阅读说明：本技术 分散树脂组合物 (Dispersion resin composition ) 是由 关口俊司 土井龙二 榊原史泰 吉元贵夫 小池谅 于 2020-03-10 设计创作，主要内容包括：课题在于提供即使降低乳化剂的添加量也可保持分散稳定性的分散树脂组合物。分散树脂组合物,其至少包含:在聚烯烃树脂中导入含有具有环状结构的α,β-不饱和羧酸衍生物的改性成分得到的改性聚烯烃树脂、和水系分散介质,改性聚烯烃树脂的式(1)表示的开环度为70以上,式(1)中,改性度K表示α,β-不饱和羧酸衍生物相对于聚烯烃树脂的含有率(重量%),开环率R表示α,β-不饱和羧酸衍生物中的环状结构的开环率(%)。(1):开环度=改性度K×开环率R。(The problem is to provide a dispersion resin composition which can maintain dispersion stability even if the addition amount of an emulsifier is reduced. A dispersion resin composition comprising at least a modified polyolefin resin obtained by introducing a modifying component containing an alpha, beta-unsaturated carboxylic acid derivative having a cyclic structure into a polyolefin resin, and an aqueous dispersion medium, wherein the modified polyolefin resin has a ring opening degree represented by formula (1) of 70 or more, and in formula (1), the degree of modification K represents the content (wt%) of the alpha, beta-unsaturated carboxylic acid derivative relative to the polyolefin resin, and the ring opening ratio R represents the ring opening ratio (%) of the cyclic structure in the alpha, beta-unsaturated carboxylic acid derivative. (1) Ring opening = modification K × ring opening ratio R.)

1. A dispersion resin composition comprising at least a modified polyolefin resin obtained by introducing a modifying component containing an alpha, beta-unsaturated carboxylic acid derivative having a cyclic structure into a polyolefin resin, and

an aqueous dispersion medium containing a water-based dispersion,

the modified polyolefin resin has a ring opening degree represented by the following formula (1) of 70 or more,

(1) degree of ring opening = degree of modification K X degree of ring opening R

In the formula (1), the modification degree K represents a content (wt%) of the α, β -unsaturated carboxylic acid derivative with respect to the polyolefin resin, and the ring opening ratio R represents a ring opening ratio (%) of a cyclic structure in the α, β -unsaturated carboxylic acid derivative.

2. The dispersion resin composition according to claim 1, wherein the content of the emulsifier is less than 10% by weight.

3. The dispersion resin composition according to claim 1 or 2, wherein the ring-opening ratio R is 60% or more.

4. The dispersion resin composition according to any one of claims 1 to 3, wherein the modified polyolefin resin has a melting point of 50 ℃ or higher.

5. A dispersion resin composition according to any one of claims 1 to 4, wherein the modified polyolefin resin has a weight average molecular weight of 1 ten thousand or more.

6. The dispersion resin composition according to any one of claims 1 to 5, wherein the polyolefin resin contains at least 1 selected from the group consisting of an ethylene-propylene copolymer, a propylene-1-butene copolymer and an ethylene-propylene-1-butene copolymer.

Technical Field

The present invention relates to a dispersion resin composition.

Background

Polyolefin resins such as polypropylene and polyethylene are thermoplastic general-purpose resins. Polyolefin resins are inexpensive and have various excellent properties such as moldability, chemical resistance, weather resistance, water resistance, and electrical characteristics. Therefore, polyolefin resins have been conventionally used in a wide range of fields as sheets, films, molded articles, and the like. However, a molded article of a nonpolar resin such as a polyolefin resin has low polarity and crystallinity unlike a polar base material such as a polyurethane resin, a polyamide resin, an acrylic resin, a polyester resin, or a metal. Therefore, it is known that a nonpolar resin molded product is a substrate that is difficult to adhere to, and adhesion and coating of substrates of the same type or different types are difficult.

In order to solve this problem, it has been proposed to use an acid-modified (modified with an unsaturated carboxylic acid and/or an acid anhydride thereof) propylene random copolymer as a treating agent or a binder before coating. In recent years, from the viewpoint of environmental problems, acid-modified propylene random copolymers have been shifted from conventional organic solvent-based paints to water-based paints. Further, when a composition containing an emulsifier and an acid-modified propylene random copolymer is applied to a substrate as a coating material and dried, the emulsifier is liable to bleed out on the surface of the coating film, resulting in the problem of appearance defects. Further, when another coating material is further applied to the coating surface of the composition, there is a problem that the adhesion between the coating materials is insufficient. Therefore, compositions containing an acid-modified propylene random copolymer and containing no emulsifier have been proposed (see, for example, patent documents 1 to 4).

Documents of the prior art

[ patent document ]

Patent document 1: international publication No. 2004/104090

Patent document 2: japanese patent laid-open No. 2007-031472

Patent document 3: japanese laid-open patent publication No. 2009-040920

Patent document 4: japanese patent laid-open No. 2007-039645.

Disclosure of Invention

Problems to be solved by the invention

The aqueous resin composition described in patent document 1 uses a solvent having high solubility in water. Thus, an aqueous dispersion of a polyolefin containing an unsaturated carboxylic acid structural unit is produced which contains substantially no aqueous processing aid having a boiling point of 185 ℃ or higher at normal pressure. In addition, for the aqueous resin compositions described in patent documents 2 and 3, a solvent having solubility in water, such as an ethylene glycol solvent or an alcohol solvent, is used. Thus, an aqueous dispersion of a modified polyolefin into which a carboxyl group or an unsaturated carboxylic acid has been introduced is produced without substantially using an emulsifier.

When an adhesive layer or a coating film having excellent adhesion, water resistance and chemical resistance is obtained using an acid-modified polyolefin resin, it is preferable to use an acid-modified polyolefin resin having a high molecular weight and a low degree of acid modification. However, the difficulty of preparing aqueous dispersions of these resins is high. The solvent having high solubility in water used in the above patent documents has inferior performance as an aqueous auxiliary agent compared with an emulsifier such as polyoxyalkylene alkyl ether. Therefore, it is difficult to obtain a good aqueous dispersion of the acid-modified polyolefin resin having a high molecular weight and a low degree of acid modification.

The aqueous resin dispersion described in patent document 4 has improved dispersibility in water by bonding a hydrophilic polymer such as a polyether resin to a propylene polymer, and can obtain an aqueous resin dispersion having a small dispersion particle diameter and excellent stability without substantially adding an emulsifier even when the polymer has a high molecular weight. However, since a structure having high hydrophilicity is introduced into a molecule, the moisture resistance of an adhesive layer or a coating film is not necessarily sufficient.

The present invention addresses the problem of providing a dispersion resin composition that can maintain dispersion stability even when the amount of emulsifier added is reduced.

Means for solving the problems

The present inventors have conducted intensive studies on the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by containing a modified polyolefin resin having a ring opening degree represented by a predetermined formula of 70 or more and an aqueous dispersion medium, and have completed the present invention.

Namely, the present inventors provide the following [1] - [ 6 ].

[1] A dispersion resin composition comprising at least a modified polyolefin resin obtained by introducing a modifying component comprising an alpha, beta-unsaturated carboxylic acid derivative having a cyclic structure into a polyolefin resin, wherein the modified polyolefin resin has a ring-opening degree represented by the following formula (1) of 70 or more,

(1) degree of ring opening = degree of modification K X degree of ring opening R

(in the formula (1), the modification degree K represents a content (wt%) of the α, β -unsaturated carboxylic acid derivative with respect to the polyolefin resin, and the ring-opening ratio R represents a ring-opening ratio (%) of a cyclic structure in the α, β -unsaturated carboxylic acid derivative).

[2] the dispersion resin composition according to the above [1], wherein the content of the emulsifier is less than 10% by weight.

[ 3 ] the dispersion resin composition according to [1] or [2], wherein the ring-opening ratio R is 60% or more.

The dispersion resin composition according to any one of [1] to [ 3 ], wherein the modified polyolefin resin has a melting point of 50 ℃ or higher.

The dispersion resin composition according to any one of [1] to [ 4 ] above, wherein the modified polyolefin resin has a weight average molecular weight of 1 ten thousand or more.

