CN113195624A

CN113195624A - Chlorinated polyolefin resin composition and use thereof

Info

Publication number: CN113195624A
Application number: CN201980086163.7A
Authority: CN
Inventors: 小池谅; 近藤圭; 土井龙二; 关口俊司
Original assignee: Nippon Paper Industries Co Ltd
Current assignee: Nippon Paper Industries Co Ltd
Priority date: 2018-12-27
Filing date: 2019-12-24
Publication date: 2021-07-30
Also published as: WO2020138117A1; JPWO2020138117A1

Abstract

The present invention aims to provide a chlorinated polyolefin resin composition which is useful for applications such as paints, primers, inks, adhesives, and heat-sealing agents and has no problem in terms of safety because it can exhibit good adhesion to a substrate such as a polyolefin resin substrate, can form a good coating film, and can exhibit good emulsifiability and stability. The present invention provides a chlorinated polyolefin resin composition comprising component (a): a chlorinated polyolefin, and a component (B): a compound having at least 1 glycidyl group represented by the formula (1). The water solubility of at least 1 of the compounds represented by the formula (1) contained in the component (B) is 20% or more. The component (A) is preferably an acid-modified chlorinated polyolefin. The chlorinated polyolefin resin composition of the present invention can be used as a coating, a primer, an ink, an adhesive or a heat sealer.

Description

Chlorinated polyolefin resin composition and use thereof

Technical Field

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

Background

Patent document 1 describes that a chlorinated polyolefin resin composition containing at least one selected from the group consisting of an α -olefin oxide and an α, ω -olefin oxide exhibits good adhesion in any form of an aqueous dispersion, a resin solution, and a solid substance.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 5484642.

Disclosure of Invention

Problems to be solved by the invention

However, in the aqueous dispersion of the chlorinated polyolefin resin composition of patent document 1, a predetermined amount of an emulsifier is used. Although further improvement in adhesiveness and water resistance can be expected by reducing the amount of the emulsifier, the emulsifying property and stability may be lowered by reducing the amount of the emulsifier, and there is still room for improvement.

The present invention has been made to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide a chlorinated polyolefin resin composition which is useful for applications such as paints, primers, inks, adhesives, and heat sealing agents, and has no problem in terms of safety, since it can exhibit good adhesion to a substrate such as a polyolefin resin substrate, can form a good coating film, and can exhibit good emulsifiability and stability.

Means for solving the problems

The present invention provides the following [ 1] to [ 7 ].

[ 1] a chlorinated polyolefin resin composition comprising:

component (A): chlorinated polyolefin, and

component (B): a compound having at least 1 group represented by the formula (1),

[ solution 1]

，

The component (B) contains at least the above-mentioned compound having a water solubility of 20% or more.

The chlorinated polyolefin resin composition according to [ 2] [ 1], which further comprises a component (C): an alpha-olefin oxide represented by the general formula (2) and/or an alpha, omega-olefin oxide represented by the general formula (3),

[ solution 2]

In the formula, m is an integer of 3-26;

[ solution 3]

Wherein n is an integer of 2 to 28.

[ 3] the chlorinated polyolefin resin composition according to [ 1] or [ 2], wherein the component (B) contains at least 1 compound having 2 or more groups represented by the formula (1).

The chlorinated polyolefin resin composition according to any one of [ 4] to [ 1] to [ 3], wherein the content of the component (B) is 0.1 to 15 parts by weight based on 100 parts by weight of the content of the component (A).

The chlorinated polyolefin resin composition according to any one of [ 5] to [ 1] to [ 4], wherein the component (A) comprises an acid-modified chlorinated polyolefin.

The chlorinated polyolefin resin composition according to any one of [ 6 ] [ 1] to [ 5], further comprising a component selected from the group consisting of (E): basic substance, component (F): an emulsifier, and component (G): at least 1 of the aqueous media.

[ 7 ] A coating material, a primer, an ink, an adhesive or a heat-sealing agent, which comprises the chlorinated polyolefin resin composition according to any one of [ 1] to [ 6 ].

Effects of the invention

When the chlorinated polyolefin resin composition of the present invention is applied to a substrate such as a polyolefin resin substrate, the composition has excellent adhesion to the substrate and can give a good coating film. Therefore, the chlorinated polyolefin resin composition of the present invention is useful for various applications such as paints, primers, inks, adhesives, heat-sealing agents, and the like.

Detailed Description

The chlorinated polyolefin resin composition of the present invention comprises component (a): a chlorinated polyolefin, and a component (B): a compound having at least 1 group represented by the formula (1).

[ component (A): chlorinated polyolefins)

Chlorinated polyolefins are resins obtained by introducing chlorine into polyolefins.

(raw polyolefin)

The polyolefin as a raw material of the chlorinated polyolefin is not particularly limited, and may be subjected to a pretreatment such as degradation, and may be either crystalline or amorphous. Examples of the polyolefin include polypropylene, propylene- α -olefin copolymer, and ethylene-vinyl acetate copolymer. The number of the polyolefin may be 1 alone or 2 or more in combination.

The propylene- α -olefin copolymer is a resin obtained by copolymerizing propylene and an α -olefin as main components. The form of the copolymer is not particularly limited, and examples thereof include a block copolymer and a random copolymer. Examples of the α -olefin component include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 4-methyl-1-pentene. The content of the propylene component in the chlorinated polyolefin using the propylene- α -olefin copolymer as a raw material is preferably 50 mol% or more. This improves the adhesion to the polyolefin resin.

