阅读说明：本技术 树脂组合物及其用途 (Resin composition and use thereof ) 是由 神埜胜 阿部仁美 矢田实 高本直辅 于 2019-09-25 设计创作，主要内容包括：课题在于,提供聚烯烃成分的比例多、可制备高固体含量的溶液、长期保存后溶液性状也良好、并且颜料分散性良好的树脂组合物；所述树脂组合物含有(A)成分：聚烯烃树脂的利用(B)成分：(甲基)丙烯酸和/或(甲基)丙烯酸酯得到的改性物,(A)成分与(B)成分的重量比((A)/(B))为90/10～30/70,(B)成分含有20重量%以上的(B1)成分：烷氧基(聚)亚烷基二醇单(甲基)丙烯酸酯。(The problem is to provide a resin composition which has a large proportion of polyolefin components, can prepare a solution with a high solid content, has good solution properties after long-term storage, and has good pigment dispersibility; the resin composition contains (A) component: utilization of polyolefin resin (B) component: a modified product obtained from (meth) acrylic acid and/or (meth) acrylic ester, wherein the weight ratio ((A)/(B)) of the component (A) to the component (B) is 90/10-30/70, and the component (B) contains 20 wt% or more of the component (B1): alkoxy (poly) alkylene glycol mono (meth) acrylates.)

1. A resin composition comprising (A) a modified polyolefin resin obtained by using (B) a (meth) acrylic acid and/or a (meth) acrylic acid ester,

the weight ratio ((A)/(B)) of the component (A) to the component (B) is 90/10-30/70,

the component (B) contains 20 wt% or more of the component (B1): an alkoxy (poly) alkylene glycol mono (meth) acrylate represented by the following general formula (I),

CH₂=C(R¹)COO-(CH₂-CH₂-O-)_n-R²・・・(I)

in the general formula (I), R¹Represents a hydrogen atom or a methyl group, R²Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n represents an integer of 1 to 18, wherein R is²When the hydrogen atom is used, n is an integer of 2 or more.

2. The resin composition according to claim 1, which has a weight average molecular weight of 10,000 to 200,000.

3. The resin composition according to claim 1 or 2, wherein the component (a) is an acid-modified polyolefin resin.

4. The resin composition according to any one of claims 1 to 3, wherein the component (A) is a chlorinated polyolefin resin or an acid-modified chlorinated polyolefin resin.

5. The resin composition according to any one of claims 1 to 4, further comprising an organic solvent.

6. A primer coating material comprising the resin composition according to any one of claims 1 to 5.

7. A binder comprising the resin composition according to any one of claims 1 to 5.

8. An adhesive comprising the resin composition according to any one of claims 1 to 5.

Technical Field

The present invention relates to a resin composition and use thereof.

Background

Since plastic substrates used for automobile parts and the like have low surface free energy and crystallinity, the coatings are difficult to adhere to the plastic substrates. As one of the methods for improving the adhesion of a coating material to a plastic substrate, a method of applying a pretreatment agent to a plastic substrate before coating has been invented and put into practical use. As the pretreatment agent, a paint mixed with a primer (primer) which is a component having good adhesion to a plastic substrate is used.

Chlorinated polyolefins are used as one of the primer components having good adhesion to plastic substrates. For example, patent document 1 discloses a primer resin composition containing a chloride of polypropylene, polyethylene, an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer, or the like as such a chlorinated polyolefin.

Since the coating material mixed with the primer component is applied to the lowermost layer of the substrate, a pigment component is often mixed in the coating material from the viewpoint of weather deterioration. In order to uniformly disperse the pigment component in the paint, a resin component having a relatively high polarity such as an acrylic resin or a polyester resin may be blended as the pigment dispersant. Since the chlorinated polyolefin as the primer component has low polarity, compatibility with the pigment or the pigment dispersant may be poor. For example, when the primer resin composition is blended with a coating material containing a pigment and a pigment dispersant, the pigment component may be precipitated.

As one of the methods for improving the compatibility of the chlorinated polyolefin with the components in the coating material, a compatibilizer may be blended in the coating material. As such a compatibilizer, chlorinated polyolefins modified with (meth) acrylic monomers are widely used.

For example, patent document 2 discloses a resin composition obtained by treating a chlorinated polyolefin resin with a (meth) acrylic monomer containing an ethylenically unsaturated bond and a hydroxyl group and graft-copolymerizing the (meth) acrylic monomer. Patent document 3 discloses a modified resin composition of a chlorinated polyolefin resin, which is obtained by using a modifier containing a predetermined (meth) acrylic monomer. In order to improve the workability, many of these modified chlorinated polyolefins are solutions dispersed in an organic solvent.

Documents of the prior art

Patent document

Patent document 1: in japanese patent No. 4420314, japanese patent application,

patent document 2: in japanese patent No. 3318925, japanese patent application,

patent document 3: international publication No. 2017/110633.

Disclosure of Invention

Problems to be solved by the invention

When the modified chlorinated polyolefin is blended in a coating material, the proportion of the chlorinated polyolefin component in the coating material decreases, and thus there is a problem that the adhesion of the coating film decreases. In order to secure the adhesion of the coating film while blending the modified chlorinated polyolefin, it is preferable to increase the ratio of the polyolefin component in the modified chlorinated polyolefin. In addition, in order to reduce the cost for producing the coating material, the solution of the modified polyolefin is also preferably large in the proportion of the resin component (i.e., high in the solid content).

