JP2008214414A - Modified polyolefin-dispersed resin composition and primer containing the same - Google Patents

Abstract

Disclosed is a modified polyolefin-dispersed resin composition that exhibits excellent adhesion and solvent resistance to non-polar substrates even under drying conditions at a low temperature of 100 ° C. or less from outside air temperature.
(A) A raw material polyolefin resin having a melting point of 60 ° C. to 165 ° C. measured by a differential scanning calorimeter is obtained from (i) chlorine, (ii) an unsaturated carboxylic acid, its anhydride, and an unsaturated carboxylic acid derivative. One or more compounds selected from the group of unsaturated carboxylic acid compounds, and (iii) a modified polyolefin resin modified with one or more polarity-imparting agents selected from radical polymerizable monomers, (b) ammonia, (c) A dispersion resin composition containing a surfactant and (d) water, a primer, an ink and a paint containing the composition.
[Selection figure] None

Description

  The present invention relates to a modified polyolefin-dispersed resin composition having good adhesion to a nonpolar resin substrate such as polypropylene at low temperature and good gasohol resistance. The dispersed resin composition of the present invention is suitable for primer application, ink application, and adhesive application during natural drying to low-temperature baking.

  Polyolefin resins such as polypropylene and polyethylene are general-purpose thermoplastic resins that are inexpensive and have many excellent properties such as moldability, chemical resistance, weather resistance, water resistance, and electrical properties. It is used in a wide range of fields as molded products. However, unlike polyolefin-based substrates such as polyurethane resins, polyamide resins, acrylic resins, polyester resins, metals, etc., these substrates made of polyolefin resins (hereinafter referred to as polyolefin substrates) have low polarity and are crystalline. Therefore, it is known as a hard-to-adhere base material, and has a drawback that it is difficult to bond and paint between the same kind and different kinds of base materials.

  In contrast, acid-modified propylene-based random copolymers and chlorinated propylene-based random copolymers modified with unsaturated carboxylic acids and / or their anhydrides are proposed as paint pretreatment agents or adhesives. It is provided as a hot melt system and a solvent system. In recent years, solvent systems have shifted to water systems from the viewpoint of environmental problems, and water-based resin compositions that adhere to polyolefin substrates have been disclosed (Patent Documents 1 to 3).

  In addition, for water-based resin compositions, low temperature drying suitability and high solids (high solid content concentration) are provided to prevent thermal denaturation of the substrate and to reduce energy and time during the drying and baking process. Is desired.

  On the other hand, in the production of water-based resin dispersions, aqueous additives such as emulsifiers and surfactants are present in the produced dispersion, so that they remain in the dried coating film, resulting in adhesion, water resistance, etc. Aqueous dispersions that do not contain an aqueous additive have been developed (Patent Documents 4 to 5), but storage stability and adhesiveness are reduced unless emulsifiers and surfactants are contained. In addition, with respect to solvent resistance, sufficient performance has not been obtained.

Japanese Patent Laid-Open No. 6-256592 Japanese Patent Laid-Open No. 2002-80686 JP-A-6-145286 JP 2003-327761 A Japanese Patent No. 3759160

  An object of the present invention is to provide a modified polyolefin-dispersed resin composition that exhibits excellent adhesion and solvent resistance to a nonpolar substrate even under drying conditions at a low temperature of 100 ° C. or lower from the outside temperature.

  As a result of diligent research in view of the above problems, the present inventors used a modified polyolefin resin having a specific melting point, and combined this with ammonia and a surfactant when producing an aqueous dispersion of the modified polyolefin resin. In addition to exhibiting the effect of improving the adhesion and dispersion stability due to the use of a surfactant, it also has excellent adhesion, solvent resistance, and moisture resistance. As a result, the present invention has been found.

That is, the present invention provides the following.
(1) A dispersion resin composition comprising the following components (a) to (d):
(A) An unsaturated carboxylic acid comprising a raw material polyolefin resin having a melting point of 60 ° C. to 165 ° C. measured by a differential scanning calorimeter, comprising (i) chlorine, (ii) an unsaturated carboxylic acid, its anhydride and an unsaturated carboxylic acid derivative One or more compounds selected from the group of acid compounds, and (iii) a modified polyolefin resin modified with one or more polarity-imparting agents selected from radically polymerizable monomers (b) ammonia (c) surfactants (d) Water (2) The dispersion resin composition as described in (1) whose melting | fusing point by the differential scanning calorimeter of the said (a) modified polyolefin resin is 20 to 100 degreeC.
(3) The polarity imparting agent is (ii) one or more compounds selected from the group of unsaturated carboxylic acid compounds consisting of unsaturated carboxylic acids, anhydrides thereof and unsaturated carboxylic acid derivatives, and (iii) radical polymerizability. The dispersion resin composition according to (1) or (2), which is a monomer.
(4) One or more unsaturated carboxylic acid anhydrides selected from itaconic anhydride and maleic anhydride, methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl The dispersion resin composition according to any one of (1) to (3), which is a combination with one or more (meth) acrylates selected from (meth) acrylates.
(5) A primer, an ink, and an adhesive containing the dispersion resin composition according to any one of (1) to (4).
(6) A primer that contains the dispersion resin composition according to any one of (1) to (4) and that is used under a condition where a drying temperature is 100 ° C. or less.