The ethylene-vinyl acetate copolymer is a resin obtained by copolymerizing ethylene with a vinyl acetate monomer. The molar ratio of ethylene to vinyl acetate in the ethylene-vinyl acetate copolymer is not particularly limited, and the vinyl acetate component is preferably 5 to 45 mol%. This improves the adhesion to polar substances and the strength of the coating film.

The melting point of the polyolefin is preferably 100 to 180 ℃, and more preferably 120 to 170 ℃.

(Chlorination)

The method for producing the chlorinated polyolefin is not particularly limited. For example, a method including a step of introducing chlorine into a polyolefin (preferably, an acid-modified polyolefin described later) is included.

When chlorine is introduced, the polyolefin may be dissolved in a chlorine-containing solvent such as chloroform. The introduction of chlorine is usually carried out by blowing chlorine gas into the reaction system. The chlorine gas may be blown in under irradiation of ultraviolet rays, or may be blown in the presence or 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 when the chlorine gas is blown in is not particularly limited, but is usually 50 to 140 ℃.

Examples of the radical reaction initiator 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, cumyl peroxyoctoate, and the like. Examples of the azonitriles include 2, 2-azobis (2-methylbutyronitrile), 2, 2-azobisisobutyronitrile, 2, 2-azobis (2, 4-dimethylvaleronitrile), 2, 2-azobis (4-methoxy-2, 4-dimethylvaleronitrile), and the like.

Chlorinated polyolefins are obtained after the end of the introduction of chlorine into the polyolefin. The chlorine-containing solvent in the system is usually distilled off under reduced pressure or the like, or replaced with an organic solvent.

(acid-modified chlorinated polyolefin)

The component (A) may be 1 chlorinated polyolefin alone or a combination of 2 or more chlorinated polyolefins having different structures, production methods, and the like, and preferably contains at least 1 acid-modified chlorinated polyolefin. This makes it possible to exhibit good dispersibility in an aqueous dispersion.

The acid-modified chlorinated polyolefin is a resin obtained by introducing an α, β -unsaturated carboxylic acid and/or a derivative thereof and chlorine into a polyolefin.

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, aconitic anhydride, nadic anhydride, (meth) acrylic acid, and (meth) acrylic acid esters. Among them, maleic anhydride is preferable in view of the graft property to polyolefin. The graft amount of the α, β -unsaturated carboxylic acid and/or its derivative is preferably 0 to 20% by weight, more preferably 0 to 10% by weight. When the amount is 20% by weight or less, the generation of unreacted materials can be suppressed. The graft weight (% by weight) can be determined by an alkali titration method or a Fourier transform infrared spectroscopy method. The α, β -unsaturated carboxylic acid and its derivative used for the acid-modified chlorinated polyolefin may be 1 kind alone or 2 or more kinds in combination.

(method of acid modification seed chlorination)

Examples of the method for producing the acid-modified chlorinated polyolefin include a method comprising the following steps:

step (1): a step for acid-modifying a polyolefin to obtain an acid-modified polyolefin; and

step (2): and a step of introducing chlorine into the acid-modified polyolefin.

Since the step (2) is the same as previously described, the step (1) will be described below. In the step (1), the acid modification includes, for example, a method of introducing an α, β -unsaturated carboxylic acid and/or a derivative thereof into a polyolefin by graft copolymerization. The conditions for graft copolymerization are not particularly limited, and the graft copolymerization may be carried out by a known method such as a melt method or a solution method. When the melting method is used, the operation is simple and the reaction can be carried out in a short time. When the solution method is used, side reactions are less and a uniform graft polymer can be obtained.

In the case of the melting method, for example, the polyolefin is heated and melted (heated and melted) in the presence of a radical reaction initiator to be reacted. The temperature for heating and melting may be the melting point or higher, and is preferably the melting point or higher and 300 ℃. For the heating and melting, a Banbury mixer, a kneader, an extruder or the like can be used. In the case of the solution method, for example, the polyolefin is dissolved in an organic solvent and then heated and stirred in the presence of a radical reaction initiator to react. The organic solvent is preferably an aromatic solvent such as toluene or xylene. The reaction temperature is preferably 100 to 180 ℃. Examples of the radical reaction initiator used in the melt method and the solution method include the radical reaction initiators exemplified in the production examples of chlorinated polyolefins.

(chlorine content)

In the present invention, the chlorinated polyolefin preferably has a chlorine content of 10% by weight or more, more preferably 15% by weight or more. Thereby, good solvent solubility can be obtained. The upper limit is preferably 45% by weight or less, more preferably 35% by weight or less. This suppresses the polarity to a certain extent or less, and sufficient adhesion to a nonpolar substrate such as a polyolefin substrate can be obtained. Therefore, the chlorinated polyolefin preferably has a chlorine content of 10 to 45% by weight, more preferably 15 to 35% by weight.

The chlorine content can be measured according to JIS-K7229. That is, the measurement can be carried out by an "oxygen bottle combustion method" in which a chlorine-containing resin is combusted in an oxygen atmosphere, the generated chlorine gas is absorbed by water, and the amount is determined by titration. The chlorine content in the examples described below is also a value measured by this method.