However, in the conventional modified chlorinated polyolefin, there is a problem that the solution stability is remarkably lowered when the proportion of the chlorinated polyolefin component is increased and the solid content is increased. For example, when a conventional chlorinated polyolefin solution is left to stand on a scale of several months, such as overseas transportation or long-term storage in stock, two-layer separation of the product or generation of aggregates may occur. In addition, when the proportion of the chlorinated polyolefin component is increased, the dispersibility of the pigment may be lowered.

For example, in the modified chlorinated polyolefin described in patent document 2, when the proportion of the chlorinated polyolefin component is increased, aggregates are likely to be generated when left standing at room temperature for 3 months. In addition, when the pigment is blended into a paint containing a pigment, the pigment is likely to precipitate. In the modified chlorinated polyolefin described in patent document 3, when the proportion of the chlorinated polyolefin component is increased, the product is likely to be separated into two layers when left to stand at room temperature for 3 months. When the pigment is blended into a paint containing a pigment, the finish of the coating film tends to be lowered.

Therefore, a modified polyolefin having a large proportion of polyolefin as an adhesion component, capable of producing a solution having a high solid content, having good solution properties even after a long-term storage for several months, and having good pigment dispersibility is desired.

The present invention addresses the problem of providing a resin composition having a high proportion of polyolefin components (resin components), capable of producing a solution having a high solid content, having good solution properties even after long-term storage, and having good pigment dispersibility.

Means for solving the problems

The present inventors have intensively studied the above problems and as a result, have found that the above problems can be solved by containing a modified product obtained by modifying a polyolefin resin with a (meth) acrylic acid and/or a (meth) acrylic ester containing 20% by weight or more of an alkoxy (poly) alkylene glycol mono (meth) acrylic ester, and have completed the present invention.

Namely, the present inventors provide the following [1] to [8 ].

[1] A resin composition comprising a component (A): utilization of polyolefin resin (B) component: a modified product obtained from (meth) acrylic acid and/or (meth) acrylic ester, wherein the weight ratio ((A)/(B)) of the component (A) to the component (B) is 90/10-30/70, and the component (B) contains 20 wt% or more of the component (B1): an alkoxy (poly) alkylene glycol mono (meth) acrylate represented by the following general formula (I):

CH₂=C(R¹)COO-(CH₂-CH₂-O-)_n-R²・・・(I)

in the general formula (I), R¹Represents a hydrogen atom orMethyl, R²Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 18. Wherein, in R²When the hydrogen atom is used, n is an integer of 2 or more.

[2] The resin composition according to the above [1], which has a weight average molecular weight of 10,000 to 200,000.

[3] The resin composition according to the above [1] or [2], wherein the component (A) is an acid-modified polyolefin resin.

[4] The resin composition according to any one of the above [1] to [3], wherein the component (A) is a chlorinated polyolefin resin or an acid-modified chlorinated polyolefin resin.

[5] The resin composition according to any one of the above [1] to [4], further comprising an organic solvent.

[6] A primer coating material containing the resin composition according to any one of [1] to [5 ].

[7] A binder (binder) containing the resin composition according to any one of the above [1] to [5 ].

[8] An adhesive (adhesive) containing the resin composition according to any one of the above [1] to [5 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a resin composition having a large proportion of polyolefin component, capable of producing a solution having a high solid content, good solution properties even after long-term storage, and good pigment dispersibility can be provided.

Detailed Description

The present invention will be described in detail below with reference to preferred embodiments thereof. In the present specification, the expression "AA to BB" means AA or more and BB or less. "(meth) acrylic acid" includes acrylic acid and methacrylic acid, and means at least any one of acrylic acid and methacrylic acid. "(meth) acrylate" includes both acrylate and methacrylate, and refers to at least any of acrylate and methacrylate.

[1. resin composition ]

The resin composition of the present invention contains the following components (A): utilization of polyolefin resin (B) component: a modified product (hereinafter, also referred to as "resin component") obtained from (meth) acrylic acid and/or a (meth) acrylic acid ester. The weight ratio ((A)/(B)) of the component (A) to the component (B) is 90/10-30/70. The component (B) contains 20% by weight or more of the component (B1): an alkoxy (poly) alkylene glycol mono (meth) acrylate represented by the general formula (I),

CH₂=C(R¹)COO-(CH₂-CH₂-O-)_n-R²・・・(I)

in the general formula (I), R¹Represents a hydrogen atom or a methyl group, R²Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 18. Wherein, in R²When the hydrogen atom is used, n is an integer of 2 or more.

(component (A): polyolefin resin)

The polyolefin resin may be a polymer of an olefin. Among the olefin polymers, the polyolefin resin is preferably a polyolefin resin obtained by using a ziegler-natta catalyst or a metallocene catalyst as a polymerization catalyst, more preferably a polypropylene resin obtained by using a ziegler-natta catalyst or a metallocene catalyst as a polymerization catalyst, or a polyolefin resin obtained by copolymerizing propylene and an α -olefin (for example, ethylene, butene, 3-methyl-1-heptene), even more preferably a propylene random copolymer obtained by using a metallocene catalyst as a polymerization catalyst, and even more preferably a polypropylene, an ethylene-propylene copolymer, a propylene-butene copolymer, or an ethylene-propylene-butene copolymer obtained by using a metallocene catalyst as a polymerization catalyst. When a metallocene catalyst is used, the obtained polyolefin resin has a narrow molecular weight distribution, excellent random copolymerization properties, a narrow composition distribution, and a wide range of copolymerizable comonomers.