  The dispersed resin composition of the present invention has excellent adhesion, solvent resistance, and moisture resistance to nonpolar substrates even under drying conditions at a low temperature of 100 ° C. or less from the outside temperature. Moreover, the dispersion resin composition of the present invention has excellent blister resistance. Furthermore, the dispersed resin composition of the present invention is therefore suitable for primer, ink, or adhesive applications that are dried under a drying condition at a low temperature of about 100 ° C. or less from a room temperature of about the outside temperature. is there.

Hereinafter, the present invention will be described in detail.
The dispersion resin composition of the present invention comprises (a) a raw material polyolefin resin having a melting point of 60 ° C. to 165 ° C. as measured by a differential scanning calorimeter, wherein (i) chlorine, (ii) an unsaturated carboxylic acid, its anhydride and From one or more compounds selected from the group of unsaturated carboxylic acid compounds consisting of saturated carboxylic acid derivatives (hereinafter sometimes abbreviated as (ii) unsaturated carboxylic acid compounds), and (iii) from radically polymerizable monomers It contains a polyolefin resin modified with one or more selected polar imparting agents, (b) ammonia, (c) a surfactant, and (d) water. The dispersion resin composition of the present invention exhibits a stable dispersion state by containing these components, and the coating film after drying at low temperature has good physical properties.

  In the present invention, (a) a modified polyolefin resin is used as the first component of the dispersion resin composition. (A) The polyolefin resin used as a raw material for the modified polyolefin resin is described in detail below. Hereinafter, the (a) polyolefin resin used as a raw material for the modified polyolefin resin may be referred to as “raw polyolefin resin” or simply “polyolefin resin”.

  Examples of the raw material polyolefin resin of the present invention include those obtained by copolymerizing ethylene or α-olefin using a Ziegler-Natta catalyst or a metallocene catalyst as a polymerization catalyst. Specific examples include resins selected from polypropylene, ethylene-propylene copolymers, propylene-butene copolymers, ethylene-propylene-butene copolymers, and the like. These resins may be used alone, or a plurality of resins may be mixed and used.

  Although the component composition of the raw material polyolefin resin used by this invention is not specifically limited, A thing whose propylene component is 60 mol% or more is preferable. When using less than 60 mol%, the adhesiveness to the propylene substrate may be reduced.

  Examples of the raw material polyolefin resin used in the present invention include polyolefin resins having a melting point (Tm) measured by a differential scanning calorimeter (DSC) of 60 to 165 ° C, preferably 60 to 125 ° C. If the melting point is less than 60 ° C, the solvent resistance of the dispersed resin composition may be lowered, and if it exceeds 165 ° C, the adhesion to the substrate may be lowered. The measurement of Tm by DSC in the present invention can be performed, for example, under the following conditions. Using a DSC measuring apparatus (Seiko Denshi Kogyo Co., Ltd.), about 10 mg of sample was melted at 200 ° C. for 5 minutes, then cooled to −60 ° C. at a rate of 10 ° C./min. The melting peak temperature when melted by raising the temperature to 200 ° C. is measured, and the temperature is evaluated as Tm. In the examples described later, Tm is measured under the conditions described above.

  The molecular weight of the raw material polyolefin resin used in the present invention is not particularly limited. However, the weight average molecular weight of the modified polyolefin resin modified with the polarity-imparting agent described later is preferably 15,000 to 200,000, more preferably 50,000 to 150,000. For this reason, when the weight average molecular weight of the raw material polyolefin resin is larger than 200,000, the resulting modified polyolefin resin is degraded in the presence of heat and radicals so that the weight average molecular weight of the modified polyolefin resin is within the above range. Is preferably adjusted to an appropriate range, for example, 200,000 or less. In addition, the weight average molecular weight and molecular weight distribution (Mw / Mn) in this invention containing an Example are the values measured by the gel permeation chromatography (standard material: polystyrene).

  Examples of the raw material polyolefin resin used in the present invention include polypropylene, ethylene-propylene copolymer, propylene-butene copolymer, and ethylene-propylene-butene copolymer produced using a metallocene catalyst as a polymerization catalyst among the above resins ( Hereinafter, at least one selected from the group consisting of a propylene-based random copolymer may be preferable.