The weight average molecular weight of the chlorinated polyolefin is preferably 200,000 or less, more preferably 80,000 or less, and further preferably 60,000 or less. The lower limit is usually 10,000 or more, more preferably 20,000 or more. The weight average molecular weight can be determined from a standard polystyrene calibration curve by a Gel Permeation Chromatography (GPC) method.

[ component (B): compounds having glycidyl groups ]

The component (B) is a compound having at least 1 glycidyl group. The glycidyl group is represented by formula (1).

[ solution 4]

(Water solubility)

The compound having at least 1 group represented by formula (1) may be water-soluble or hydrophobic, but is preferably water-soluble. When the component (B) is 1 of the compounds having at least 1 group represented by the formula (1), the compound is preferably water-soluble. When the component (B) is a combination of 2 or more compounds having at least 1 group represented by the formula (1), at least 1 of them is preferably water-soluble, and more preferably all the compounds are water-soluble. The water solubility of a compound can be expressed by the water solubility. The water solubility of the compound is usually 20% or more, preferably 25% or more, more preferably 30% or more, and further preferably 31% or more. The upper limit is not particularly limited as long as it is 100% or less.

The water solubility can be measured by the following method. An aqueous solution was prepared by mixing 18g of water with 2g of the sample (component (B)), 6g of the obtained aqueous solution was collected in a centrifuge tube, centrifuged, and 4.5g of the supernatant was separated and freeze-dried. The weight X of the sample dissolved in water was calculated from the weight W after freeze-drying (including the weight of the centrifuge tube), and the water solubility (%) was calculated by substituting the weight X into the following equation. The conditions for the operations such as mixing of water and a sample, centrifugal separation, freeze drying, and the like may be the same as in the examples.

(formula) Water solubility (%). X/2X 100

(number of groups represented by the formula (1) (number of functional groups))

The compound having at least 1 group represented by the formula (1) preferably has 2 or more of the groups. The upper limit is not particularly limited, but is preferably 10 or less, and more preferably 7 or less.

(mother skeleton)

The structure other than the group of the compound having at least 1 group represented by the formula (1) is not particularly limited. For example, the presence or absence of a saturated bond and an unsaturated bond, the presence or absence of a linear, branched, or cyclic structure is not limited, and an atom other than carbon (for example, oxygen atom) may be contained. The parent skeleton is also not particularly limited, and examples thereof include (poly) glycerin (e.g., glycerin, diglycerin, and polyglycerin), trimethylolpropane, (poly) alkylene glycol (e.g., ethylene glycol and polyethylene glycol), and phenol (poly) ethylene oxide.

(epoxy equivalent)

The epoxy equivalent of the compound having at least 1 group represented by formula (1) is usually 100 or more, preferably 110 or more. The upper limit is usually 500 or less, preferably 300 or less, and more preferably 200 or less.

(examples of Compounds)

Examples of the compound having at least 1 group represented by the formula (1) include (poly) glycerol polyglycidyl ethers (e.g., diglycerol polyglycidyl ether, triglycerol polyglycidyl ether, polyglycerol polyglycidyl ether), (poly) alkylene glycol diglycidyl ethers (e.g.,(poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether), (poly) ethylene glycol glycidyl ether, trimethylolpropane polyglycidyl ether, phenol (EO)₅Glycidyl ether, p-tert-butylphenyl glycidyl ether. Among them, preferred are glycerol polyglycidyl ether, diglycerol polyglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, phenol (EO)₅A glycidyl ether.

The component (B) may be 1 kind of compound having at least 1 group represented by the formula (1) alone, or may be a combination of 2 or more kinds of the above-mentioned compounds. Component (B) preferably contains at least 1 compound having 2 or more groups represented by formula (1). Further, the component (B) preferably contains at least 1 compound having at least 1 group represented by the formula (1) and having a water solubility of 70% or more.

(content of component (B))

In the composition of the present invention, the content of the component (B) is preferably 0.1 part by weight or more, more preferably 1 part by weight or more, and further preferably 3 parts by weight or more, relative to 100 parts by weight of the content of the component (a). Thereby, stability to chlorinated polyolefin can be well expressed. The upper limit is preferably 15 parts by weight or less, more preferably 10 parts by weight or less, and further preferably 8 parts by weight or less. This can exhibit good adhesion to the polyolefin.

[ component (C): olefin oxide represented by the general formulae (2) and (3)

The component (C) is at least one of an alpha-olefin oxide and an alpha, omega-olefin oxide. They are each represented by the general formula (2) and the general formula (3).

[ solution 5]

The component (C) may be 1 kind alone or a combination of 2 or more kinds selected from the group consisting of the α -olefin oxide represented by the general formula (2) and the α, ω -olefin oxide represented by the general formula (3). That is, 1 kind of the α -olefin oxide represented by the general formula (2); 1 kind of alpha, omega-olefin oxide shown in a general formula (3); a combination of 2 or more kinds of α -olefin oxides represented by the general formula (2); a combination of 2 or more α, ω -olefin oxides represented by the general formula (3); and any one of combinations of 1 or more kinds of α -olefin oxides represented by the general formula (2) and 1 or more kinds of α, ω -olefin oxides represented by the general formula (3).