The "propylene random copolymer" herein refers to polypropylene or a polyolefin resin obtained by random copolymerization of propylene and α -olefin, and examples thereof include polypropylene, ethylene-propylene copolymers, propylene-butene copolymers, ethylene-propylene-diene copolymers, and ethylene-propylene-butene copolymers. The number of (co) polymers constituting the polyolefin resin may be 1 alone or a combination of a plurality of (co) polymers.

As the metallocene catalyst, a known one can be used. For example, a catalyst obtained by combining the component (1) and the component (2), and if necessary, the component (3) may be mentioned. Among them, the metallocene catalyst is preferably a catalyst obtained by combining the component (1) and the component (2) and, if necessary, the component (3).

Component (1): a metallocene complex which is a transition metal compound of group 4 to 6 of the periodic Table of the elements having at least 1 conjugated five-membered ring ligand.

Component (2): an ion-exchange layered silicate.

Component (3): an organoaluminum compound.

The structure of the polyolefin resin may be any of an isotactic structure, a random structure, a syndiotactic structure, and the like that can be obtained by a general polymer compound. Among these structures, in view of adhesion to a polyolefin substrate, particularly adhesion under low-temperature drying, a polyolefin resin having an isotactic structure which can be obtained when a metallocene catalyst is used is preferable.

The content of the propylene structural unit is preferably 60% by weight or more, more preferably 70% by weight or more, and still more preferably 80% by weight or more, as the component composition of the polyolefin resin. When the propylene component is 60% by weight or more, the adhesiveness (adhesiveness) to a propylene base material can be further improved.

The content of the propylene structural unit in the polyolefin resin may be a ratio of the raw materials used or a value calculated by NMR analysis.

The polyolefin resin is preferably an acid-modified polyolefin resin obtained by graft-modifying an α, β -unsaturated carboxylic acid or a derivative thereof (hereinafter, also referred to as "acid component"). By graft-modifying with an acid component, the adhesion, solution stability and pigment dispersibility of the resin composition can be further improved.

Examples of the α, β -unsaturated carboxylic acid and its derivative include maleic acid, maleic anhydride, fumaric acid, citraconic anhydride, mesaconic acid, itaconic anhydride, aconitic acid, and aconitic anhydride. Among them, maleic anhydride, aconitic anhydride and itaconic anhydride are preferable, and maleic anhydride is more preferable.

The acid component may be at least 1 compound selected from the group consisting of α, β -unsaturated carboxylic acids and derivatives thereof, and may be a combination of 1 or more α, β -unsaturated carboxylic acids and 1 or more derivatives thereof, a combination of 2 or more α, β -unsaturated carboxylic acids, and a combination of 2 or more α, β -unsaturated carboxylic acid derivatives.

The graft modification with an acid component can be performed by radically reacting the polyolefin resin with an acid component in the presence of a radical initiator.

The radical initiator may be appropriately selected from known radical initiators. Among them, organic peroxide compounds are preferable. Examples of the organic peroxide-based compound include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, 1, 4-bis [ (t-butylperoxy) isopropyl ] benzene, 1-bis (t-butylperoxy) -3,5, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) -cyclohexane, cyclohexanone peroxide, t-butyl peroxybenzoate, t-butyl peroxyisobutyrate, t-butyl peroxy-3, 5, 5-trimethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisopropylcarbonate, and cumyl peroxyoctoate. Among them, di-tert-butyl peroxide, dicumyl peroxide and dilauryl peroxide are preferable.

The radical initiator may be 1 kind of radical initiator alone or a combination of plural kinds of radical initiators.

The amount of the radical initiator added in the graft modification reaction with the acid component is preferably 0.1 to 100% by mass, and more preferably 1 to 50% by mass, based on the total mass (mass) of the polyolefin resin. When the content is 0.1% by mass or more, a sufficient grafting efficiency can be maintained. When the content is 100% by mass or less, the decrease in the weight average molecular weight of the polyolefin resin can be prevented.

The graft weight of the acid-modified polyolefin resin is preferably 2 to 20 wt%, more preferably 5 to 15 wt%. By setting the graft weight in the above range, the adhesion to the substrate can be improved.

The graft weight of the acid-modified polyolefin resin may be determined by an alkali titration method based on the following formula in accordance with JIS K0070: 1992.

The polyolefin resin is preferably a chlorinated polyolefin resin (hereinafter also referred to as "chlorinated polyolefin resin") or a chlorinated acid-modified polyolefin resin (hereinafter also referred to as "acid-modified chlorinated polyolefin resin"). By the chlorination, the adhesion of the polyolefin resin to the nonpolar resin substrate and the compatibility with other components can be further improved.

Examples of the method for chlorinating the polyolefin resin include the following methods: after dissolving the polyolefin resin or the acid-modified polyolefin resin in a chlorine-based solvent such as chloroform, chlorine gas is blown to introduce chlorine atoms into the polyolefin resin or the acid-modified polyolefin resin.

The blowing of chlorine gas may be performed under ultraviolet irradiation, both in the presence and in the absence of a radical reaction initiator. The pressure at which the chlorine gas is blown in is not limited, and may be normal pressure or pressurized. The temperature at which the chlorine gas is blown is not particularly limited, but is usually 50 to 140 ℃.