The dispersion resin composition according to any one of [1] to [ 5 ] above, wherein the polyolefin resin contains at least 1 selected from the group consisting of an ethylene-propylene copolymer, a propylene-1-butene copolymer and an ethylene-propylene-1-butene copolymer.

Effects of the invention

According to the present invention, a dispersion resin composition can be provided which can maintain dispersion stability even if the amount of an emulsifier added is reduced.

Detailed Description

The present invention will be described in detail below based on preferred embodiments. In the present specification, the expression "AA to BB" means AA or more and BB or less.

[1. Dispersion resin composition ]

The dispersion resin composition of the present invention contains at least: a modified polyolefin resin obtained by introducing a modifying component comprising an alpha, beta-unsaturated carboxylic acid derivative having a cyclic structure into a polyolefin resin, and an aqueous dispersion medium. The modified polyolefin resin has a ring opening degree represented by formula (1) of 70 or more.

(1) Degree of ring opening = degree of modification K X degree of ring opening R

(in the formula (1), the modification degree K represents the content (wt%) of the α, β -unsaturated carboxylic acid derivative with respect to the polyolefin resin, and the ring-opening ratio R represents the ring-opening ratio (%) of the cyclic structure in the α, β -unsaturated carboxylic acid derivative).

When the ring-opening degree represented by formula (1) of the modified polyolefin resin is 70 or more, a dispersion resin composition capable of maintaining dispersion stability can be obtained even if the amount of the emulsifier to be added is reduced. This is presumed to be due to the following reason.

The modification degree K is the amount of the α, β -unsaturated carboxylic acid derivative having a cyclic structure introduced into the polyolefin resin. The ring-opening ratio R is the ring-opening ratio of a cyclic structure in the α, β -unsaturated carboxylic acid derivative. In the present invention, the cyclic structure of the α, β -unsaturated carboxylic acid derivative is opened by water molecules. Therefore, the ring-opened structure has a dicarboxylic group. That is, in the modified polyolefin resin of the present invention, the ring opening degree can be said to be a parameter concerning the amount of carboxyl groups present in the modified polyolefin resin.

In the aqueous dispersion medium, the carboxyl group is present as a carboxylic acid ion having a conjugate acid such as an organic amine as a counter ion due to the presence of a neutralizing agent such as an organic amine. The carboxylate ions have a negative charge. Therefore, the modified polyolefin resin of the present invention is dispersed and stabilized by the electrostatic repulsive force of each carboxylic acid ion in the aqueous dispersion medium. Therefore, it is presumed that the dispersion resin composition of the present invention can maintain dispersion stability even if the amount of the emulsifier is reduced.

Modified polyolefin resins obtained by introducing an α, β -unsaturated carboxylic acid derivative having a cyclic structure such as maleic anhydride into a polyolefin resin have been known. However, conventionally known modified polyolefin resins can exhibit various effects by using a cyclic structure of an α, β -unsaturated carboxylic acid derivative introduced into a polyolefin resin for a chemical reaction. Therefore, it is desirable that the cyclic structure of the α, β -unsaturated carboxylic acid derivative introduced into the polyolefin resin is not opened, that is, the ring opening degree is low.

In the present invention, the modified polyolefin resin has a ring opening degree of the cyclic structure of the α, β -unsaturated carboxylic acid derivative of 70 or more, that is, has an increased ring opening degree.

It is effective to increase the degree of modification while maintaining dispersion stability while reducing the amount of the emulsifier to be added. However, if the degree of modification is excessively increased, the water resistance tends to be lowered. Therefore, particularly when water resistance of a coating film or an adhesive layer is required, it is preferable not to increase the degree of modification in order to reduce the amount of an emulsifier to be added and to maintain dispersion stability. The present inventors have conducted various studies and found that it is effective to reduce the amount of an emulsifier to be added and to maintain dispersion stability even when the ring-opening ratio is increased instead of increasing the degree of modification.

A modified polyolefin resin obtained by introducing an alpha, beta-unsaturated carboxylic acid derivative having a cyclic structure such as maleic anhydride into a polyolefin resin, wherein the cyclic structure is opened by water molecules. Therefore, for example, the ring opening ratio R is observed to increase with time by contacting water molecules in the atmosphere. However, moisture in the atmosphere cannot reach the inside of the modified polyolefin resin. Therefore, the increase in the open loop ratio R tends to be stable in a certain range.

The level at which the increase in the ring opening ratio R becomes stable depends on the environmental humidity and the specific surface area of the resin. In general, the higher the specific surface area, the higher the level at which the ring opening ratio R becomes stable. However, even in the form of particles that are generally used, the ring opening ratio R does not exceed 50% in a state of long-term exposure to the atmosphere.

The present inventors have made extensive studies in order to improve the ring-opening ratio as much as possible, considering that the dispersion stability can be effectively improved even in a state where the degree of modification is kept relatively low, and as a result, have found that the ring-opening ratio R can be made to exceed 50% by keeping the modified polyolefin resin for a certain period of time under conditions of high humidity and high temperature, and the dispersion stability of the dispersion resin composition can be greatly improved.

[1-1. modified polyolefin resin ]

The modified polyolefin resin is obtained by introducing a modifying component containing an α, β -unsaturated carboxylic acid derivative having a cyclic structure into a polyolefin resin. The modified polyolefin resin has a ring opening degree represented by the above formula (1) of 70 or more, preferably 100 or more. When the ring opening degree is 70 or more, dispersion stability can be maintained even if the amount of the emulsifier is reduced in the case of preparing a dispersion resin composition using a modified polyolefin resin obtained by introducing a modifying component of an α, β -unsaturated carboxylic acid derivative having a cyclic structure into a polyolefin resin. The upper limit is preferably 600 or less, more preferably 450 or less, and still more preferably 300 or less.

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

The modification degree K is the graft weight (wt%) of the α, β -unsaturated carboxylic acid derivative. That is, the modification degree K represents the proportion of the α, β -unsaturated carboxylic acid derivative having a cyclic structure introduced into the polyolefin resin. The degree of modification K can be set according to the degree of ring opening of the modified polyolefin resin. The degree of modification K is more preferably 1.2 to 6.0% by weight, still more preferably 1.4 to 5.0% by weight.

The degree of modification K can be adjusted by the amount of the α, β -unsaturated carboxylic acid derivative having a cyclic structure and the radical initiator used, the reaction temperature, the reaction time, and the like when the α, β -unsaturated carboxylic acid derivative having a cyclic structure is introduced into the polyolefin resin.

The degree of modification K can be calculated in accordance with JIS K-0070(1992) as follows.

About 0.5g of the modified polyolefin resin and about 100g of toluene were precisely weighed into a 300ml separable flask equipped with a condenser and a thermometer, and dissolved with stirring while heating on a thermal stirrer until the internal temperature reached 80 ℃. After the resin was dissolved, 15ml of methanol was added thereto and the mixture was kept for 5 minutes. Then, 5 to 6 drops of an indicator (1% phenolphthalein-methanol solution) was added, and the mixture was titrated with 0.1mol/L potassium hydroxide-ethanol solution. At this time, the degree of modification K of the modified polyolefin resin can be calculated from the amount of the dropwise added required for neutralization by the following formula. The degree of modification K is measured using a sample which is purified by dissolving the modified polyolefin resin before ring-opening treatment in an organic solvent such as toluene and then dropping the solution into a large excess of methanol to precipitate the solution.

K={B×f×F/(S×1000)}×100。

Here, K represents the degree of modification (wt%), B represents the titration amount (ml) of the potassium hydroxide-ethanol solution, F represents a factor of 0.1mol/L of the potassium hydroxide-ethanol solution, F is the formula weight of the α, β -unsaturated carboxylic acid derivative × 1/10, and S represents the weight (g) of the modified polyolefin resin.

The ring-opening ratio R is the ring-opening ratio (%) of the cyclic structure in the α, β -unsaturated carboxylic acid derivative. That is, the ring opening ratio R represents the ring opening ratio of the α, β -unsaturated carboxylic acid derivative having a cyclic structure introduced into the polyolefin resin. The ring-opening ratio R can be set according to the ring-opening degree of the modified polyolefin resin. The ring-opening ratio R is preferably 50 to 100%, more preferably 60 to 80%.