(Compound represented by the general formula (2))

M in the general formula (2) is an integer of 3 or more, preferably 7 or more. This can exhibit appropriate polarity, and the chlorinated polyolefin can be well compatible with the chlorinated polyolefin, and therefore can exhibit good performance as a stabilizer. In addition, the volatility is sufficiently low, and problems such as deterioration of the appearance of the coating film due to evaporation at the time of drying the coating film, and volatilization in a reduced pressure step at the time of concentration or solidification can be suppressed. m is an integer of 26 or less, preferably 15 or less. Accordingly, the amount of oxygen per unit weight of ethylene oxide (oxirane) is appropriate, and excellent stability can be obtained as the chlorinated polyolefin resin composition in an amount added without impairing the physical properties. m is an integer of 3 to 26, preferably 7 to 15. When m is an integer of 7 to 15, the loss due to volatilization in the pressure reduction step and the amount of oxygen per unit weight of ethylene oxide can be well balanced in the production of the chlorinated polyolefin resin composition, and therefore, even if the amount of the compound represented by the general formula (2) is small, the compound can effectively exert its effect as a stabilizer. When the chlorinated polyolefin resin composition of the present invention is used in an ink for food packaging materials or the like, the mutagenicity may be required to be negative in a typical mutagenicity test Ames test in view of safety. In this case, since the compound represented by the general formula (2) and having m of 7 to 15 is negative in the Ames test, the resin composition of the present invention is preferably used as the component (C) in the above-mentioned applications.

In the present invention, when the component (a) contains at least an acid-modified chlorinated polyolefin, the component (C) preferably contains at least an α -olefin oxide represented by the general formula (2), and more preferably an α -olefin oxide represented by the general formula (2). The α -olefin oxide represented by the general formula (2) has 1 epoxy group in 1 molecule. Therefore, when the chlorinated polyolefin resin composition of the present invention comprises the acid-modified chlorinated polyolefin and the α -olefin oxide represented by the general formula (2), the crosslinking reaction with the acid anhydride or the organic acid in the composition can be effectively suppressed. In this case, in the case where the chlorinated polyolefin resin composition further contains a solvent, the solution stability of the composition can be favorably maintained.

(Compound represented by the general formula (3))

N in the general formula (3) is an integer of 2 or more, preferably an integer of 10 or more. Thereby, the same advantages as those in the case where m of the general formula (2) is 3 or more can be obtained. n is an integer of 28 or less, preferably 20 or less. Thereby, the same advantages as those in the case where m of the general formula (2) is 26 or less can be obtained. n is an integer of 2 to 28, preferably 10 to 20. When n is an integer of 10 to 20, the loss due to volatilization in the pressure reduction step and the amount of ethylene oxide per unit weight can be well balanced in the production of the chlorinated polyolefin resin composition, and therefore, the chlorinated polyolefin resin composition can effectively exhibit its efficacy as a stabilizer with a smaller amount of addition.

(content of component (C))

In the composition of the present invention, the content of the component (C) is preferably 0.1 to 15 parts by weight relative to 100 parts by weight of the content of the component (a). When the amount is 0.1 part by weight or more, the stability to chlorinated polyolefin can be favorably exhibited. When the amount is 15 parts by weight or less, the adhesion to polyolefin can be favorably exhibited.

[ content ratio of component (B) to component (C) ]

In the composition of the present invention, the content of the component (C) is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, and further preferably 40 parts by weight or more, relative to 100 parts by weight of the content of the component (B). The upper limit is preferably 1000 parts by weight or less, more preferably 800 parts by weight or less, and further preferably 200 parts by weight or less. Therefore, the amount of the organic solvent is preferably 10 to 1000 parts by weight, more preferably 20 to 800 parts by weight, and still more preferably 40 to 200 parts by weight.

[ component (D): other stabilizers ]

The chlorinated polyolefin resin composition of the present invention may contain a component (D): stabilizers other than the components (B) and (C). Examples of the stabilizer other than the components (B) and (C) include epoxidized soybean oil, epoxy compounds having a glycidyl ether structure (e.g., phenyl glycidyl ether), metallic soaps such as calcium stearate and lead stearate, inorganic acid salts such as lead oxide and tribasic lead sulfate, and organic metal compounds such as dibutyltin dilaurate and dibutyltin maleate. The component (D) may be 1 stabilizer alone or a combination of 2 or more stabilizers.

[ Total content of stabilizer ]

In the chlorinated polyolefin resin composition of the present invention, the total content of the components (B), (C) and (D) is preferably 0.1 part by weight or more with respect to 100 parts by weight of the content of the component (a). This can exhibit a good stabilization effect on chlorinated polyolefin. The upper limit is preferably 15 parts by weight or less, more preferably 12 parts by weight or less. This can exhibit good adhesion to a substrate such as polyolefin. Therefore, the total content of the components (B), (C) and (D) is preferably 0.1 to 15 parts by weight, more preferably 0.1 to 12 parts by weight, based on 100 parts by weight of the component (A).

[ optional ingredients ]

(Components (E) to (G): basic substance, emulsifier, aqueous medium)

The chlorinated polyolefin resin composition may further comprise an ingredient selected from the group consisting of ingredient (E): basic substance, component (F): emulsifier, and ingredient (G): at least 1 in an aqueous medium. By containing them, the chlorinated polyolefin resin composition can form an aqueous dispersion. In the aqueous dispersion, a resin component composed of an acid-modified chlorinated polyolefin resin is usually emulsified and/or dispersed in an aqueous medium.