As the radical reaction initiator, an organic peroxide-based compound or azonitrile can be used. The organic peroxide-based compound may be the above-mentioned compound.

In the step of chlorinating the polyolefin resin or the acid-modified polyolefin resin, the chlorine-containing solvent in the system is usually distilled off under reduced pressure or the like, or replaced with an organic solvent.

The chlorinated polyolefin resin or the acid-modified chlorinated polyolefin resin preferably has a chlorine content of 10 to 40% by weight, more preferably 15 to 30% by weight. When the chlorine content is in the above range, the polarity of the resin component can be adjusted to a certain range, and therefore, the compatibility with other resins in the coating material becomes good, and sufficient adhesiveness to a nonpolar substrate such as a polyolefin substrate can be obtained.

The chlorinated polyolefin resin or the acid-modified chlorinated polyolefin resin may have a chlorine content in accordance with JIS-K7229: 1995.

The lower limit of the weight average molecular weight (Mw) of the polyolefin resin is preferably 10,000 or more, more preferably 20,000 or more. When the weight average molecular weight is 10,000 or more, the cohesive force of the resin composition is sufficient, and the adhesion to the substrate is excellent. The upper limit is preferably 200,000 or less, more preferably 150,000 or less. When the weight average molecular weight is 200,000 or less, compatibility with other resins other than the resin component of the resin composition of the present invention contained in the coating material becomes good, and a substance having excellent adhesion to the substrate can be obtained.

The weight average molecular weight can be determined from a standard polystyrene calibration curve by a Gel Permeation Chromatography (GPC) method. The measurement conditions of GPC are as follows:

the device comprises the following steps: HLC-8320GPC (TOSOH Co., Ltd.)

Column: TSK-gel G-6000H X L, G-5000H X L, G-4000H X L, G-3000H X L, G-2000H X L (manufactured by TOSOH Co., Ltd.)

Eluent: THF (tetrahydrofuran)

Flow rate: 1mL/min

Temperature: 40 ℃ for pump incubator and column incubator

Injection amount: 100 μ L

Standard substance: polystyrene EasiCal PS-1 (Agilent Technology).

(component (B): meth (acrylic acid) and/or (meth) acrylic ester)

"(meth) acrylic acid and/or (meth) acrylate" means a compound containing at least 1 (meth) acryloyl group (means at least any one of an acryloyl group and a methacryloyl group) in a molecule.

(B) Component (a) contains component (B1): an alkoxy (poly) alkylene glycol mono (meth) acrylate represented by the general formula (I).

CH₂=C(R¹)COO-(CH₂-CH₂-O-)_n-R²・・・(I)

In the general formula (I), R¹Represents a hydrogen atom or a methyl group, R²Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 18. Wherein, in R²When the hydrogen atom is used, n is an integer of 2 or more.

(B) The content of component (B1) in component (A) is 20% by weight or more. Thus, when the resin composition is blended into a coating material, a suitable interaction occurs between the structural unit in the general formula (I) and the pigment component, and thus the dispersibility of the pigment can be improved. Further, the structural unit in the general formula (I) can improve the dispersibility of the resin component in the dispersion medium, and therefore can improve the solution stability of the dispersion liquid. Since the solution stability of the dispersion liquid is improved, the solution stability can be maintained even if the proportion of the resin component in the dispersion liquid is increased (even if the solid content is high).

In the component (B), the component (B1) may be 1 kind alone or 2 or more kinds.

Examples of the component (B1) include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methylcarbitol (meth) acrylate, ethylcarbitol (meth) acrylate, methoxytetraethyleneglycol (meth) acrylate, ethoxytetraethyleneglycol (meth) acrylate, n-butoxytetraethyleneglycol (meth) acrylate, polyethylene glycol (meth) acrylate, and ethoxypolyethylene glycol (meth) acrylate. Among them, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methyl carbitol (meth) acrylate, and ethyl carbitol (meth) acrylate are preferable.

(B) The component (B) may contain (meth) acrylic acid and/or (meth) acrylic acid ester (hereinafter, also referred to as "component (B2)") other than the component (B1).

Examples of the component (B2) include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, and the like.

Examples of the type of the functional group of the component (B) include a hydroxyl group, a carboxyl group, an alkoxysilyl group, an amide group, and a mercapto group. The resin component in the resin composition may have only 1 kind of these functional groups, or may have 2 or more kinds.

When the resin component in the resin composition has such a functional group, the adhesion of the coating film is improved due to the interaction with other components in the top coating composition, the affinity of the coating film is improved, and the like. In addition, the pigment is properly interacted with the pigment, and the pigment dispersibility is improved.

Typical methods for obtaining a modified product by modifying a polyolefin resin using the component (B) include a solution method in which a polyolefin resin is dispersed in an organic solvent to perform a modification reaction, and a melting method in which a polyolefin resin is heated and melted to perform a modification reaction.

In the case of the solution method, the polyolefin resin is dissolved in an organic solvent, and then reacted with the component (B) in the presence of a radical reaction initiator by heating and stirring. The solution method has the advantages of less side reactions and uniform graft polymer.

As the organic solvent, an aromatic hydrocarbon solvent such as toluene or xylene is preferably used. The reaction temperature is preferably 60 to 180 ℃.

In the case of the melting method, the polyolefin resin is heated and melted (heated and melted) in the presence of a radical reaction initiator to react with the component (B). The melting method has the advantages of simple operation and reaction in a short time.