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

  A polyolefin resin synthesized using a metallocene catalyst has characteristics such as a narrow molecular weight distribution, excellent random copolymerizability, a narrow composition distribution, and a wide range of comonomer that can be copolymerized, and is preferable as a raw material polyolefin resin used in the present invention. .

  The (a) modified polyolefin resin of the present invention is obtained by modifying the above-mentioned raw material polyolefin resin. In the modification, (i) chlorine, (ii) unsaturated carboxylic acid compound and ( iii) One or more selected from radically polymerizable monomers are used. You may use these polarity-imparting agents in combination of 2 types or all 3 types.

When using two or more kinds of the above-mentioned polarity imparting agents, (i) a combination of chlorine and (ii) an unsaturated carboxylic acid compound; (i) chlorine, (ii) an unsaturated carboxylic acid compound, and (iii) A combination with a radical polymerizable monomer; (ii) a combination of an unsaturated carboxylic acid compound and (iii) a radical polymerizable monomer is preferred.
On the other hand, from the environmental aspect, it is preferable to select and use each compound other than chlorine. That is, (ii) an unsaturated carboxylic acid compound alone or (ii) a combination of an unsaturated carboxylic acid compound and (iii) a radical polymerizable monomer is preferred. Among these, a combination of (ii) an unsaturated carboxylic acid compound and (iii) a radical polymerizable monomer is particularly preferable.

  In the following description, the resin obtained when at least chlorine is used as the polarity imparting agent for the raw material polyolefin resin is a chlorinated modified polyolefin resin, and when chlorine is not used as the polarity imparting agent, it is non-chlorinated. A polyolefin resin is used. Regardless of whether chlorine is used as the polarity-imparting agent, the polyolefin resin modified with the polarity-imparting agent is generally used as a modified polyolefin resin.

  The chlorine content in the chlorinated modified polyolefin resin is not particularly limited, but is preferably 2 to 35% by weight, and particularly preferably 4 to 25% by weight. If it is less than 2% by weight, the adhesion to various nonpolar substrates is improved, but the solubility in organic solvents may be reduced. On the other hand, if it exceeds 35% by weight, the adhesion to various nonpolar substrates may be reduced.

  The chlorine content can be measured according to JIS-K7229. That is, it can be measured using an “oxygen flask combustion method” in which a chlorine-containing resin is burned in an oxygen atmosphere, the generated gaseous chlorine is absorbed with water, and quantified by titration.

  In the present invention, the unsaturated carboxylic acid means an unsaturated compound containing a carboxyl group, and the unsaturated carboxylic acid derivative means a mono- or diester, amide, imide or the like of the compound, and its anhydride (unsaturated). Saturated carboxylic acid anhydride) means an anhydride of the compound. Examples of unsaturated carboxylic acid compounds, anhydrides thereof, and unsaturated carboxylic acid derivatives include fumaric acid, maleic acid, itaconic acid, citraconic acid, aconitic acid, nadic acid and their anhydrides, methyl fumarate, ethyl fumarate , Propyl fumarate, butyl fumarate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, methyl maleate, ethyl maleate, propyl maleate, butyl maleate, dimethyl maleate, diethyl maleate, malein Examples thereof include dipropyl acid, dibutyl maleate, maleimide, N-phenylmaleimide and the like, preferably itaconic anhydride and maleic anhydride. Of these, unsaturated carboxylic acid anhydrides are preferred. Unsaturated carboxylic acid, its anhydride, and unsaturated carboxylic acid derivative can be used individually or in mixture of 2 or more types.

  The graft weight of the (ii) unsaturated carboxylic acid compound in the modified polyolefin resin is preferably from 0.1 to 20% by weight, particularly preferably from 0.5 to 12% by weight. When (i) chlorine is not used as the polarity imparting agent, the graft weight of (ii) unsaturated carboxylic acid compound in the non-chlorinated modified polyolefin resin is preferably 0.5 to 20% by weight. Particularly preferred is 1 to 10% by weight.

  When only the unsaturated carboxylic acid type compound (ii) is used as the polarity imparting agent, if the graft weight is less than the above preferred range, the adhesiveness of the adhesive composition to the polar adherend is lowered. On the other hand, when the amount is too large, a large amount of unreacted substances are generated, and adhesion to a non-polar non-adhered body is unfavorable.

  (Ii) The grafted weight% of the unsaturated carboxylic acid compound can be determined by alkali titration method or Fourier transform infrared spectroscopy, and the numerical values shown in Examples described later are those measured by this method.