The chlorinated polyolefin resin composition can further improve the dispersibility in the component (G) by including the component (E) to neutralize the acid component of the acid-modified chlorinated polyolefin as the component (a). Examples of the basic substance include sodium hydroxide, potassium hydroxide, ammonia, methylamine, propylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, morpholine, dimethylethanolamine, and the like, and preferable examples thereof include ammonia, triethylamine, 2-amino-2-methyl-1-propanol, morpholine, dimethylethanolamine, and the like. The component (E) may be 1 kind of basic substance or a combination of 2 or more kinds of basic substances.

The content of the component (E) may be adjusted to an arbitrary amount depending on the amount of the acidic component in the chlorinated polyolefin resin composition. The amount is such that the pH of the chlorinated polyolefin resin composition is usually 5 or more, preferably 6 or more. Thereby, the dispersion can be sufficiently neutralized and stable dispersibility can be maintained. Therefore, deterioration of storage stability due to reasons that the acid-modified chlorinated polyolefin is not dispersed in other components or is easily precipitated or separated over time even when dispersed can be prevented. On the other hand, the upper limit is usually an amount up to pH10 or less. This makes it possible to maintain good compatibility with other components and operational safety. Therefore, the content of the component (E) is such an amount that the pH of the chlorinated polyolefin resin composition becomes preferably 5 or more, more preferably 6 to 10.

The chlorinated polyolefin resin composition can be stabilized in dispersibility of the acid-modified chlorinated polyolefin in an aqueous medium by containing the component (F). Examples of the emulsifier include surfactants. The surfactant is not particularly limited, and examples thereof include nonionic surfactants and anionic surfactants, and nonionic surfactants are preferable. This makes it possible to obtain a chlorinated polyolefin resin composition (aqueous dispersion) having more excellent stability such as moisture resistance.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene derivatives, polyoxyethylene fatty acid esters, polyoxyethylene polyol 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. Preferred are polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene alkylamines.

Examples of the anionic surfactant include alkyl sulfate, polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, α -olefin sulfonate, methyltaurate, sulfosuccinate, ether sulfonate, ether carboxylate, fatty acid salt, naphthalenesulfonic acid formalin condensate, alkylamine salt, quaternary ammonium salt, alkylbetaine, alkylamine oxide, and the like. Preferred are polyoxyethylene alkyl ether sulfate and sulfosuccinate.

The component (F) may be 1 kind of emulsifier, or a combination of 2 or more kinds of emulsifiers.

The amount of the component (F) added is generally 35% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less, further preferably 5% by weight or less, and further more preferably substantially no, relative to 100% by weight of the component (a). Thus, the amount of the emulsifier can be set to an appropriate amount, and the lowering of the adhesiveness and the moisture resistance due to the excessive amount of the emulsifier can be prevented. In addition, an excessive amount of the emulsifier causes problems such as a plasticizing effect and a bleeding phenomenon when the chlorinated polyolefin resin composition is formed into a dry film, and causes blocking, but these problems can be prevented by setting the amount to the above-mentioned amount. The amount of emulsifier added should be as small as possible.

The chlorinated polyolefin resin composition can contain the component (G) to disperse or emulsify the resin component in the composition. The aqueous medium may be selected from water and hydrophilic substances. The hydrophilic substance may be any substance that exhibits hydrophilicity, and is preferably a polar substance insoluble in the acid-modified chlorinated polyolefin, and examples thereof include alcohol-based, ketone-based, and ester-based hydrophilic substances. Among them, alcohol-based or ketone-based hydrophilic substances are preferable, and methanol, ethanol, isopropanol, and acetone are more preferable. The component (G) may be used in combination with 1 type of aqueous medium or 2 or more types of aqueous media.

(component (H): crosslinking agent)

When the chlorinated polyolefin resin composition contains at least 1 of the components (E) to (G), the chlorinated polyolefin resin composition may further contain a component (H): a crosslinking agent. The crosslinking agent may be any compound that can react with a group such as a hydroxyl group, a carboxyl group, or an amino group present in the acid-modified chlorinated polyolefin and other components such as the components (E) and (F) to form a crosslinked structure, and may be either a water-soluble crosslinking agent or an aqueous dispersion of the crosslinking agent (a crosslinking agent in a state of being dispersed in water by any method). Examples of the crosslinking agent include a blocked isocyanate compound, an aliphatic or aromatic epoxy compound, an amine compound, and an amino resin. The component (H) may be 1 kind of crosslinking agent alone or a combination of 2 or more kinds of crosslinking agents. The method of adding the crosslinking agent is not particularly limited, and the timing of adding the crosslinking agent may be either during the step of hydrating or after hydrating.

(component (I): organic solvent)

The chlorinated polyolefin resin composition may further comprise the component (I): an organic solvent. Thereby, the chlorinated polyolefin resin composition can form a resin solution.

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 and methyl butyl ketone, alicyclic solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane, and aliphatic solvents such as nonane and decane. The component (I) may be 1 organic solvent alone or a combination of 2 or more organic solvents. The content of the component (I) is preferably 10 to 95 parts by weight, more preferably 30 to 90 parts by weight, based on 100 parts by weight of the chlorinated polyolefin.