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

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

The wave number is 1700 to 1750cm^-1The peak appearedBelongs to a peak derived from a carbonyl group of a ring-opened α, β -unsaturated carboxylic acid derivative, and the peak height is defined as A. The wave number is 1750-1820 cm^-1The peak appearing was ascribed to a peak derived from a carbonyl group of an α, β -unsaturated carboxylic acid derivative having no ring opening, and the peak height was designated as B. The ring-opening ratio R (%) can be calculated from the formula (A/(A + B). times.100). The open loop ratio in the later-described example is a value calculated by this method.

The melting point of the modified polyolefin resin is preferably 50-120 ℃, more preferably 60-110 ℃, and further preferably 60-100 ℃. When the melting point is 50 ℃ or higher, sufficient adhesiveness can be exhibited. On the other hand, if the melting point is 120 ℃ or lower, excellent adhesion can be exhibited even when the firing is performed at a relatively low temperature.

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

Details of the melting point measured by DSC are as follows.

About 5mg of the sample was kept in a molten state by heating at 150 ℃ for 10 minutes in accordance with JIS K7121(1987) using a DSC measuring apparatus (for example, "DISCOVERY DSC 2500", manufactured by TA Instrument, Japan). Cooling at a speed of 10 ℃/min to-50 ℃, and then keeping for 5 minutes. Then, the melting peak temperature at the time of melting at 10 ℃/min to 150 ℃ was measured, and this temperature was defined as the melting point.

The modified polyolefin resin preferably has a weight average molecular weight of 10,000 to 200,000, more preferably 50,000 to 180,000, and still more preferably 70,000 to 170,000.

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

The measurement conditions of GPC are as follows. The weight average molecular weight of the modified polyolefin resin in examples described later is a value measured under the conditions.

Measurement apparatus HLC-8320GPC (manufactured by Tosoh corporation)

Eluent tetrahydrofuran

Column TSKgel (manufactured by Tosoh corporation)

Polystyrene (manufactured by Tosoh, GL Sciences Inc.)

The detector is a differential refractometer (manufactured by Tosoh).

The average particle diameter of the modified polyolefin resin in the dispersion resin composition is preferably 50nm or more, more preferably 60nm or more, and still more preferably 70nm or more. On the other hand, the upper limit thereof is preferably 250nm or less, more preferably 230nm or less, and still more preferably 210nm or less. The average particle size indicates the degree of dispersion, and a smaller value indicates better dispersibility.

In the present specification, the average particle diameter is a Z-average particle diameter measured by a dynamic light scattering method. Examples of the measuring apparatus include Zetasizer Nano ZS manufactured by Malvern.

(polyolefin resin)

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

The polyolefin resin may be a copolymer of 1 kind of single olefin polymer or 2 or more kinds of olefin polymers. When the polyolefin resin is a copolymer, the polyolefin resin may be a random copolymer or a block copolymer.

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

Here, "polypropylene" means a polymer whose basic unit is a structural unit derived from propylene. "ethylene-propylene copolymer" means a copolymer whose basic units are structural units derived from ethylene and propylene. "propylene-1-butene copolymer" means a copolymer whose basic units are structural units derived from propylene and butene. "ethylene-propylene-1-butene copolymer" means a copolymer whose basic units are structural units derived from ethylene, propylene and butene. These (co) polymers may contain a small amount of structural units derived from other olefins in addition to the basic units, as long as the properties inherent in the resin are not significantly impaired.

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

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

The lower limit of the melting point of the polyolefin resin is preferably 50 ℃ or higher, and more preferably 60 ℃ or higher. When the melting point of the polyolefin resin is 50 ℃ or higher, the modified polyolefin resin can exhibit sufficient coating film strength when used in applications such as inks and paints. Therefore, the adhesion to the substrate can be sufficiently exhibited. Further, when used as an ink, blocking during printing can be suppressed. The upper limit thereof is preferably 120 ℃ or lower, more preferably 110 ℃ or lower, and still more preferably 100 ℃ or lower. When the melting point of the polyolefin resin is 120 ℃ or lower, excessive curing of the coating film can be suppressed when the modified polyolefin resin is used for ink, coating material, or the like. Therefore, the coating film can exhibit appropriate flexibility.

One embodiment of the melting point of the polyolefin resin is preferably 50 to 120 ℃, more preferably 60 to 110 ℃, and still more preferably 60 to 100 ℃.

(modifying Components)

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

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

As a method for introducing the modifying component containing the α, β -unsaturated carboxylic acid derivative having a cyclic structure into the polyolefin resin, a known method can be used. Examples of such a method include a method in which a polyolefin resin is melted or dissolved in a solvent, and a modifying component containing an α, β -unsaturated carboxylic acid derivative having a cyclic structure and a radical initiator are added to modify the resin.

As the radical initiator, for example, a known radical initiator can be selected. As the radical initiator, there may be mentioned, for example, peroxides (e.g., di-t-butyl peroxide, t-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, t-butyl peroxybenzoate, methyl ethyl ketone peroxide, di-t-butyl diperoxyphthalate) and azonitriles (e.g., azobisisobutyronitrile).

As the reaction apparatus, for example, a reaction tank having a jacket which can be heated with warm water or steam, or a twin-screw extruder can be used.

The reaction may be carried out batchwise or continuously.

A graft polymer having a polyolefin as a main chain and a side chain containing a structural unit derived from a modifying component containing an α, β -unsaturated carboxylic acid derivative having a cyclic structure is usually obtained by introducing the modifying component containing the α, β -unsaturated carboxylic acid derivative having a cyclic structure into a polyolefin resin.

[ production method ]

The method for producing the modified polyolefin resin is not particularly limited. One example is as follows.

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

Next, a modifying component containing an α, β -unsaturated carboxylic acid derivative having a cyclic structure is introduced into the polyolefin resin. The modification method can be carried out by a known method, for example, a graft polymerization method. A radical initiator may be used in the graft polymerization reaction. Examples of the method for obtaining the modified polyolefin resin include a solution method in which a polyolefin resin and a modifying component containing an α, β -unsaturated carboxylic acid derivative having a cyclic structure are dissolved by heating in a solvent such as toluene, and a radical initiator is added; a melt kneading method in which a polyolefin resin, a modifying component containing an α, β -unsaturated carboxylic acid derivative having a cyclic structure, and a radical initiator are added to a Banbury mixer, a kneader, an extruder, or the like and kneaded. Here, the modifying component containing the α, β -unsaturated carboxylic acid derivative having a cyclic structure may be added at once or sequentially.

In the graft polymerization reaction, the modifying component containing the α, β -unsaturated carboxylic acid derivative having a cyclic structure is preferably used in an amount of 1.0 to 12.0 parts by mass based on 100 parts by mass of the polyolefin resin, from the viewpoint of grafting in a preferable amount.

The preferable range of the addition amount of the radical initiator is as follows with respect to 100% by mass of the total of the modifying components containing the α, β -unsaturated carboxylic acid derivative having a cyclic structure. The lower limit of the amount of addition is preferably 1% by mass or more, and more preferably 10% by mass or more. If the amount of the radical initiator added is 1% by mass or more, the grafting efficiency can be maintained. On the other hand, the upper limit of the amount added is preferably 200 mass% or less, more preferably 100 mass% or less. It is economical if the amount of the radical initiator added is 200 mass% or less.

The unreacted materials not graft-polymerized to the polyolefin resin can be removed by, for example, extraction with a lean solvent. Thus, a graft polymer was obtained.

The modified polyolefin resin can be produced by reacting the resulting graft polymer with water molecules so that the ring-opening degree becomes 70 or more. For example, the modified polyolefin resin can be produced by immersing the modified polyolefin resin in water, subjecting the modified polyolefin resin to a ring-opening treatment under humidified conditions, or the like. At this time, the ring-opening ratio (%) and the ring-opening degree can be adjusted by changing water, the temperature of the humidified condition, the immersion time, and the time for placing under the humidified condition.

By increasing the ring-opening ratio of the modified polyolefin resin as much as possible, the dispersion stability can be effectively improved while the degree of modification is kept relatively low. As a method for increasing the ring-opening rate, for example, the ring-opening rate can be increased to 60 to 70% by filling water in the bottom of a container, placing the particles of the modified polyolefin resin on a dummy bottom so that the particles do not directly contact with water, sealing the container, and keeping the container in a dryer at 50 ℃ for 3 days or more. Further, the open ring ratio can be increased to 65 to 80% by continuously filling the closed space with water vapor and storing the pellets of the modified polyolefin resin at 50 ℃ and a humidity of 100% for 2 days or more. In either method, the storage temperature is increased to higher than room temperature, and the reactivity of the cyclic structure and water molecules is improved and the vapor pressure is increased, whereby water molecules can easily enter the inside of the particles. As a result, the ring opening ratio can be increased as compared with the case of storage in normal air or immersion in water only at room temperature.