  The radical polymerizable monomer in the present invention means a (meth) acrylic compound or a vinyl compound. The (meth) acrylic compound is a compound containing at least one (meth) acryloyl group (meaning acryloyl group and / or methacryloyl group) in the molecule. Examples of radical polymerizable monomers 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, hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate N, N-dimethylaminoethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) Acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-methylene-bis (meth) acrylamide, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylamide, (meth) acryloylmorpholine, n-butyl vinyl ether, 4-hydroxybutyl vinyl ether, dode Vinyl ether and the like. In particular, methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, and lauryl (meth) acrylate are preferable. Among these, these methacrylates are preferable. These can be used alone or in admixture of two or more, and the mixing ratio can be freely set.

As the (meth) acrylic compound, those containing 20% by weight or more of at least one compound selected from (meth) acrylic acid esters represented by the following general formula (I) are also preferable. When the (meth) acrylic compound is used, the molecular weight distribution of the modified polyolefin resin can be narrowed, and the solvent solubility of the modified polypropylene resin and the compatibility with other resins can be further improved.
CH ₂ = CR ₁ COOR ₂ (I)
(In formula (I), R ₁ = H or CH ₃ , R ₂ = C _n H _{2n + 1} , n = 1 to 18)
In addition, it is preferable that n in the said general formula (I) is an integer of 8-18.

  (Iii) The graft weight of the radically polymerizable monomer in the modified polyolefin resin is preferably from 0.1 to 30% by weight, particularly preferably from 0.5 to 20% by weight. When only the radically polymerizable monomer is used as the polarity imparting agent (iii), if the graft weight is less than 0.1% by weight, the solubility of the modified polyolefin resin, the compatibility with other resins, and the adhesive strength are lowered. . On the other hand, if it is more than 30% by weight, the reactivity is high, so an ultra high molecular weight product is formed and the solvent solubility is deteriorated, and the amount of homopolymer or copolymer that is not grafted to the polyolefin skeleton is increased.

  When chlorine is not used as the polarity imparting agent, the graft weight of the radical polymerizable monomer in the non-chlorinated modified polyolefin resin is preferably 0.5 to 30% by weight, particularly preferably 1 to 20% by weight.

  In the present invention, it is most preferable to use a combination of an unsaturated carboxylic acid anhydride and a methacrylic acid ester among the above-described polarity imparting agents, whether or not chlorinated.

  The method for obtaining a modified polyolefin resin by modifying the raw material polyolefin resin using (ii) an unsaturated carboxylic acid compound or (iii) a radical polymerizable monomer as a polarizing agent is not particularly limited. It is possible to carry out by a known method for graft-polymerizing a polarity imparting agent to a polyolefin resin to obtain a modified polyolefin resin. For example, by using a solution method in which a mixture of a polyolefin resin and a polarizing agent is heated and dissolved in a solvent such as toluene and a radical generator is added, a Banbury mixer, a kneader, an extruder, etc., a polyolefin resin, a polarizing agent, Examples thereof include a method of obtaining a modified polyolefin resin by a melt kneading method in which an ethylene α-olefin copolymer and a radical generator are added and kneaded. In the case of using one or more compounds selected from (ii) an unsaturated carboxylic acid compound and (iii) a radical polymerizable monomer as the polarity imparting agent, these may be added all at once or sequentially.

  Moreover, the order at the time of carrying out the graft polymerization of the polarity imparting agent with respect to the polyolefin resin is not particularly limited.

  The radical generator that can be used for the reaction of graft-polymerizing the polarity imparting agent to the polyolefin resin can be appropriately selected from known ones. Particularly preferred are organic peroxide compounds. For example, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, dilauryl peroxide , Cumene hydroperoxide, t-butyl hydroperoxide, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, Cyclohexanone peroxide, t-butylperoxybenzoate, t-butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-Butylperoxyisopropyl carbonate, cumylpa Oxy octoate, and the like. Among these, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and dicumyl peroxide dilauryl peroxide are preferable. The amount of the radical generator added to the polyolefin resin is preferably 1 to 50% by weight, particularly preferably 1 to 30% by weight, based on the weight of the polarity-imparting agent. If the amount added is less than this range, the graft ratio may be lowered, and if it exceeds, it is uneconomical.

  When a compound selected from (ii) an unsaturated carboxylic acid compound and (iii) a radically polymerizable monomer is used as a polarity imparting agent, styrene, o-, p-, α-methylstyrene, divinylbenzene are used as reaction aids. , Hexadiene, dicyclopentadiene and the like may be added.