(component (J): Diluent)

The chlorinated polyolefin resin composition may further contain a component (J): a diluent. This improves the storage stability. Examples of the diluent include alcohols and propylene-based glycol ethers (propylene-containing glycol ethers). Examples of the alcohol include methanol, ethanol, propanol, isopropanol, and butanol. Examples of the propylene glycol ether include propylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol-t-butyl ether. Component (J) may be 1 diluent alone or a combination of 2 or more diluents. The content of the component (J) is usually 1 to 20% by weight based on the content of the component (I).

(other optional ingredients)

The chlorinated polyolefin resin composition may further contain other optional components than the components (a) to (J) depending on the use, purpose, and the like. Examples of optional components in the case where the chlorinated polyolefin resin composition is an aqueous dispersion include alkyd resin, aqueous acrylic resin, aqueous urethane resin, modified polyolefin resin other than the component (a), lower alcohols, lower ketones, lower esters, preservatives, leveling agents, antioxidants, light stabilizers, ultraviolet absorbers, dyes, pigments, metal salts, and acids.

[ form of chlorinated polyolefin resin composition and production method ]

The chlorinated polyolefin resin composition of the present invention can be used in various forms (formulation types). Examples of the form include a solution (e.g., a resin solution and an aqueous dispersion) and a solid substance, and can be appropriately selected according to the purpose and the like. The chlorinated polyolefin resin composition of the present invention is preferably in the form of a solution, more preferably an aqueous dispersion. The method for producing the chlorinated polyolefin resin composition may include at least a step of adding the component (B) to the component (a), and may be appropriately selected depending on the form of the composition.

(aqueous dispersion)

The method for producing the aqueous dispersion is not particularly limited. For example, the components (a) and (B) and other components used as needed may be added to the reaction system and dispersed. The order of addition of the respective raw materials is not limited.

Examples of the method for producing the aqueous dispersion include a method of adding each component to the reaction system at once or successively to disperse or emulsify the components, and specifically include a method including the following steps:

step (1): a step (resin solidification step) of molding the component (a) (preferably, the acid-modified chlorinated polyolefin) to obtain a solid (for example, pellets); and

step (2): a step of adding at least the component (B) to a solid substance to emulsify the solid substance (emulsification step).

In the step (1), the molding can be performed by using an appropriate molding apparatus. In the step (1), before the component (A) is supplied to the molding apparatus, it is generally preferable to remove (concentrate) at least a part of the chlorinated solvent remaining in the component (A), and it is preferable to adjust the concentration of the solid component to be preferably 30% or more, more preferably 35% or more, and still more preferably 40% or more.

In the step (2), components (E) to (G) are usually added in addition to the component (B). At least 1 selected from the components (D), (H) and optional components may be further added as necessary. The addition may be made at once or successively. The step (2) may be carried out in the presence of an amphiphilic solvent. Examples of the amphiphilic solvent include ethylene glycol monobutyl ether (butyl cellosolve) and propylene glycol monopropyl ether. The step (2) may be performed in the presence of a melting aid such as toluene.

The emulsification method is not particularly limited, and examples thereof include forced emulsification, phase inversion emulsification, phase D emulsification, and gel emulsification. The emulsification is usually carried out by stirring. The stirring method is not particularly limited, and examples thereof include single stirring using a device such as a stirring blade, a disperser, and a homogenizer, and composite stirring using 2 or more of the above devices in combination. As other examples of the stirring device, a sand mill and a multi-shaft extruder may be cited. The temperature conditions during stirring are not particularly limited, and stirring at a high temperature is preferred, and cooling is performed after completion. The internal pressure of the reaction system may be controlled (preferably 0.2MPa or more) and maintained (for example, for 1 hour) until cooling after completion of the stirring. Thereby, the melting aid can be efficiently and almost completely removed from the obtained aqueous dispersion.

In the aqueous dispersion, generally, the resin component is emulsified and/or dispersed in an aqueous medium. The average particle diameter of the resin component is preferably 300nm or less, more preferably 200nm or less. This improves the storage stability of the aqueous dispersion and the compatibility with other resins. In addition, the aqueous dispersion can be inhibited from lowering in stability such as adhesion to a substrate, solvent resistance (alcohol-gasoline resistance, etc.), moisture resistance, blocking resistance, etc. The lower limit of the particle size is not particularly limited. The lower limit of the average particle diameter is preferably not too small and is generally 30nm or more. This can suppress an increase in the amount of the surfactant to be added, and can suppress a decrease in the stability of the adhesive property to the substrate, moisture resistance, solvent resistance, and the like. The average particle diameter in the present invention can be measured by particle size distribution measurement using a light diffusion method, and the numerical values in the examples described later are the numerical values measured by this method.

Examples of the method for adjusting the average particle diameter include adjustment by the amount of a surfactant added and adjustment by the stirring force when the resin is emulsified in an aqueous medium. In order to adjust the average particle diameter of the resin component to 300nm or less, it is preferable to use a method of adding water to an organic solvent or the like to cause phase inversion, that is, a phase inversion emulsification method, a stirring method with high shear force, that is, a composite stirring method, or a method using a device such as a sand mill or a multi-shaft extruder, in the preparation of an aqueous dispersion.