[1-2. aqueous Dispersion Medium ]

The dispersion resin composition of the present invention contains an aqueous dispersion medium. The aqueous dispersion medium may be water alone, or a water-soluble solvent may be used in combination with water. Examples of the water-soluble solvent include lower alcohols such as methanol, ethanol, and isopropanol; lower ketones such as dimethylformamide, tetrahydrofuran, acetone, and methyl ethyl ketone.

The amount of the aqueous dispersion medium used is not particularly limited, and may be arbitrarily changed depending on the use of the dispersion resin composition. For example, the solid content concentration of the modified polyolefin resin is preferably 10 to 50% by weight, and more preferably 20 to 40% by weight.

[1-3. emulsifiers ]

As the emulsifier, a conventionally known emulsifier added for the purpose of stabilizing the dispersion when the modified polyolefin resin is dispersed in an aqueous dispersion medium can be used. Examples thereof include nonionic surfactants and anionic surfactants.

Examples of the nonionic surfactant include polyoxyethylene polyol fatty acid esters such as polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene derivatives, polyoxyethylene fatty acid esters and polyoxyethylene sorbitan fatty acid esters, polyoxyethylene polyoxypropylene polyols, sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oils, polyoxyalkylene polycyclic phenyl ethers, polyoxyethylene alkylamines, alkylalkanolamides, and polyalkylene glycol (meth) acrylates.

Examples of the anionic surfactant include alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate salts, alkylbenzene sulfonate salts, α -olefin sulfonate salts, methyltaurate salts, sulfosuccinate salts, ether sulfonate salts, ether carboxylate salts, fatty acid salts, naphthalenesulfonic acid formalin condensates, polyoxyethylene phenyl ether phosphate salts, polyoxyethylene alkyl ether phosphate salts, dioctyl sulfosuccinate ester salts, alkylamine salts, quaternary ammonium salts, alkylbetaines, and alkylamine oxides.

In the dispersion resin composition of the present invention, the content of the emulsifier is preferably less than 10% by weight, more preferably less than 5% by weight. The lower limit is not particularly limited, and an emulsifier may not be contained. If the content of the emulsifier is less than 10% by weight, the decrease in adhesion due to the addition of the emulsifier can be suppressed.

The dispersion resin composition of the present invention is useful as an intermediate medium for substrates having low adhesion (adhesiveness) and difficult to apply a coating material or the like, and is useful as an adhesive between polyolefin substrates such as polypropylene and polyethylene having poor adhesion (adhesiveness). In this case, the substrate may be used regardless of whether it is surface-treated by plasma, corona, or the like.

In addition, the dispersion resin composition of the present invention can exhibit excellent adhesion between a metal and a resin. Examples of the metal include aluminum, aluminum alloy, nickel, and stainless steel. Examples of the resin include nonpolar resins such as polyolefin resins, polyurethane resins, polyamide resins, acrylic resins, polyester resins, and polyethylene terephthalate resins. Therefore, the dispersion resin composition of the present invention can be used as a binder, a primer, a binder for a coating material, and a binder for ink, or as a component of these.

The dispersion resin composition of the present invention may contain at least 1 component selected from the group consisting of a solution, a curing agent and an adhesive component in addition to the modified polyolefin resin and the aqueous dispersion medium.

(solution)

The solution may be an organic solvent. Examples of the organic solvent include aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone, methyl butyl ketone, and ethyl cyclohexanone; aliphatic or alicyclic hydrocarbon solvents such as cyclohexanone, methylcyclohexane, nonane, and decane. From the viewpoint of environmental problems, organic solvents other than aromatic solvents are preferred, and mixed solvents of alicyclic hydrocarbon solvents and ester solvents or ketone solvents are more preferred.

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

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

Further, the solution is preferably a compound represented by the following general formula (1) and having a molecular weight of less than 200.

R-O-(C_lH_2lO)_mH ･ ･ ･ ･ ･ ･ formula (1).

In the general formula (1), R is C_nH_2n+1And n is an integer of 10 or less. N is preferably an integer of 8 or less, more preferably an integer of 7 or less, still more preferably an integer of 6 or less, yet more preferably an integer of 5 or less, and particularly preferably an integer of 4 or less.

In the general formula (1), l is an integer of 5 or less, preferably 4 or less, and more preferably 3 or less.

In the general formula (1), m is an integer of 5 or less, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, and yet more preferably 1.

The compound represented by the general formula (1) and having a molecular weight of less than 200 is preferably a glycol ether compound. The diol ether compound has a structure in which a hydrogen atom of a diol such as ethylene glycol, propylene glycol, or butylene glycol is substituted with an alkyl group.

The compound represented by the general formula (1) has a hydrophobic group and a hydrophilic group in one molecule. Thus, the modified polyolefin resin can be easily dispersed and emulsified in water by adding the compound represented by the general formula (1). Therefore, the dispersion resin composition of the present invention can maintain good storage stability.

More specifically, examples of the compound represented by the general formula (1) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol monohexyl ether, ethylene glycol monodecyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether. Of these, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, and propylene glycol monopropyl ether are preferred.

The molecular weight of the compound represented by the general formula (1) is less than 200. This can suppress an increase in the boiling point of the modified polyolefin resin aqueous dispersion composition (the dispersion resin composition of the present invention). As a result, after the application of the aqueous dispersion composition or a primer containing the aqueous dispersion composition, etc., high-temperature or long-time drying of the coating film can be omitted.

The molecular weight of the compound represented by the general formula (1) is determined from the relative atomic mass (12C =12) approved by the IUPAC atomic weight commission.

The compound represented by the general formula (1) and having a molecular weight of less than 200 may be the compound represented by the general formula (1) alone or a combination of 2 or more compounds represented by the general formula (1). In the latter case, the mixing ratio of each compound is not particularly limited.

(curing agent)

Examples of the curing agent include polyisocyanate compounds, epoxy compounds, polyamine compounds, polyol compounds, and crosslinking agents in which functional groups thereof are blocked with a protecting group.

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

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

(bonding component)

As the adhesive component, a known adhesive component such as a polyester adhesive, a polyurethane adhesive, or an acrylic adhesive can be used in a range not to impair the desired effect.

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

[ primer coating composition, adhesive agent ]

The dispersion resin composition of the present invention can be used as a primer, an adhesive for coating materials, or an adhesive for ink. The dispersion resin composition of the present invention is excellent in solution stability and useful as a primer for finish coating of polyolefin substrates such as bumpers of automobiles and as a coating adhesive excellent in adhesion to a topcoat coating and a clear coat.

[ examples ]

The present invention will be described in detail below with reference to examples. The following examples are intended to illustrate the present invention without limiting it. The measurement method of the physical property values and the like is the above-described measurement method unless otherwise described. In addition, "part" means part by mass unless otherwise specified.

[ degree of modification K (% by weight) ]the degree of modification K is calculated in the following manner in accordance with JIS K-0070 (1992). First, about 0.5g of a modified polyolefin resin and about 100g of toluene were precisely weighed and put into a 300ml separable flask equipped with a condenser and a thermometer, and dissolved by stirring while heating the flask on a thermal stirrer until the internal temperature reached 80 ℃. After the resin was dissolved, 15ml of methanol was added and the mixture was kept for 5 minutes. Then, 5 to 6 drops of an indicator (1% phenolphthalein-methanol solution) was added, and the mixture was titrated with 0.1mol/L potassium hydroxide-ethanol solution. Then, the degree of modification K of the modified polyolefin resin was calculated from the amount of titration required for neutralization by the following formula.

K={B×f×9.806/(S×1000)}×100

K represents the degree of modification (wt%), B represents the titration amount (ml) of the potassium hydroxide-ethanol solution, f represents a factor of 0.1mol/L of the potassium hydroxide-ethanol solution, 9.806 is the formula weight of maleic anhydride X1/10, and S represents the weight (g) of the modified polyolefin resin.