  When the polar imparting agent is used in combination with (i) chlorine, (ii) unsaturated carboxylic acid compound, and (iii) one or more compounds selected from radical polymerizable monomers, the chlorination step is the last step. It is preferable to do. That is, after graft polymerization of (ii) an unsaturated carboxylic acid compound and (iii) one or more compounds selected from radically polymerizable monomers to a polyolefin resin by the above-described solution method or melt-kneading method. A method of chlorination by the method described later is preferred. If the chlorination step is carried out before graft polymerization with (ii) an unsaturated carboxylic acid compound and (iii) one or more compounds selected from radically polymerizable monomers, dehydrochlorination may be caused by graft polymerization. However, if necessary, graft polymerization can be performed by a low temperature solution method.

  Note that (iii) when a compound containing an ester such as (meth) acrylic acid ester is used as the radical polymerizable monomer, the ester may be decomposed by chlorination. Therefore, these compounds are preferably graft polymerized after the chlorination step. As a method for chlorination, for example, after dissolving a modified polyolefin resin graft-polymerized with a polarity-imparting agent in a solvent such as chloroform, gaseous chlorine can be used while irradiating ultraviolet rays or in the presence of the radical generator. A method of obtaining a chlorinated modified polyolefin resin by blowing is preferred. Since the introduction rate of chlorine varies depending on differences in factors such as the type of polyolefin resin, reaction scale, reactor, etc., the chlorine content can be adjusted while monitoring the amount and time of chlorine blowing.

  The melting point of the modified polyolefin resin of the present invention is preferably in the range of 20 ° C to 100 ° C, more preferably 60 ° C to 90 ° C. If the melting point is less than 20 ° C, the solvent resistance of the dispersed resin composition may be lowered, and if it exceeds 100 ° C, the adhesion to the substrate may be lowered.

  In addition, when the temperature at which the resin dispersion is applied to a substrate such as polyolefin and dried (hereinafter sometimes referred to as “baking temperature”) is lower than the melting point of the modified polyolefin resin, a film-forming aid is used. The physical properties of the coated film after drying can be improved. As film-forming aids, ethylene glycol mono-ethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-ethyl ether acetate, ethylene glycol methyl ether acetate, diethylene glycol mono-ethyl ether, diethylene glycol mono- Examples include n-butyl ether and diethylene glycol mono-ethyl ether acetate.

  In the dispersion resin composition of the present invention, the higher the content of (a) the modified polyolefin resin, the better the drying properties, but it is usually 20% to 50% by weight, preferably 30% by weight to the composition. 50% by weight. If the content of the (a) modified polyolefin resin in the dispersion resin composition exceeds 50% by weight, the (a) modified polyolefin resin particles tend to cause secondary aggregation, which is not preferable. On the other hand, when the content is lower than 20% by weight, the water content in the dispersed resin composition is relatively increased, and a drying load is applied.

  The dispersed resin composition of the present invention contains (b) ammonia as the second component. Ammonia is added for the purpose of neutralizing the acid component in the modified polyolefin. A feature of the dispersed resin composition of the present invention is that ammonia is used in making the aqueous solution. Ammonia is a deleterious substance that is difficult to handle, and has not been conventionally used as a basic substance. However, the present inventors have used ammonia as a basic substance, so that in addition to adhesion and solvent resistance, water resistance and dispersion stability can be obtained even though the resulting dispersion resin composition contains a surfactant. It has been found that the property can be improved, and that these characteristics can be exhibited even under low-temperature impression conditions with respect to a substrate such as a nonpolar substrate.

  The pH of the dispersion resin composition of the present invention is preferably 5 or more, more preferably 6 to 10. Therefore, the content of (b) ammonia can be appropriately adjusted so that the pH of the dispersion resin of the present invention is in the above-mentioned range, that is, 5 or more. If the pH is less than 5, neutralization is insufficient, so that the modified polyolefin resin does not disperse in water, or even if dispersed, precipitation and separation are likely to occur over time, and storage stability may be deteriorated. Moreover, when it exceeds pH 10, there exists a possibility of producing a problem in the compatibility with another component, and the safety | security on an operation | work.

  Ammonia can be added to the dispersed resin composition as an aqueous solution. The concentration of the aqueous solution may be small, and the added amount may be small, which is advantageous in terms of process. However, high concentration ammonia is harmful to the human body and is very difficult to handle, so it is preferably used as an aqueous solution of about 25%.

  The dispersed resin composition of the present invention contains (c) a surfactant as the third component. (C) The surfactant is used to disperse and emulsify the modified polyolefin resin in water and maintain good storage stability, and any of nonionic surfactants and anionic surfactants can be used. Nonionic surfactants are preferred because the water resistance of the emulsified aqueous resin composition is better.

  Nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene derivatives, polyoxyethylene fatty acid esters, polyoxyethylene polyhydric alcohol fatty acid esters, polyoxyethylene Oxyethylene polyoxypropylene polyol, sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ether, polyoxyethylene alkylamine, alkylalkanolamide, polyalkylene glycol (meth) acrylate, N, N-polyoxyalkylene -Alkylamine etc. are mentioned. Preferable examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, N, N-polyoxyalkylene-alkylamines, and the like.