(resin solution)

The method for producing the chlorinated polyolefin resin composition of the present invention in the case where the chlorinated polyolefin resin composition further contains an organic solvent includes, for example, a method of adding the component (B) to the component (A) and then replacing the chlorinated solvent remaining in the reaction system with the organic solvent, a method of adding the component (B) to the component (A), then removing the chlorinated solvent remaining in the system, and then adding the essential components such as the component (I). Before the component (B) is added to the component (A), the chlorinated solvent is preferably concentrated in advance. Examples of the method for removing the chlorinated solvent include distillation and drying under reduced pressure, and in this case, a drum dryer, an extruder with a vent, and the like can be used.

(solid substance)

The chlorinated polyolefin resin composition of the present invention may be a solid (e.g., pellets). The solid means not containing a solvent (liquid component) such as an organic solvent, an aqueous medium or the like. Examples of the method for producing a solid include a method in which the component (B) is added to the component (A) and then the chlorinated solvent is removed, and a method in which the chlorinated polyolefin resin composition as a resin solution is desolventized.

After removing the chlorinated solvent, the product may be used as it is as the composition of the present invention, or may be formed into a desired shape as needed. Examples of the molding apparatus include an extruder, a water-cooled pelletizer, and the like.

[ use ]

The chlorinated polyolefin resin composition of the present invention can be used in various applications such as paints, inks, primers, adhesives, and heat-sealing agents. Among them, the compounds are preferably used as a coating material for polyolefin substrates, an ink for polyolefin substrates, an adhesive for polyolefin substrates, a primer for polyolefin substrates, and a heat sealing agent for polyolefin substrates.

The chlorinated polyolefin resin composition of the present invention may contain additives such as antioxidants, light stabilizers, ultraviolet absorbers, pigments, dyes, and inorganic fillers, if necessary.

The chlorinated polyolefin resin composition of the present invention can be used in combination with resins such as alkyd resins, acrylic resins, polyacrylate polyols, polyester resins, polyester polyols, polyurethane resins, and other chlorinated polyolefins, if necessary.

Examples

Example 1

(1) Maleation of

100 parts by weight of a crystalline polypropylene resin having a melt index of 60g/10min (measured in accordance with JIS K7210-1 (2014)) and a melting point of 146 ℃,2 parts by weight of maleic anhydride, and 1.5 parts by weight of a di-t-butyl peroxide as an initiator were thoroughly mixed, and then fed into a twin-screw extruder having an L/D of 34 and a φ of 40mm so that a residence time of 10 minutes was set. The reaction was carried out while setting the reaction zone (barrel 3 to barrel 5) to 200 ℃ for the barrel temperature, and the maleic anhydride-modified propylene copolymer was obtained by degassing in barrel 7 and removing unreacted maleic anhydride. The grafting amount of maleic anhydride was 1.5% by weight. In each of examples and comparative examples, the graft amount of maleic anhydride was measured by the alkali titration method.

(2) Chlorination of

5kg of the copolymer obtained in (1) was charged into a 50L reactor equipped with a glass liner, 33L of chloroform was added, and after sufficiently dissolving the copolymer at 97 ℃ under a pressure of 0.2MPa, 5g of 2, 2-azobisisobutyronitrile as an initiator was added, and the internal pressure of the reactor was controlled to 0.2MPa, and gaseous chlorine was blown into the reactor to conduct chlorination reaction, thereby obtaining a maleic anhydride-modified chlorinated propylene copolymer solution having a degree of chlorination of 28% (sufficient solids: component (A): 13%.

(3) Solidification of

The copolymer solution obtained in (2) was concentrated to about 40% in solid content by an evaporator, and then the component (C): 4.5 parts by weight of a stabilizer (1, 2-epoxyhexadecane, hereinafter referred to as "α 16"). Chloroform was removed by a twin-screw extruder with a vent hole provided with a vent hole for distilling off the reaction solvent under reduced pressure, and the maleic anhydride-modified chlorinated propylene-based copolymer was extruded into a strand shape and pelletized by a pelletizer to obtain chlorinated polyolefin 1 (maleic anhydride-modified chlorinated propylene-based copolymer, weight average molecular weight 40,000).

(4) Emulsification

Into a 3L-sized four-necked flask equipped with a stirrer, a cooling tube and a dropping funnel were charged 200g of the obtained granular chlorinated resin, 4g of pure water and the component (F): 20g of surfactant (polyoxyethylene oleyl ether), component (B): 10g (5 parts by weight per 100 parts by weight of the component (A)) of a stabilizer Denacol EX-313 (glycerol polyglycidyl ether, epoxy equivalent 141g/eq, water solubility 99%, Nagase ChemteX Co., Ltd.), 60g of methylcyclohexane and 60g of n-butylcellosolve, and the mixture was kneaded at 85 ℃ for 1 hour. Then, 18g of morpholine was added thereto, and the mixture was held for 1 hour, and then 820g of warm water at 90 ℃ was added thereto over about 2 hours. Then, the resulting mixture was subjected to a reduced pressure treatment to remove methylcyclohexane and n-butyl cellosolve, and then cooled to room temperature while being stirred, thereby obtaining an aqueous dispersion composition of a maleic anhydride-modified chlorinated propylene copolymer.