[ Ring opening ratio R (%)]A modified polyolefin resin is dissolved in an organic solvent to obtain a solution. Coating the solution on a KBr plate, drying to form a film, and observing with FT-IR (FT/IR-4100, manufactured by Nippon spectral Co., Ltd.) to 400-4000 cm^-1Infrared absorption spectrum of (1). It is to be noted that the analysis was performed by means of attached software ("Spectro Manager", Japan Spectroscopy Co., Ltd.).

The wave number is 1700 to 1750cm^-1The peak appeared is ascribed to a peak derived from the carbonyl group of the ring-opened α, β -unsaturated carboxylic acid derivative, and the peak height thereof is denoted as a. At wave number of 1750 to 1820cm^-1Peaks appearing were assigned as originating from no openingThe peak height of the carbonyl group of the cyclic α, β -unsaturated carboxylic acid derivative is denoted as B. The open loop ratio R (%) is calculated by substituting the peak heights a and B into (a/(a + B) × 100).

[ degree of opening ] was calculated by the product of the value of modification degree K and the degree of opening R.

[ melting Point (. degree. C.) ] measured according to JIS K7121 (1987). More specifically, about 5mg of the sample was heated at 150 ℃ for 10 minutes by using a DSC measuring apparatus ("DISCOVERY DSC 2500", TA Instrument, Japan), and the sample was kept in a molten state. Cooling at a speed of 10 ℃/min to-50 ℃, and then keeping for 5 minutes. Then, the melting peak temperature at the time of melting at 10 ℃/min to 150 ℃ was measured, and this temperature was defined as the melting point.

[ weight average molecular weight (Mw) ] is a value measured under the following measurement conditions.

Measurement apparatus HLC-8320GPC (manufactured by Tosoh corporation)

Eluent tetrahydrofuran

Column TSKgel (manufactured by Tosoh corporation)

Polystyrene (manufactured by Tosoh, GL Sciences Inc.)

Detector, differential refractometer (made by Tosoh)

The temperature is 40 DEG C

The flow rate was 1.0 mL/min.

Average particle diameter (nm) the average particle diameter of the dispersion resin composition immediately after production was measured using a particle size distribution measuring apparatus (Zetasizer Nano ZS, Malvern co., ltd.) by a dynamic light scattering method. The following test was conducted only on a dispersion resin composition whose average particle size was measurable.

[ stability in centrifugal separation ] the dispersed resin composition immediately after production was treated with a centrifuge at room temperature and 4000rpm for 10 minutes, and the presence or absence of separation and the generation of precipitates were visually checked, and evaluated according to the following criteria.

A: absence of abnormalities

B, a small amount of precipitate was confirmed

And C, layer separation, gel and a large amount of precipitate were confirmed.

[ evaluation of filterability ] the filtration rate and the amount of residue when 200mL of the modified polyolefin resin aqueous dispersion (dispersion resin composition) was filtered through a wire mesh (#400) were evaluated according to the following criteria.

Speed of filtration

A, filtering is finished in less than 1 minute

B, filtering is finished for more than 1 minute and less than 5 minutes

C, filtering for more than 5 minutes and less than 10 minutes

D, filtering for more than 10 minutes and less than 15 minutes

E, incomplete filtration after more than 15 minutes.

Amount of residue

A is none or trace

B in small amount

C, existing in a large amount.

[ Water resistance (Using a usual base Material) ]

< preparation of test piece >

The surface of an ultrahigh-rigidity polypropylene plate was degreased with isopropyl alcohol, and then the modified polyolefin resin aqueous dispersion composition was spray-coated to a film thickness (dry coating film) of 10 to 15 μm, and preheated at the melting point of the resin +15 ℃ for 5 minutes. Subsequently, the coating film was subjected to viscosity adjustment using a specific diluent for a curing agent in the form of a primer, and then spray-coated so that the dry film thickness was about 20 μm, and the coating film was allowed to stand at room temperature for 10 minutes. Further, ECOROCK Hiper Clear S (Rock Paint Co., Ltd.) was mixed with a predetermined curing agent as a varnish on the coating film, and the viscosity was adjusted with a special diluent, and then the mixture was spray-coated so that the dry film thickness was 25 to 30 μm, and the mixture was allowed to stand at room temperature for 10 minutes. Then, a test piece was prepared by performing a calcination treatment at the melting point of the resin +15 ℃ for 30 minutes.

< evaluation of appearance of coating film >

The test piece prepared above was immersed in warm water at 40 ℃ for 10 days, and then the appearance of the coating film (presence or absence of foam) was visually observed and evaluated according to the following criteria.

Appearance of coating film

A: absence of abnormalities

B, generating bubbles of 2mm or less, but being at a level that causes no practical problems

C-bubbles exceeding 2mm were generated.

< evaluation of adhesion >

Then, checkered cuts (a total of 100 checkers were formed by 11 cuts × 11 cuts) reaching the substrate were introduced into the coating film at 2mm intervals by a cutter. After 3 times of peeling operations at an angle of 180 ° by adhering transparent adhesive tape (made by Nichiban co., Ltd.) to the cut, the adhesion was evaluated by the number of non-peeled checkers out of the number of checkers 100.

[ Water resistance (use of a base material having poor adhesion) ]

Test pieces were produced in the same manner as described above except that a polypropylene plate (blend 7 is a recycled material) having poor adhesion was used as the base material, and the appearance and adhesion of the coating film were evaluated.

Production example 1

100.0 parts of a propylene-butene random copolymer [ P-B ] (propylene content: 70 mol%, butene content: 30 mol%, Tm =75 ℃), 4.0 parts of maleic anhydride, 2.6 parts of lauryl methacrylate, and 1.5 parts of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane were kneaded with a twin-screw extruder set to 220 ℃ to react. The strand of the reactant discharged from the die provided at the outlet of the extruder was cut by a pelletizer, thereby obtaining pellets of the reactant. The reaction mixture was purified by putting the particles in a large excess of ethyl acetate and stirring at 45 ℃ for 3 hours, thereby obtaining reactants having a weight average molecular weight of 78,000, a Tm of 70 ℃, and graft weights of maleic anhydride and lauryl methacrylate of 2.6 wt% and 1.8 wt%, respectively.

The purified reactant is added to a vessel with a false bottom and water is added to the bottom of the vessel to the extent that the reactant does not directly contact water. Then, the vessel was sealed and the vessel was kept in a hot air dryer at 50 ℃ for 3 days (relative humidity 100%), to thereby obtain a modified polyolefin resin having a ring opening ratio of 64%, i.e., a ring opening ratio of 166.

Production example 2

100.0 parts of a propylene-butene random copolymer [ P-B ] (propylene component: 70 mol%, butene component: 30 mol%, Tm =75 ℃) was heated and dissolved in 400g of o-xylene in a four-necked flask equipped with a stirrer, a condenser and a dropping funnel. While the temperature in the system was kept at 140 ℃ and stirred, 3.2 parts of maleic anhydride was added at a time, followed by dropwise addition of 1.2 parts of di-t-butyl peroxide over 1 hour. Then, the reaction was further carried out for 3 hours.

After the reaction was completed, the reaction mixture was cooled to 40 ℃ or lower, and then the reaction mixture was purified by adding a large excess of methyl ethyl ketone to obtain a reaction mixture having a weight average molecular weight of 118,000, a Tm of 70 ℃ and a maleic anhydride graft weight of 1.9 wt%.

The purified reactant is added to a vessel with a false bottom and water is added to the bottom of the vessel to the extent that the reactant does not directly contact water. Then, the vessel was sealed and the vessel was kept in a hot air dryer at 50 ℃ for 3 days (relative humidity 100%), to thereby obtain a modified polyolefin resin having a ring opening ratio of 61%, i.e., a ring opening ratio of 116.

(production example 3)

A modified polyolefin resin having a weight-average molecular weight of 79,000, a Tm of 80 ℃, graft weights of maleic anhydride and octyl methacrylate of 1.9 wt% and 1.5 wt%, respectively, a ring opening ratio of 63%, i.e., a ring opening ratio of 120 was obtained in the same manner as in production example 1 except that 100.0 parts of propylene-butene random copolymer [ P-B ] (propylene component 80 mol%, butene component 20 mol%, Tm =85 ℃), 2.9 parts of maleic anhydride, 2.3 parts of octyl methacrylate, and 1.2 parts of dilauryl peroxide were kneaded and reacted with a twin-screw extruder set to 190 ℃ and the temperature at the time of purification was changed to 55 ℃.