  As an anionic surfactant, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, α-olefin sulfonate, methyl taurate, sulfosuccinate, ether sulfonate, ether carboxylate, Examples include fatty acid salts, naphthalenesulfonic acid formalin condensates, alkylamine salts, quaternary ammonium salts, alkylbetaines, and alkylamine oxides. Among these, polyoxyethylene alkyl ether sulfate and sulfosuccinate are preferable.

  The addition amount of the surfactant is preferably from 0.1 to 30% by weight, more preferably from 5 to 20% by weight, based on the dispersed resin composition. When the amount exceeds 30% by weight, the excess emulsifier more than the amount that forms the aqueous resin composition significantly lowers the adhesion and water resistance, and causes a plastic effect and bleed phenomenon when formed into a dry film, thus blocking. This is not preferable because it is likely to occur.

  In the dispersion resin composition of this invention, (d) water is contained as a 4th component. By adding water to the above three components (a) to (c), in particular, the (a) modified polyolefin resin can be dispersed in water. As water, deionized water, distilled water, or the like can be used.

  In the dispersed resin composition of the present invention, the average particle size of the modified polyolefin resin emulsified and dispersed in water is preferably adjusted to 300 nm or less, more preferably 200 nm or less. If it exceeds 300 nm, the storage stability of the dispersion resin composition and the compatibility with other resins deteriorates, and the physical properties of the film such as adhesion to a substrate, solvent resistance, water resistance, blocking resistance, etc., deteriorate. There is a fear. In addition, the particle size can be made as small as possible, but in this case, generally the amount of emulsifier added is increased, and the physical properties of the film such as adhesion to the substrate, water resistance, and solvent resistance are reduced. Tend to appear. Therefore, in general, it is preferable to adjust to 50 nm or more. In addition, the average particle diameter in this invention can be measured by the particle size distribution measurement using a light-diffusion method, and the numerical value in the below-mentioned Example is obtained by this method. The particle diameter can be adjusted by appropriately selecting the amount and type of emulsifier added, the stirring force when emulsifying the resin in water, and the like.

  The method for producing the dispersed resin composition may be performed according to any known method such as forced emulsification, phase inversion emulsification, D phase emulsification, and gel emulsification. Further, in the production, it is possible to use a single stirring device such as a stirring blade, a disper, a homogenizer or the like, a composite stirring device combining these, a sand mill, a multi-screw extruder, or the like. However, in order to make the average particle size of the dispersed resin composition 300 nm or less, a phase inversion emulsification method or a method using a composite stirring, a sand mill, a multi-screw extruder, or the like having a high shear force is preferable.

  In the present invention, a cross-linking agent may be used in the dispersed resin composition depending on the application and purpose. The crosslinking agent means a compound that reacts with a hydroxyl group, a carboxyl group, an amino group, or the like present in a modified polyolefin resin, a surfactant, a basic substance or the like to form a crosslinked structure. The water-soluble crosslinking agent itself can be used, or one that is dispersed in water by some method can be used. Specific examples include blocked isocyanate compounds, aliphatic or aromatic epoxy compounds, amine compounds, amino resins, and the like. The method for adding the crosslinking agent is not particularly limited. For example, it can be added during or after the hydration process.

  The dispersed resin composition of the present invention can function as an intermediate medium for a substrate that has low adhesiveness and is difficult to apply such as paint. For example, it is also useful as an adhesive between polyolefin-based substrates such as polypropylene and polyethylene having poor adhesion, and can be used regardless of the presence or absence of surface treatment with plasma, corona, etc. on the surface of the substrate. Further, the dispersion stability of the paint can be improved by laminating the dispersion resin composition of the present invention on the surface of the polyolefin base material by a hot melt method and further coating the paint on the polyolefin resin base material. Furthermore, it is also suitable for polar substrates such as polyester such as polyethylene terephthalate, polyurethane and polyamide. That is, the modified polyolefin resin of the present invention can be suitably used as an adhesive, a primer, a paint binder, an ink binder, and the like. In particular, it is suitable as a primer or a primer used under low temperature drying, in particular, a drying temperature of 100 ° C. or less.

  In the dispersion resin composition of the present invention, an aqueous acrylic resin, an aqueous urethane resin, a lower alcohol, a lower ketone, a lower ester, an antiseptic, a leveling agent, an antioxidant, a light stabilizer, if necessary, depending on the use. Ultraviolet absorbers, dyes, pigments, metal salts, acids and the like can be blended.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these. Examples are given in the attached table.