The temperature for heating and melting may be equal to or higher than the melting point of the polyolefin resin, and is preferably equal to or higher than the melting point of the polyolefin resin and equal to or lower than 300 ℃. For the melting by heating, a Banbury mixer, a kneader, an extruder or the like can be used.

Examples of the radical reaction initiator used for modification using the component (B) include organic peroxide compounds and azonitriles.

Examples of the organic peroxide-based compound include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, dilauryl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, cumene hydroperoxide, t-butyl hydroperoxide, 1-bis (t-butylperoxy) -3,5, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) -cyclohexane, cyclohexanone peroxide, t-butyl peroxybenzoate, t-butyl peroxyisobutyrate, t-butyl peroxy-3, 5, 5-trimethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisopropylcarbonate, and cumyl peroxyoctoate.

As for the radical reaction initiator, a substance having an appropriate half-life temperature may be selected depending on the temperature at which radical polymerization is carried out.

In the resin component of the resin composition, the weight ratio ((A)/(B)) of the polyolefin resin to the component (B) is in the range of 90/10-30/70. When the weight ratio ((a)/(B)) is in such a range, a resin composition having excellent pigment dispersibility and excellent adhesion to a substrate can be obtained.

An embodiment of the resin composition may further contain the above-mentioned resin component (a modified product of the polyolefin resin obtained by the component (B)) and an organic solvent. This embodiment can be said to be a dispersion liquid in which the resin component is dispersed in 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 cyclohexane, and aliphatic or alicyclic hydrocarbon solvents such as cyclohexane, methyl cyclohexane, nonane and decane.

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

In addition, in order to improve the storage stability of the dispersion, 1 kind of alcohol (for example, methanol, ethanol, propanol, isopropanol, butanol) or 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.

[2. coating material, adhesive, and adhesive for primer ]

The primer coating of the present invention, the adhesive of the present invention (adhesive for coating or adhesive for ink), and the adhesive of the present invention contain the resin composition. Therefore, the adhesive composition is excellent in adhesiveness, solution stability and pigment dispersibility, and can be suitably used as a coating adhesive which is excellent in adhesion between a primer when a polyolefin substrate such as a bumper of an automobile is top-coated and a top-coat paint or a clear paint (clear).

The primer coating of the present invention, the binder of the present invention (binder for coating or binder for ink), and the binder of the present invention can be used in the form of a solution, powder, sheet, or the like according to the application. In addition, in this case, additives such as an antioxidant, a light stabilizer, an ultraviolet absorber, an inorganic filler, and the like may be blended as necessary.

Examples

The present invention will be described in detail below with reference to examples. The following examples are intended to illustrate the present invention and are not intended to limit the present invention. Unless otherwise stated, the measurement methods of the physical property values and the like are the measurement methods described above. Further, "part" means part by weight.

[ weight average molecular weight (Mw) ]:

measurement was carried out by GPC under the following conditions:

the device comprises the following steps: HLC-8320GPC (TOSOH Co., Ltd.)

Column: TSK-gel G-6000H X L, G-5000H X L, G-4000H X L, G-3000H X L, G-2000H X L (manufactured by TOSOH Co., Ltd.)

Eluent: THF (tetrahydrofuran)

Flow rate: 1mL/min

Temperature: 40 ℃ for pump incubator and column incubator

Injection amount: 100 μ L

Standard substance: polystyrene EasiCal PS-1 (Agilent Technology).

[ chlorine content (% by weight%) ]:

according to JIS-K7229: 1995.

[ maleic anhydride content (% by weight) ]:

by an alkali titration method, according to JIS K0070: 1992.

[ weight ratio of polyolefin resin to component (B) ((A)/(B)) ]:

calculated from the amounts of the respective components used.

Preparation example 1 preparation of acid-modified chlorinated polyolefin resin (A-1)

100 parts of a propylene random copolymer (the content of propylene structural units: 96% by weight and the content of ethylene structural units: 4% by weight) as a polyolefin resin prepared by using a metallocene catalyst as a polymerization catalyst, 10 parts of maleic anhydride as an α, β -unsaturated carboxylic acid cyclic anhydride, and 2 parts of di-tert-butyl peroxide as a radical initiator were uniformly mixed, and fed to a biaxial extruder (L/D =60, diameter =15mm, barrel 1 to barrel 14).

The reaction was carried out under the conditions of a residence time of 10 minutes, a rotation speed of 200rpm, a cylinder temperature of 100 ℃ (barrels 1 and 2), 200 ℃ (barrels 3 to 8), 90 ℃ (barrels 9 and 10), and 110 ℃ (barrels 11 to 14). Then, a reduced pressure treatment was performed to remove unreacted maleic anhydride, to obtain an acid-modified polypropylene resin modified with maleic anhydride.

100 parts of the acid-modified polypropylene resin was charged into a glass-lined reaction vessel. Adding chloroform at 2kgf/cm²After the resin was sufficiently dissolved at a temperature of 110 ℃ under the pressure of (3), 2 parts of azobisisobutyronitrile as a radical initiator was added, and the pressure in the autoclave was controlled to 2kgf/cm²While blowing chlorine gas, chlorination was carried out.

After the reaction was completed, 6 parts of an epoxy compound (Eposizer W-100EL, manufactured by Dainippon ink chemical industries, Ltd.) was added as a stabilizer, and the mixture was fed to a vented extruder having a suction part for desolvation at the screw shaft part, desolvated, and solidified to obtain an acid-modified chlorinated polyolefin resin (A-1) as an acid-modified chlorinated polypropylene resin. The weight average molecular weight of the acid-modified chlorinated polyolefin resin obtained was 90,000, the content of maleic anhydride was 10% by weight, and the content of chlorine was 10% by weight.

