted plate is washed with water and dried, and the cellophane adhesive tape is adhered to the coated surface, peeled off with one end of the tape, and the paint film lifted by chipping is removed, and the degree of peeling scratches is evaluated according to the following criteria. did. The evaluation of peeling scratches was performed within a frame of 70 mm length x 70 mm width of the impacted part.
A: The best. The peeled area ratio per evaluation area is 0.0% or more and less than 0.7%.
B: Good. The peeled area ratio per evaluation area is 0.7% or more and less than 1.2%.
C: Inferior. The peeled area ratio per evaluation area is 1.2% or more and less than 3.5%.
D: Inferior. The peeled area ratio per evaluation area is 3.5% or more.

In the item “resin skeleton” in Table 1, “P” represents propylene, “E” represents ethylene, and “B” butadiene.

In Table 2, “2EHA” is 2-ethylhexyl acrylate, “HEA” is 2-hydroxyethyl acrylate, “BA” is butyl acrylate, “INA” is isononyl acrylate, “AA” is acrylic acid, “LMA” "" Represents lauryl methacrylate, "LA" represents lauryl acrylate, "HEMA" represents 2-hydroxyethyl methacrylate, and "EA" represents ethyl acrylate.
The ratio of C _4-12 is the weight percentage (%) of the (meth) acrylic acid ester having 4 to 12 carbon atoms and represented by the general formula (I) with respect to the total weight of the blended monomers. is there.

According to Table 3, it can be seen that the modified polyolefin resin of the example is superior in chipping resistance as compared with Comparative Example 1. Moreover, it turns out that the modified polyolefin resin of an Example has no problem in the adhesiveness to the polypropylene which is a nonpolar base material, and stability when it is set as a resin dispersion liquid or a coating material.

Claims

Component (A): Polyolefin resin or modified product thereof, Component (B): Containing structural unit (i) derived from (meth) acrylic acid ester represented by the following general formula (I), glass transition temperature (Tg) A modified polyolefin resin, which is a copolymer grafted with a polymer having a temperature of 0 ° C. or lower.
CH 2 = C (R 1 ) COOR 2 (I)
(In Formula (I), R 1 represents a hydrogen atom or methyl, R 2 represents a group represented by —C n H 2n + 1 , and n represents an integer of 1 to 18)
The modified polyolefin resin according to claim 1, wherein the structural unit (i) has 4 to 12 carbon atoms.
The modified polyolefin resin according to claim 2, wherein the content of the structural unit (i) in the component (B) is 40% by weight or more and 100% by weight or less.
The modified polyolefin resin according to any one of claims 1 to 3, wherein the component (A) is a chlorinated polyolefin resin.
The modified polyolefin resin according to any one of claims 1 to 4, wherein the component (B) has a weight average molecular weight of 1,000 or more and 100,000 or less.
The modified polyolefin resin according to any one of claims 1 to 5, wherein the hydroxyl value of the component (B) is 5 mgKOH / g or more and 560 mgKOH / g or less.
The modified polyolefin according to any one of claims 1 to 6, wherein the weight ratio of component (A) to component (B) (component (A) / component (B)) is 20/80 or more and 80/20 or less. Resin.
The modified polyolefin resin according to any one of claims 1 to 7, having a weight average molecular weight of 10,000 or more and 200,000 or less.
A dispersion composition comprising the modified polyolefin resin according to any one of claims 1 to 8 and a dispersion medium.
A primer comprising the modified polyolefin resin according to any one of claims 1 to 8 or the dispersion composition according to claim 9.
Component (A): Polyolefin resin or modified product thereof, Component (B): Containing structural unit (i) derived from (meth) acrylic acid ester represented by the following general formula (I), glass transition temperature (Tg) A process for producing a modified polyolefin resin, comprising a step of graft polymerization of a polymer having a temperature of 0 ° C. or lower.
CH 2 = C (R 1 ) COOR 2 (I)
(In Formula (I), R 1 represents a hydrogen atom or methyl, R 2 represents a group represented by —C n H 2n + 1 , and n represents an integer of 1 to 18)