Example 1
100 parts by weight of polypropylene (100 mol% of propylene component, weight average molecular weight 90,000, Tm = 90 ° C.) produced using a metallocene catalyst as a polymerization catalyst, 2 parts by weight of maleic anhydride, 1.5 parts by weight of methyl (meth) acrylate, 1.5 parts by weight of di-t-butyl peroxide was sufficiently mixed in advance and kneaded and reacted using a twin screw extruder set at a barrel temperature of 170 ° C. Vacuum degassing was performed in the extruder to remove residual unreacted substances. The obtained non-chlorinated modified polyolefin resin had a weight average molecular weight of 77,000, a maleic anhydride graft weight of 1.7% by weight, a methyl (meth) acrylate graft weight of 1.3% by weight, and a Tm of 90%. ° C.

  A stirrer, a condenser, a thermometer, and a funnel were attached. In a four-necked flask, 100 g of the obtained non-chlorinated modified polypropylene resin composition, 20 g of a surfactant (polyoxyethylene lauryl ether), 25% ammonia water ( 10 g of a neutralizing agent and 20 g of toluene (solvent) were added and kneaded at 120 ° C. for 30 minutes. Thereafter, 290 g of deionized water at 90 ° C. was added over 90 minutes. Subsequently, the solvent was removed under reduced pressure, and then cooled to room temperature with stirring. The obtained non-chlorinated modified polyolefin dispersed resin composition had an average particle diameter of 93 nm and a pH of 7.0.

Example 2
In Example 1, 2 parts by weight of maleic anhydride is 4 parts by weight of itaconic anhydride, 1.5 parts by weight of methyl (meth) acrylate is 3 parts by weight of lauryl methacrylate, and 1.5 parts by weight of di-t-butyl peroxide. Was changed to 1.5 parts by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and kneaded under the same conditions to carry out a modification reaction. The obtained non-chlorinated modified polyolefin resin had a weight average molecular weight of 75,000, a graft weight of itaconic acid of 2.5% by weight, a graft weight of lauryl methacrylate of 2.7% by weight, and a Tm of 90 ° C. .
The same operation as in Example 1 was performed on 100 g of the obtained non-chlorinated modified polyolefin resin. The obtained non-chlorinated modified polyolefin dispersed resin composition had an average particle size of 126 nm and a pH of 6.9.

Example 3
100 parts by weight of a propylene-based random copolymer produced by using a Ziegler-Natta catalyst as a polymerization catalyst (propylene component 75 mol%, ethylene component 5 mol%, butene component 20 mol%, weight average molecular weight 65,000, Tm = 70 ° C.) Then, 6 parts by weight of maleic anhydride, 3 parts by weight of ethyl (meth) acrylate, and 1.5 parts by weight of di-t-butyl peroxide were subjected to a kneading reaction using a twin screw extruder set at a barrel temperature of 160 degrees. Vacuum degassing was performed in the extruder to remove residual unreacted substances. The obtained non-chlorinated modified polyolefin resin has a weight average molecular weight of 55,000, a graft weight of maleic anhydride of 5.2% by weight, a graft weight of di-t-butyl peroxide of 1.3% by weight, Tm. Was 70 ° C.

  A stirrer, a condenser, a thermometer, and a funnel were attached. In a four-necked flask, 100 g of the obtained non-chlorinated modified polypropylene resin composition, 20 g of a surfactant (polyoxyethylene alkylamine), 25% ammonia water ( 18 g of neutralizing agent) and 18 g of methylcyclohexane (solvent) were added and kneaded at 120 ° C. for 30 minutes. Thereafter, 290 g of deionized water at 90 ° C. was added over 90 minutes. Subsequently, the solvent was removed under reduced pressure, and then cooled to room temperature with stirring. The resulting non-chlorinated modified polyolefin dispersed resin composition had an average particle size of 163 nm and a pH of 8.3.

Example 4
In a twin screw extruder in which a propylene random copolymer (propylene component 96 mol%, ethylene component 4 mol%, weight average molecular weight 100,000, Tm = 125 ° C.) produced using a metallocene catalyst as a polymerization catalyst was set to 350 ° C. The resulting mixture was thermally degraded to obtain a propylene random copolymer. 100 parts by weight of the deteriorated propylene random copolymer, 4 parts by weight of maleic anhydride, and 3 parts by weight of zircumiperoxide were mixed well in advance and kneaded using a twin screw extruder set at 180 ° C. Vacuum degassing was performed in the extruder to remove the remaining unreacted material, and a maleic anhydride-modified polyolefin resin was obtained. 2 kg of this resin is put into a glass-lined 50 L reaction kettle, 20 L of chloroform is added, gaseous chlorine is blown from the bottom of the reaction kettle while irradiating ultraviolet rays under a pressure of ² kg / cm ² , and contains chlorine. A sample with a rate of 18% was obtained. Next, chloroform as a solvent was distilled off with an evaporator to prepare a solid content of 30% by weight. A stabilizer (t-butylphenyl glycidyl ether) was added to the chloroform solution in an amount of 1.5% by weight with respect to the resin, followed by solidification in a twin screw extruder set at a barrel temperature of 90 ° C. The obtained chlorinated polyolefin resin had a weight average molecular weight of 92,000, a maleic anhydride graft weight of 3.5% by weight, a chlorine content of 15.5%, and a Tm of 85 ° C.