Preparation example 2 preparation of chlorinated polyolefin resin (A-2)

100 parts of a propylene random copolymer (content of propylene structural units: 80% by weight, content of ethylene structural units: 20% by weight) as a polyolefin resin prepared by using a metallocene catalyst as a polymerization catalyst was charged into a glass-lined reaction vessel. Adding chloroform at 2kgf/cm²After the resin was sufficiently dissolved at a temperature of 110 ℃ under the pressure of (3), 4 parts of azobisisobutyronitrile as a radical initiator was added, and the pressure in the autoclave was controlled to 3kgf/cm²While blowing chlorine gas, chlorination was carried out.

After the reaction was completed, 6 parts of an epoxy compound (Eposizer W-100EL, manufactured by Dainippon ink chemical industries, Ltd.) was added as a stabilizer, and the mixture was fed to a vented extruder equipped with a suction part for desolvation at the screw shaft part, desolvated, and solidified to obtain a chlorinated polyolefin resin (A-2). The weight average molecular weight of the obtained chlorinated polyolefin resin was 20,000, and the chlorine content was 40% by weight.

Preparation example 3 preparation of polyolefin resin (A-3)

100 parts of a propylene random copolymer (content of propylene structural units: 80% by weight, content of ethylene structural units: 20% by weight) as a polyolefin resin prepared by using a metallocene catalyst as a polymerization catalyst and 6 parts of di-tert-butyl peroxide as a radical initiator were uniformly mixed and fed to a twin-screw extruder (L/D =60, diameter =15mm, barrels 1 to 14).

The reaction was carried out under the conditions of a residence time of 10 minutes, a rotation speed of 200rpm, a cylinder temperature of 100 ℃ (barrels 1 and 2), 200 ℃ (barrels 3 to 8), 90 ℃ (barrels 9 and 10), and 110 ℃ (barrels 11 to 14) to obtain a polyolefin resin (A-3). The weight average molecular weight of the obtained polyolefin resin was 50,000.

A list of the polyolefin resins prepared in preparation examples 1 to 3 is shown in Table 1 below.

[ Table 1]

Preparation example	Kinds of polyolefin resins	Modification with or without MAH	With or without chlorination	Content of MAH (% by weight)	Degree of chlorination (% by weight)	Weight average molecular weight
							1	A-1	Is provided with	Is provided with	10	10	90,000
2	A-2	Is free of	Is provided with	-	40	20,000
							3	A-3	Is free of	Is free of	-	-	50,000

MAH: maleic anhydride.

Example 1 preparation of a dispersion of the resin component (C-1)

100 parts of the acid-modified chlorinated polyolefin resin (A-1) obtained in preparation example 1 was dissolved in 50 parts of toluene, and 5 parts of an epoxy compound (Eposizer W-131, DIC) was added. 5.5 parts of a peroxide ester-based peroxide (PERBUTYL O, manufactured by NOF corporation) was added thereto at 85 ℃ under a nitrogen atmosphere. Then, monomers (10.7 parts of methyl methacrylate, 26.7 parts of cyclohexyl methacrylate, 26.7 parts of 2-methoxyethyl acrylate, and 2.7 parts of 2-hydroxyethyl acrylate) as polymerizable (meth) acrylic esters represented by the component (B-1) shown in Table 2 were added, and the reaction was carried out at 85 ℃ for 6 hours. After the reaction was completed, toluene, cyclohexane and 1-butanol were added so that the final solvent composition was toluene/cyclohexane/1-butanol =76/20/4 (wt%), yielding a dispersion of the resin component (C-1) having a solid content of 50 wt%. The weight average molecular weight of the resin component modified with the low-molecular weight compound was 200,000.

Example 2 preparation of dispersion of resin component (C-2)

100 parts of the chlorinated polyolefin resin (A-2) obtained in preparation example 2 was dissolved in 50 parts of toluene, and 5 parts of an epoxy compound (Eposizer W-131, DIC) was added thereto. 5.5 parts of a peroxide ester-based peroxide (PERBUTYL O, manufactured by NOF corporation) was added thereto at 85 ℃ under a nitrogen atmosphere. Then, monomers (46.7 parts of methyl methacrylate, 140.0 parts of cyclohexyl methacrylate, and 46.7 parts of 2-methoxyethyl acrylate) as polymerizable (meth) acrylate represented by the component (B-2) shown in Table 2 were added, and the reaction was carried out at 85 ℃ for 6 hours. After the reaction was completed, toluene, cyclohexane and 1-butanol were added so that the final solvent composition was toluene/cyclohexane/1-butanol =76/20/4 (wt%), yielding a dispersion of the resin component (C-2) having a solid content of 50 wt%. The weight average molecular weight of the resin component modified with the low-molecular weight compound was 30,000.