Production example 4

A modified polyolefin resin having a weight-average molecular weight of 121,000, a Tm of 80 ℃, a graft weight of maleic anhydride of 2.3% by weight, a ring-opening ratio of 61%, that is, a ring-opening ratio of 140 was obtained in the same manner as in production example 2, except that 100.0 parts of propylene-butene random copolymer [ P-B ] (propylene component 80 mol%, butene component 20 mol%, Tm =85 ℃) and 3.8 parts of maleic anhydride were used.

Production example 5

A modified polyolefin resin having a weight-average molecular weight of 150,000, a Tm of 80 ℃, graft weights of maleic anhydride and octyl methacrylate of 1.7 wt% and 1.3 wt%, respectively, a ring-opening ratio of 60%, i.e., a ring-opening ratio of 102 was obtained in the same manner as in production example 3, except that the temperature of the twin-screw extruder was changed to 170 ℃.

(production example 6)

A modified polyolefin resin having a weight-average molecular weight of 75,000, a Tm of 95 ℃, a graft weight of maleic anhydride of 2.0 wt%, a ring-opening ratio of 61%, that is, a ring-opening ratio of 122 was obtained in the same manner as in production example 1 except that 100.0 parts of the propylene-butene random copolymer [ P-B ] (90 mol% of the propylene component, 10 mol% of the butene component, Tm =100 ℃), 3.0 parts of maleic anhydride, and 2.0 parts of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane were kneaded and reacted in a twin-screw extruder set to 200 ℃, and the temperature during the purification operation was changed to 60 ℃.

Production example 7

100.0 parts of a propylene-butene random copolymer [ P-B ] (propylene content: 90 mol%, butene content: 10 mol%, Tm =100 ℃ C.), 3.0 parts of maleic anhydride and 2.0 parts of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane were kneaded by a twin-screw extruder set at 180 ℃ to react. The strand of the reactant discharged from the die provided at the outlet of the extruder was cut by a pelletizer to obtain pellets of the reactant. The reaction mixture was purified by putting the reaction mixture in a large excess of ethyl acetate and stirring at 60 ℃ for 3 hours to obtain a reaction mixture having a weight average molecular weight of 98,000, a Tm of 95 ℃ and a graft weight of maleic anhydride of 1.7% by weight.

The particles of the purified reactant are stored for 2 days or more in a closed space in which saturated steam (steam pressure 0.3MPa) is continuously supplied so as to reach 60 to 70 ℃ and the relative humidity is 100%, thereby obtaining a modified polyolefin resin having an open ring ratio of 72%, i.e., an open ring ratio of 122.

Production example 8

A modified polyolefin resin having a weight-average molecular weight of 133,000, a Tm of 95 ℃, a graft weight of maleic anhydride of 1.7% by weight, and a ring-opening ratio of 62%, i.e., a ring-opening ratio of 105 was obtained in the same manner as in production example 6, except that the set temperature of the twin-screw extruder was changed to 165 ℃.

Production example 9

100.0 parts of a propylene-ethylene random copolymer [ P-E ] (89 mol% in propylene content, 11 mol% in ethylene content, Tm =65 ℃ C.), 4.0 parts of maleic anhydride, 4.0 parts of lauryl methacrylate and 2.0 parts of di-t-butyl peroxide were kneaded by a twin-screw extruder set at 220 ℃ to react, and the reaction mixture was degassed under reduced pressure in the extruder to remove the remaining unreacted product, thereby obtaining a reaction product having a weight average molecular weight of 54,000 and a Tm of 64 ℃. The reaction was purified by placing it in a large excess of acetone and the graft weights of maleic anhydride and lauryl methacrylate were determined to be 3.2 wt.% and 3.0 wt.%, respectively.

The purified reactant is added to a vessel with a false bottom and water is added to the bottom of the vessel to the extent that the reactant does not directly contact water. Then, the vessel was sealed and the vessel was kept in a hot air dryer at 50 ℃ for 3 days (relative humidity 100%), to thereby obtain a modified polyolefin resin having a ring opening ratio of 65%, that is, a ring opening ratio of 208.

Production example 10

A modified polyolefin resin having a weight-average molecular weight of 149,000, a Tm of 64 ℃, a graft weight of maleic anhydride of 2.8% by weight, a ring-opening ratio of 61%, i.e., a ring-opening ratio of 171 was obtained in the same manner as in production example 2, except that 100.0 parts of propylene-ethylene random copolymer [ P-E ] (propylene component 89 mol%, ethylene component 11 mol%, Tm =65 ℃) and 3.8 parts of maleic anhydride were used.

Production example 11

A modified polyolefin resin having a weight-average molecular weight of 125,000, a Tm of 60 ℃, a graft weight of maleic anhydride of 2.6 wt%, a ring-opening ratio of 63%, i.e., a ring-opening ratio of 164 was obtained in the same manner as in production example 2, except that 100.0 parts of a propylene-ethylene-1-butene random copolymer [ P-E-B ] (65 mol% in propylene, 24 mol% in ethylene, 11 mol% in 1-butene, Tm =65 ℃) and 3.7 parts of maleic anhydride were used.

Production example 12

The reaction product particles (not subjected to ring-opening treatment) obtained in the same manner as in production example 9 were charged with a large excess of methyl ethyl ketone and were purified by stirring at 45 ℃ for 3 hours. The purified reaction product was allowed to stand in the air (about 25 ℃ C., about 50RH%) for 1 day, thereby obtaining a modified polyolefin resin having a weight average molecular weight of 54,000, a Tm of 64 ℃, graft weights of maleic anhydride and lauryl methacrylate of 3.2% by weight and 3.0% by weight, respectively, and a ring opening ratio of 24%, i.e., a ring opening ratio of 77.

Production example 13

The reaction product (purified and not subjected to ring-opening treatment) was obtained in the same manner as in production example 11. The purified reaction product was allowed to stand in the air (about 25 ℃ C., about 50RH%) for 1 day, thereby obtaining a modified polyolefin resin having a weight average molecular weight of 125,000, a Tm of 60 ℃, a graft weight of maleic anhydride of 2.6 wt%, and a ring-opening ratio of 28%, i.e., a ring-opening ratio of 73.

Production example 14

Pellets of the reaction product (purified and not subjected to ring-opening treatment) obtained in the same manner as in production example 7 were placed in a vessel to which water was added, the vessel was sealed in a state in which the reaction product was immersed in water, and the reaction product was stored at room temperature (about 25 ℃) for 3 days, whereby a modified polyolefin resin having a weight-average molecular weight of 98,000, a Tm of 95 ℃, a maleic anhydride graft weight of 1.7 wt%, a ring-opening ratio of 48%, that is, a ring-opening ratio of 82 was obtained.

Production example 15

The reaction product obtained in the same manner as in production example 1 was purified. The measurement was carried out promptly without particularly carrying out the treatment for promoting ring opening of the purified reactant, and as a result, a modified polyolefin resin having a weight average molecular weight of 78,000, a Tm of 70 ℃, graft weights of maleic anhydride and lauryl methacrylate of 2.6 wt% and 1.8 wt%, respectively, a ring opening ratio of 17%, that is, a ring opening degree of 44 was obtained.

Production example 16

The reaction product obtained in the same manner as in production example 2 was purified. The purified reactants were added to a vessel with a false bottom and water was added to the bottom of the vessel to the extent that the reactants did not directly contact the water. Then, the vessel was sealed, and the resulting product was stored in a hot air dryer at 50 ℃ for 8 hours (relative humidity 100%) to obtain a modified polyolefin resin having a weight average molecular weight of 118,000, a Tm of 70 ℃, a graft weight of maleic anhydride of 1.9 wt%, a ring opening ratio of 32%, i.e., a ring opening ratio of 61.

Production example 17

The reaction product obtained in the same manner as in production example 4 was purified. The purified reaction product was allowed to stand in the air (about 25 ℃ C., about 50RH%) for 1 day, whereby a modified polyolefin resin having a weight average molecular weight of 121,000, a Tm of 80 ℃, a graft weight of maleic anhydride of 2.3 wt%, and a ring-opening ratio of 25%, i.e., a ring-opening ratio of 58 was obtained.