Examples 2 to 7 and comparative examples 1 to 2

The component (B) added in the emulsification step was changed to Denacol EX-321 (trimethylolpropane polyglycidyl ether), EX-421 (diglycerol polyglycidyl ether), EX-810 (ethylene glycol diglycidyl ether), EX-830 (polyethylene glycol diglycidyl ether), and EX-145 (phenol (EO)) as shown in Table 1₅Glycidyl ether), EX-314 (glycerol polyglycidyl ether), EX-211 (neopentyl glycol diglycidyl ether), and EX-252 (hydrogenated bisphenol A diglycidyl ether) (all manufactured by Nagase ChemteX, the respective water solubilities and epoxy equivalent are shown in Table 2), and aqueous acid-modified polypropylene copolymer resin compositions of examples 2 to 7 and comparative examples 1 to 2 were obtained in the same manner as in example 1.

Example 8

The same procedures as in example 1 were repeated except for changing the amount of the component (F) added in the emulsification step to 40g of a surfactant (polyoxyethylene laurylamine), to obtain an aqueous acid-modified polypropylene copolymer resin composition of example 8.

< Water solubility >

18g of water and 2g of component (B) were added to a glass tube with a sealed plug, mixed with shaking sufficiently for 1 minute, and then allowed to stand overnight to obtain an aqueous solution. 6g of the resulting aqueous solution was collected in a centrifuge tube and centrifuged at 10000rpm for 3 minutes. After centrifugation, 4.5g of the supernatant was collected and freeze-dried (a freeze-dryer (FD-1) manufactured by tokyo physical and chemical instruments, 12 hours), and the weight W of the residue after freeze-drying (including the weight of the centrifuge tube) was measured. The weight X of the component (B) dissolved in water was calculated by subtracting the weight of the centrifugal tube from W, and the weight was substituted into the following formula to obtain the water solubility.

(formula) Water solubility (%) (X/2). times.100

< average particle diameter >

The aqueous acid-modified polypropylene copolymer resin compositions obtained in examples and comparative examples were measured for the initial average particle diameter (μm) immediately after emulsification, the average particle diameter (μm) after 1 month of storage (25 ℃ C., condition), and the average particle diameter (μm) after 2 months of storage (25 ℃ C., condition) by a dynamic light scattering method using "Zetasizer", manufactured by Toyama DKK corporation.

< storage stability >

The average particle size at the initial stage and the average particle size after 1 month were compared, and the storage stability was evaluated by the following criteria.

(evaluation criteria)

A: the fluctuation ratio of the average particle diameter is 10% or less.

B: the fluctuation ratio of the average particle diameter is more than 10% and less than 20%.

C: the fluctuation ratio of the average particle diameter is more than 20%.

< adhesion >

The aqueous acid-modified polypropylene copolymer resin compositions obtained in examples and comparative examples were adjusted to a solid content of 30 wt%, coated on a polypropylene substrate, dried at 80 ℃ for 5 minutes, then coated with a two-pack urethane coating, and dried at 80 ℃ for 30 minutes to prepare test pieces (coated sheets), respectively.

Linear cuts reaching the substrate were applied to the coating film of the coating plate at 1mm intervals in a longitudinal and transverse direction, 100 intervals (checkerboard) were prepared, and the cellophane adhesive tape was adhered thereto and peeled off in a 180 ° direction. The operation of adhering and peeling the cellophane adhesive tape was performed 10 times at the same 100 intervals, and the adhesiveness (adhesiveness) was evaluated by the following criteria. When the interval between the coating films to be peeled is 50 or less, there is no problem in practical use.

(evaluation criteria)

A: no peeling of the coating film was observed.

B: the intervals between the coating films to be peeled are 50 or less.

C: the number of coating films peeled off was more than 50.

[ Table 1]

。

As is clear from table 1, in the examples using the components (a) and (B), an aqueous dispersion having an appropriate average particle diameter, good storage stability, and good adhesiveness can be obtained, as compared with the comparative examples using a compound having a water solubility of less than 20% instead of the component (B). These results show that the chlorinated polyolefin resin composition of the present invention can form a good coating film because it can exhibit good adhesion to a substrate such as a polyolefin resin substrate, and can exhibit good emulsifiability and stability.

Claims

1. A chlorinated polyolefin resin composition comprising:

component (A): chlorinated polyolefin, and

[ solution 1]

，

The component (B) contains at least the compound having a water solubility of 20% or more.

2. The chlorinated polyolefin resin composition according to claim 1, further comprising an ingredient (C): an alpha-olefin oxide represented by the general formula (2) and/or an alpha, omega-olefin oxide represented by the general formula (3),

[ solution 2]

In the formula, m is an integer of 3-26;

[ solution 3]

Wherein n is an integer of 2 to 28.

3. The chlorinated polyolefin resin composition according to claim 1 or 2, wherein component (B) comprises at least 1 compound having 2 or more groups represented by formula (1).

4. The chlorinated polyolefin resin composition according to any one of claims 1 to 3, wherein the content of the component (B) is 0.1 to 15 parts by weight relative to 100 parts by weight of the content of the component (A).

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

6. The chlorinated polyolefin resin composition according to any one of claims 1 to 5, further comprising an ingredient selected from the group consisting of ingredient (E): basic substance, component (F): an emulsifier, and component (G): at least 1 of the aqueous media.

7. A coating, a primer, an ink, an adhesive or a heat sealer, comprising the chlorinated polyolefin resin composition according to any one of claims 1 to 6.