Example 3 preparation of dispersion of resin component (C-3)

100 parts of the polyolefin resin (A-3) obtained in preparation example 3 was dissolved in 50 parts of toluene, and 5 parts of an epoxy compound (Eposizer W-131, DIC) was added thereto. 5.5 parts of a peroxide ester-based peroxide (PERBUTYL O, manufactured by NOF corporation) was added thereto at 85 ℃ under a nitrogen atmosphere. Then, monomers (10.7 parts of methyl methacrylate, 26.7 parts of cyclohexyl methacrylate, 26.7 parts of 2-methoxyethyl acrylate, and 2.7 parts of 2-hydroxyethyl acrylate) as polymerizable (meth) acrylate represented by the component (B-1) shown in table 2 were added, and a reaction was carried out at 85 ℃ for 6 hours, and after the reaction was completed, toluene, cyclohexane, and 1-butanol were added so that the final solvent composition was toluene/cyclohexane/1-butanol =76/20/4 (wt%), to obtain a dispersion of the resin component (C-3) having a solid content of 50 wt%. The weight average molecular weight of the resin component modified with the low molecular weight compound was 80,000.

Comparative example 1 preparation of dispersion of resin component (C-4)

100 parts of the acid-modified chlorinated polyolefin resin (A-1) obtained in preparation example 1 was dissolved in 50 parts of toluene, and 5 parts of an epoxy compound (Eposizer W-131, DIC) was added. 5.5 parts of a peroxide ester-based peroxide (PERBUTYL O, manufactured by NOF corporation) was added thereto at 85 ℃ under a nitrogen atmosphere. Then, the polymerizable (meth) acrylate monomers (13.3 parts of methyl methacrylate, 46.7 parts of cyclohexyl methacrylate, and 6.7 parts of 2-hydroxyethyl acrylate) represented by the component (B' -3) shown in Table 2 were added thereto, and the reaction was carried out at 85 ℃ for 6 hours. After the reaction was completed, toluene, cyclohexane and 1-butanol were added so that the final solvent composition was toluene/cyclohexane/1-butanol =76/20/4 (wt%), yielding a dispersion of the resin component (C-4) having a solid content of 50 wt%. The weight average molecular weight of the resin component modified with the low-molecular weight compound was 200,000.

Comparative example 2 preparation of Dispersion of resin component (C-5)

100 parts of the acid-modified chlorinated polyolefin resin (A-1) obtained in preparation example 1 was dissolved in 50 parts of toluene, and 5 parts of an epoxy compound (Eposizer W-131, DIC) was added. 5.5 parts of a peroxide ester-based peroxide (PERBUTYL O, manufactured by NOF corporation) was added thereto at 85 ℃ under a nitrogen atmosphere. Then, monomers (64.0 parts of methyl methacrylate, 160.0 parts of cyclohexyl methacrylate, 160.0 parts of 2-methoxyethyl acrylate, and 16.0 parts of 2-hydroxyethyl acrylate) as polymerizable (meth) acrylic esters represented by the component (B-1) shown in Table 2 were added, and the reaction was carried out at 85 ℃ for 6 hours. After the reaction was completed, toluene, cyclohexane and 1-butanol were added so that the final solvent composition was toluene/cyclohexane/1-butanol =76/20/4 (wt%), yielding a dispersion of the resin component (C-5) having a solid content of 50 wt%. The weight average molecular weight of the resin component modified with the low molecular weight compound was 100,000.

Comparative example 3 preparation of Dispersion of resin component (C-6)

100 parts of the acid-modified chlorinated polyolefin resin (A-1) obtained in preparation example 1 was dissolved in 50 parts of toluene, and 1 part of an epoxy compound (Eposizer W-131, DIC) was added. 5.5 parts of a peroxide ester-based peroxide (PERBUTYL O, manufactured by NOF corporation) was added thereto at 85 ℃ under a nitrogen atmosphere. Then, monomers (0.8 parts of methyl methacrylate, 2.1 parts of cyclohexyl methacrylate, 2.1 parts of 2-methoxyethyl acrylate, and 0.2 part of 2-hydroxyethyl acrylate) as polymerizable (meth) acrylic esters represented by the component (B-1) shown in Table 2 were added, and the reaction was carried out at 85 ℃ for 6 hours. After the reaction was completed, toluene, cyclohexane and 1-butanol were added so that the final solvent composition was toluene/cyclohexane/1-butanol =76/20/4 (wt%), yielding a dispersion of the resin component (C-6) having a solid content of 50 wt%. The weight average molecular weight of the resin component modified with the low-molecular weight compound was 110,000.

A list of monomers used as polymerizable (meth) acrylates in examples 1 to 3 and comparative examples 1 to 3 is shown in Table 2 below.

[ Table 2]

MMA: methacrylic acid methyl ester

CHMA: cyclohexyl methacrylate

2 MTA: 2-Methoxyethyl acrylate

HEA: 2-hydroxyethyl acrylate.

For the prepared dispersion liquid of the resin component, stability of the dispersion liquid was evaluated, and a test piece was prepared and adhesion test was confirmed. In addition, the dispersion liquid, the pigment and the compatibilizer were mixed to prepare a coating, and the pigment dispersibility and the hue stability were evaluated. The details of the composition of the resin components and the evaluation results are recorded in table 3. The details of the evaluation method and the test method are as follows.

[ evaluation of stability of dispersion ]:

after the dispersions of the resin components prepared in examples and comparative examples, in which the solid content of the resin component was 50%, were stored at room temperature for 3 months, the properties of the solutions were visually observed. The evaluation results in A to C showed no practical problem.

A: thickening and separation of the solution were not confirmed, and the same overview as immediately after the preparation was obtained.

B: although thickening and separation of the solution were not observed, the solution was cloudy compared with the solution immediately after the preparation.