Production example 18

The reaction product obtained in the same manner as in production example 7 was purified. The purified reaction product was charged into a vessel containing water, the vessel was sealed in a state in which the reaction product was immersed in water, and the reaction product was stored at room temperature (about 25 ℃) for 1 day, whereby a modified polyolefin resin having a weight average molecular weight of 98,000, a Tm of 95 ℃, a graft weight of maleic anhydride of 1.7 wt%, a ring opening ratio of 38%, that is, a ring opening ratio of 65 was obtained.

Production example 19

The reaction product obtained in the same manner as in production example 10 was purified. As a result of rapid measurement without particularly carrying out treatment for promoting ring opening of the purified reactant, a modified polyolefin resin having a weight average molecular weight of 149,000, a Tm of 64 ℃, a graft weight of maleic anhydride of 2.8 wt%, a ring opening ratio of 18%, that is, a ring opening ratio of 50 was obtained.

Production example 20

A modified polyolefin resin having a weight-average molecular weight of 103,000, a Tm of 95 ℃, a graft weight of maleic anhydride of 1.6% by weight, and a ring-opening ratio of 73%, i.e., a ring-opening ratio of 117 was obtained in the same manner as in production example 7, except that the set temperature of the twin-screw extruder was changed to 170 ℃.

Production example 21

A modified polyolefin resin having a weight-average molecular weight of 112,000, a Tm of 80 ℃, a graft weight of maleic anhydride of 4.3% by weight, a ring-opening ratio of 70%, that is, a ring-opening ratio of 301 was obtained in the same manner as in production example 2, except that 100.0 parts of a propylene-butene random copolymer [ P-B ] (propylene component 80 mol%, butene component 20 mol%, Tm =85 ℃) and 7.9 parts of maleic anhydride were used.

Production example 22

A modified polyolefin resin having a weight-average molecular weight of 105,000, a Tm of 80 ℃, a graft weight of maleic anhydride of 6.0% by weight, a ring-opening ratio of 72%, that is, a ring-opening ratio of 432 was obtained in the same manner as in production example 2, except that 100.0 parts of propylene-butene random copolymer [ P-B ] (propylene component 80 mol%, butene component 20 mol%, Tm =85 ℃) and 10.7 parts of maleic anhydride were used.

Production example 23

A modified polyolefin resin having a weight-average molecular weight of 133,000, a Tm of 78 ℃, graft weights of maleic anhydride and lauryl methacrylate of 3.8 wt% and 3.5 wt%, respectively, and a ring-opening ratio of 70%, i.e., a ring-opening ratio of 266 was obtained in the same manner as in production example 9, except that 100.0 parts of a propylene-ethylene random copolymer [ P-E ] (propylene component 91 mol%, ethylene component 9 mol%, Tm =75 ℃), 5.0 parts of maleic anhydride, 5.0 parts of lauryl methacrylate, and 2.5 parts of di-tert-butyl peroxide were used.

(example 1)

100g of the modified polyolefin resin obtained in production example 1, 50g of methylcyclohexane, and 50g of propylene glycol monopropyl ether were charged into a four-necked flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, and kneaded at an internal temperature of the flask of 85 ℃ for 30 minutes. Then, 4g of morpholine was added thereto, and the mixture was kneaded at a flask inner temperature of 85 ℃ for 60 minutes. Then, 290g of deionized water at 90 ℃ was added over 60 minutes. Subsequently, a portion of the methylcyclohexane and propylene glycol monopropyl ether was removed under reduced pressure. Then, the resulting mixture was cooled to room temperature while stirring, to obtain a modified polyolefin resin aqueous dispersion composition (dispersion resin composition) having a solid content adjusted to 30% by weight with deionized water. The content of methylcyclohexane and propylene glycol monopropyl ether in the modified polyolefin resin aqueous dispersion composition was confirmed by gas chromatography, and as a result, the content was 0.02% by weight and 2.5% by weight, respectively, with respect to the modified polyolefin resin aqueous dispersion composition.

(example 2)

100g of the modified polyolefin resin obtained in production example 2, 30g of toluene and 100g of ethylene glycol monobutyl ether were charged into a four-necked flask equipped with a stirrer, a condenser, a thermometer and a funnel, and kneaded at an internal temperature of the flask of 85 ℃ for 30 minutes. Subsequently, 5g of N, N-dimethylethanolamine was added to the mixture to adjust the flask inner temperature to 85 ℃ and kneading was carried out for 60 minutes. Then, 290g of deionized water at 90 ℃ was added over 60 minutes. Next, toluene and a part of ethylene glycol monobutyl ether were removed under reduced pressure. Then, the resulting mixture was cooled to room temperature while stirring, to obtain a modified polyolefin resin aqueous dispersion composition (dispersion resin composition) having a solid content adjusted to 30% by weight with deionized water. The contents of toluene and ethylene glycol monobutyl ether in the modified polyolefin resin aqueous dispersion composition were confirmed by gas chromatography, and as a result, the contents were 0.02 wt% and 1.5 wt%, respectively, with respect to the modified polyolefin resin aqueous dispersion composition.

(example 3)

A modified polyolefin resin aqueous dispersion composition (dispersion resin composition) was obtained in the same manner as in example 1, except that the modified polyolefin resin obtained in production example 3 was used. The content of methylcyclohexane and propylene glycol monopropyl ether in the modified polyolefin resin aqueous dispersion composition was 0.02% by weight and 2.3% by weight, respectively, based on the modified polyolefin resin aqueous dispersion composition.

(example 4)

A modified polyolefin resin aqueous dispersion composition was obtained in the same manner as in example 2, except that the modified polyolefin resin obtained in production example 4 was used. The contents of toluene and ethylene glycol monobutyl ether in the modified polyolefin resin aqueous dispersion composition were 0.02 wt% and 2.1 wt%, respectively, with respect to the modified polyolefin resin aqueous dispersion composition.

(example 5)

100g of the modified polyolefin resin obtained in production example 5, 5g of EMULGEN420 (manufactured by Kao corporation, polyoxyethylene alkyl ether), 30g of toluene and 100g of ethylene glycol monobutyl ether were charged into a four-necked flask equipped with a stirrer, a condenser, a thermometer and a funnel, and kneaded at an internal temperature of 85 ℃ for 30 minutes. Subsequently, 5g of N, N-dimethylethanolamine was added to the mixture to adjust the flask inner temperature to 85 ℃ and kneading was carried out for 60 minutes. Then, 290g of deionized water at 90 ℃ was added over 60 minutes. Next, toluene and a part of ethylene glycol monobutyl ether were removed under reduced pressure. Then, the resulting mixture was cooled to room temperature while stirring, to obtain a modified polyolefin resin aqueous dispersion composition (dispersion resin composition) having a solid content adjusted to 30% by weight with deionized water. The contents of toluene and ethylene glycol monobutyl ether in the modified polyolefin resin aqueous dispersion composition were confirmed by gas chromatography, and as a result, the contents were 0.02% by weight and 1.5% by weight, respectively, based on the modified polyolefin resin aqueous dispersion composition.

(example 6)

A modified polyolefin resin aqueous dispersion composition (dispersion resin composition) was obtained in the same manner as in example 1, except that the modified polyolefin resin obtained in production example 6 was used. The content of methylcyclohexane and propylene glycol monopropyl ether in the modified polyolefin resin aqueous dispersion composition was 0.02% by weight and 2.0% by weight, respectively, based on the modified polyolefin resin aqueous dispersion composition.

(example 7)

A modified polyolefin resin aqueous dispersion composition (dispersion resin composition) was obtained in the same manner as in example 2, except that the modified polyolefin resin obtained in production example 7 was used. The contents of toluene and ethylene glycol monobutyl ether in the modified polyolefin resin aqueous dispersion composition were 0.01 wt% and 1.3 wt%, respectively, with respect to the modified polyolefin resin aqueous dispersion composition.