C: although no separation of the solution was seen, slight thickening was observed, or a shadow (haze) was observed upon shaking.

D: the solution separated into two layers, was greatly thickened, or aggregates were visually observed.

[ preparation of test piece ]:

the surface of an ultra-high rigidity polypropylene plate is degreased with isopropyl alcohol, a dispersion of a resin component is spray-coated so that a dry coating film is 10 to 15 [ mu ] m, and preheating is performed for 5 minutes at the melting point of the resin component +15 ℃. Subsequently, a 1K substrate containing a resin component was spray-coated, left to stand for 10 minutes, and then a 2K varnish was applied. Then, the test piece was prepared by baking the resin composition at a melting point of the resin component +15 ℃ for 30 minutes. The following adhesion test was performed using this test piece.

[ adhesion test ]:

linear cuts reaching the base were added to the coating film of the test piece at 1mm intervals in a horizontal and vertical direction to prepare 100 areas (checkerboard), and the test piece was peeled off in a 180 ° direction with a cellophane tape adhered thereto. For the same 100 areas, the cellophane tape was peeled off after being adhered 10 times, and the adhesiveness (adhesiveness) was evaluated according to the following criteria. When the number of the peeled coating film areas is 50 or less (i.e., evaluation A to C), there is no practical problem.

A: the coating film was not peeled off.

B: the number of the coating film regions to be peeled is 1 or more and 10 or less.

C: the number of the peeled coating film areas is more than 10 and 50 or less.

D: the area of the coating film peeled off was more than 50.

[ dispersion of pigment and preparation of pigment-blended coating ]:

40 parts of a dispersion liquid containing a resin component and having a solid content of 50%, 20 parts of a pigment, 10 parts of xylene, 10 parts of butyl acetate and glass beads having the same volume were put into a batch SG mill and dispersed for 4 hours (60mm impeller, 2000 rpm). Further, 20 parts of an acrylic resin was blended and stirred with a disperser to prepare pigment-blended paints (blue, yellow, red). The details of the resin components and pigments used are shown in table 3. The details of the pigment and the acrylic resin are as follows.

Blue pigment: fastogen Blue 5480 (manufactured by Dainippon ink Co., Ltd.)

Yellow pigment: HOSTAPEARM YELLOW H3g (manufactured by Clariant corporation)

Red pigment: irgazine DPP Red BO (manufactured by Ciba Specialty Co., Ltd.)

Acrylic resin: dianal BR-116 (MITSUBISHI RAYON CO., LTD. manufactured)

The pigment-blended coating materials (blue, yellow and red) were evaluated for pigment dispersibility and color stability by the following methods. The evaluation results are shown in table 3.

[ pigment dispersibility of pigment-blended coating ]:

the obtained paint was stored at room temperature for 3 days, and then the state of separation of the pigment was visually observed. Further, the pigment dispersibility was evaluated by the following evaluation criteria using a fineness meter (particles ゲージ) according to the JISK-5600-2-5 dispersibility test. If the pigment component is dispersed at less than 10 μm (i.e., if it is evaluated as A to C), there is no practical problem.

A: the pigment was uniformly dispersed in the coating material, and the color tone was not changed from that immediately after the preparation.

B: although the pigment was uniformly dispersed in the paint, when the paint was shaken, a shadow (haze) was observed in the paint.

C: the pigment component is dispersed with a fineness of less than 10 μm.

D: the pigment component has a fineness meter of 10 μm or more.

[ color tone stability of pigment-blended coating ]:

the pigment-blended coating was stored at room temperature for 3 days, then coated on a tin plate using an 8 mil doctor blade, and dried at 60 ℃ for 3 minutes. The dried product was subjected to color measurement using a digital color difference meter (manufactured by Suga Test Instruments Co., Ltd.). From this value and the initial value before storage, Δ E is obtained. If the value of Δ E is 10 or less (i.e., evaluation A to C), there is no practical problem.

A: the value of Δ E is 0.5 or less.

B: the value of Δ E is higher than 0.5 and 2 or less.

C: the value of Δ E is higher than 2 and 10 or less.

D: the value of Δ E is higher than 10.

[ Table 3]

According to the test results, in example 1, since the weight ratio of (a)/(B) in the resin components of the resin composition falls within the specified range, the dispersion liquid was good in stability, adhesion and pigment dispersibility. In example 2, the component (a) was not acid-modified and therefore had slightly poor adhesion to the substrate, but the proportion of the component (B) in the resin component of the resin composition was high, so that the dispersion was excellent in stability, pigment dispersibility and color tone stability. In example 3, since the component (a) in the resin component was neither acid-modified nor chlorinated, the compatibility with a solvent and the compatibility with a pigment/compatibilizer were slightly poor, and the adhesion to a substrate was also slightly poor. However, since the modification is carried out with the component (B1), the performance satisfying practical use is secured.

In comparative example 1, since the component (B1) was not blended with the component (B), the compatibility between the polyolefin resin and the organic solvent and the compatibility between the resin component of the resin composition and the pigment and the compatibilizing resin could not be ensured, and the stability, adhesion, pigment dispersibility, and color tone stability of the dispersion were poor. In comparative example 2, the proportion of the component (a) in the resin components of the resin composition was low, so that the adhesion was very poor, and the practical use was not suitable. In comparative example 3, since the proportion of the component (B) in the resin component of the resin composition was low, the dispersion stability, pigment dispersibility, and color tone stability were poor, and thus it was not suitable for practical use.