(example 8)

A modified polyolefin resin aqueous dispersion composition (dispersion resin composition) was obtained in the same manner as in example 5, except that the modified polyolefin resin obtained in production example 8 was used. The contents of toluene and ethylene glycol monobutyl ether in the modified polyolefin resin aqueous dispersion composition were 0.02 wt% and 2.5 wt%, respectively, with respect to the modified polyolefin resin aqueous dispersion composition.

(example 9)

A modified polyolefin resin aqueous dispersion composition (dispersion resin composition) was obtained in the same manner as in example 1, except that the modified polyolefin resin obtained in production example 9 was used. The content of methylcyclohexane and propylene glycol monopropyl ether in the modified polyolefin resin aqueous dispersion composition was 0.02% by weight and 2.0% by weight, respectively, based on the modified polyolefin resin aqueous dispersion composition.

(example 10)

A modified polyolefin resin aqueous dispersion composition (dispersion resin composition) was obtained in the same manner as in example 2, except that the modified polyolefin resin obtained in production example 10 was used. The contents of toluene and ethylene glycol monobutyl ether in the modified polyolefin resin aqueous dispersion composition were 0.02 wt% and 1.9 wt%, respectively, with respect to the modified polyolefin resin aqueous dispersion composition.

(example 11)

A modified polyolefin resin aqueous dispersion composition (dispersion resin composition) was obtained in the same manner as in example 1, except that the modified polyolefin resin obtained in production example 11 was used. The content of methylcyclohexane and propylene glycol monopropyl ether in the modified polyolefin resin aqueous dispersion composition was 0.02% by weight and 2.6% by weight, respectively, based on the modified polyolefin resin aqueous dispersion composition.

(example 12)

A modified polyolefin resin aqueous dispersion composition (dispersion resin composition) was obtained in the same manner as in example 5, except that the modified polyolefin resin obtained in production example 12 was used. The contents of toluene and ethylene glycol monobutyl ether in the modified polyolefin resin aqueous dispersion composition were 0.02 wt% and 2.1 wt%, respectively, with respect to the modified polyolefin resin aqueous dispersion composition.

(example 13)

A modified polyolefin resin aqueous dispersion composition (dispersion resin composition) was obtained in the same manner as in example 2, except that the modified polyolefin resin obtained in production example 13 was used. The contents of toluene and ethylene glycol monobutyl ether in the modified polyolefin resin aqueous dispersion composition were 0.02 wt% and 2.8 wt%, respectively, with respect to the modified polyolefin resin aqueous dispersion composition.

(example 14)

A modified polyolefin resin aqueous dispersion composition (dispersion resin composition) was obtained in the same manner as in example 2, except that the modified polyolefin resin obtained in production example 14 was used. The contents of toluene and ethylene glycol monobutyl ether in the modified polyolefin resin aqueous dispersion composition were 0.02 wt% and 2.5 wt%, respectively, with respect to the modified polyolefin resin aqueous dispersion composition.

(example 15)

A modified polyolefin resin aqueous dispersion composition (dispersion resin composition) was obtained in the same manner as in example 2, except that the modified polyolefin resin obtained in production example 20 was used. The contents of toluene and ethylene glycol monobutyl ether in the modified polyolefin resin aqueous dispersion composition were 0.01 wt% and 1.4 wt%, respectively, with respect to the modified polyolefin resin aqueous dispersion composition.

(example 16)

A modified polyolefin resin aqueous dispersion composition (dispersion resin composition) was obtained in the same manner as in example 2, except that the modified polyolefin resin obtained in production example 21 was used. The contents of toluene and ethylene glycol monobutyl ether in the modified polyolefin resin aqueous dispersion composition were 0.02 wt% and 2.4 wt%, respectively, with respect to the modified polyolefin resin aqueous dispersion composition.

(example 17)

A modified polyolefin resin aqueous dispersion composition (dispersion resin composition) was obtained in the same manner as in example 2, except that the modified polyolefin resin obtained in production example 22 was used. The contents of toluene and ethylene glycol monobutyl ether in the modified polyolefin resin aqueous dispersion composition were 0.02 wt% and 2.7 wt%, respectively, with respect to the modified polyolefin resin aqueous dispersion composition.

(example 18)

A modified polyolefin resin aqueous dispersion composition (dispersion resin composition) was obtained in the same manner as in example 2, except that the modified polyolefin resin obtained in production example 23 was used. The contents of toluene and ethylene glycol monobutyl ether in the modified polyolefin resin aqueous dispersion composition were 0.01 wt% and 1.8 wt%, respectively, with respect to the modified polyolefin resin aqueous dispersion composition.

Comparative example 1

A modified polyolefin resin aqueous dispersion composition (dispersion resin composition) was obtained in the same manner as in example 1, except that the modified polyolefin resin obtained in production example 15 was used. The content of methylcyclohexane and propylene glycol monopropyl ether in the modified polyolefin resin aqueous dispersion composition was 0.02% by weight and 2.4% by weight, respectively, based on the modified polyolefin resin aqueous dispersion composition.

Comparative example 2

The procedure of example 2 was repeated, except that the modified polyolefin resin obtained in production example 16 was used. However, in the preparation of the aqueous dispersion, aggregates of the modified polyolefin resin are formed, and an aqueous modified polyolefin resin dispersion cannot be obtained.

Comparative example 3

The procedure of example 1 was repeated, except that the modified polyolefin resin obtained in production example 17 was used. However, in the preparation of the aqueous dispersion, aggregates of the modified polyolefin resin are formed, and an aqueous modified polyolefin resin dispersion cannot be obtained.

Comparative example 4

The procedure of example 2 was repeated, except that the modified polyolefin resin obtained in production example 18 was used. However, in the preparation of the aqueous dispersion, aggregates of the modified polyolefin resin are formed, and an aqueous modified polyolefin resin dispersion cannot be obtained.

Comparative example 5

The procedure of example 1 was repeated, except that the modified polyolefin resin obtained in production example 19 was used. However, in the preparation of the aqueous dispersion, aggregates of the modified polyolefin resin are formed, and an aqueous modified polyolefin resin dispersion cannot be obtained.

The evaluation results of the types of the base resins, the melting points, the weight average molecular weights, the modification degrees K (wt%), the ring-opening ratios R (%), the ring-opening degrees, the average particle diameters, the amounts of the emulsifiers used, and the filterability (filtration rates, amounts of residues) of the dispersed resin compositions obtained in examples 1 to 18 and comparative examples 1 to 5 are listed in table 1.

[ Table 1]

From the results of comparative examples 1 to 5, it is understood that if the ring opening degree of the modified polyolefin resin is less than 70, the average particle diameter exceeds 250nm, or the emulsification is poor. Therefore, if a dispersion resin composition is produced from the modified polyolefin resin, it is found that the dispersibility is poor. On the other hand, from the results of examples 1 to 18, it is understood that if the ring opening degree of the modified polyolefin resin is 70 or more, the average particle diameter is 250nm or less. Therefore, if a dispersion resin composition is produced from a modified polyolefin resin, the dispersibility is excellent regardless of the type of the base resin and even if the blending amount of the emulsifier is less than 10% by weight. Therefore, the dispersion resin composition of the present invention can maintain dispersion stability even if the amount of the emulsifier added is reduced.

Further, as is clear from a comparison of the results of examples 7 and 14, when the dispersion resin composition having an opening ratio of 60% or more was compared with the dispersion resin composition having an opening ratio of less than 60%, the average particle diameter tended to be small and the filterability tended to be good. Therefore, a more preferable dispersion resin composition can be obtained.

[ Table 2]

As is clear from table 2, the dispersion resin composition of the present invention was evaluated as "a" or "B" in terms of stability during centrifugal separation, and the dispersion stability was maintained. Regarding the evaluation of water resistance using a general base material, there was no abnormality in the appearance evaluation and the adhesion was excellent. Further, regarding the evaluation of water resistance using a substrate having poor adhesion, the appearance evaluation was not abnormal, or even when bubbles were generated, adhesion at a level of 2mm or less was secured in practical use.

On the other hand, in comparative example 1, the evaluation of stability at the time of centrifugal separation was "C", and the dispersion stability was poor. Regarding the evaluation of water resistance using a usual base material, the appearance evaluation produced bubbles of 2mm or less, and adhesion was inferior compared with the dispersion resin composition of the present invention. In addition, in the evaluation of water resistance using a substrate having poor adhesion, bubbles exceeding 2mm were generated, and adhesion was not exhibited.