  A stirrer, a condenser, a thermometer, and a funnel were attached. In a four-necked flask, 100 g of the obtained chlorinated modified polypropylene resin composition, 20 g of a surfactant (N, N-polyoxyalkylene-alkylamine), 25% -Aqueous ammonia (neutralizing agent) 18 g and toluene (solvent) 25 g were added and kneaded at 120 ° C for 30 minutes. Thereafter, 290 g of deionized water at 90 ° C. was added over 60 minutes. Subsequently, the solvent was removed under reduced pressure, and then cooled to room temperature with stirring. The obtained chlorinated modified polyolefin dispersed resin composition had an average particle size of 105 nm and a pH of 7.1.

Comparative Examples 1-2
The same operation as in Example 1 was performed using 100 g of the non-chlorinated modified polyolefin resin obtained in Examples 1 and 2 as a neutralizing agent and using 2-methyl-2-amino-1-propanol instead of the aqueous ammonia solution. It was. The non-chlorinated modified polyolefin-dispersed resin composition obtained from each had an average particle size of 120 nm and 142 nm, and pH of 8.5 and 8.0.

Comparative Example 3
The same operation as in Example 1 was performed using 100 g of the non-chlorinated modified polyolefin resin obtained in Example 3 as a neutralizing agent and using morpholine instead of the aqueous ammonia solution. The obtained non-chlorinated modified polyolefin dispersed resin composition had an average particle size of 151 nm and a pH of 9.0.

Comparative Example 4
The same operation as in Example 4 was carried out using 100 g of the chlorinated modified polyolefin resin obtained in Example 4 as a neutralizing agent and using morpholine instead of the aqueous ammonia solution. The obtained chlorinated modified polyolefin dispersed resin composition had an average particle size of 99 nm and a pH of 8.0.

<Evaluation of various coating film properties>
After adjusting the dispersion resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4 to 30 wt%, test pieces were obtained by the following method.

  The surface of the ultra-rigid polypropylene plate was degreased with isopropyl alcohol, and the dispersion resin composition was spray-coated so that the dried coating film was 10 μm or more and 15 μm or less, and preheating was performed at 30 ° C. for 30 minutes or at 80 ° C. for 5 minutes. . Next, the base (undercoat) paint (solvent type) containing only the pigment component is spray-coated and allowed to stand for 10 minutes, and then the clear (top coat) paint containing two types of clear resin component and curing agent ( Solvent system) was painted. Then, the baking process for 30 minutes at 30 degreeC or 30 minutes at 80 degreeC was performed, and the test piece was prepared. Tests 1 to 4 were performed using this test piece.

<Test 1: Cross-cut adhesion>
Using a cutter knife, cut into 100 grids that reach the substrate at intervals of 2 mm on the coating film, and after applying cellophane adhesive tape on it, peel it in the 180 ° direction, and peel the coating film 10 times. Was determined.

<Test 2: Gasoline resistance>
The gasoline resistance was determined by immersing the test piece in regular gasoline and measuring the time required for the mixed solution to penetrate 2 mm into the coating film. “Time until the mixed solution penetrates into the coating film by 2 mm” means that when the test piece is immersed in gasoline, the solvent soaks from the end of the test piece between the polypropylene substrate and the coating film. Although the phenomenon of lifting from the substrate occurs, it means the time until the lifting of the coating film reaches 2 mm from the end of the test piece.

Judgment evaluation ×: Less than 30 minutes Δ: 30 minutes or more to less than 1 hour ○: 1 hour or more to less than 2 hours ◎: 2 hours or more

<Test 3: Gasohol resistance>
Gasohol resistance was determined by immersing the test piece in a mixed solution of regular gasoline / ethanol = 90/10 (vol / vol) and measuring the time until the mixed solution penetrated 2 mm into the coating film. “Time until the mixed solution penetrates 2 mm into the coating film” means that when the test piece is immersed in the mixed solution, the solvent soaks between the polypropylene substrate and the coating film from the end of the test piece. Means a time until the coating film lifts up to 2 mm from the end of the test piece.

Judgment evaluation ×: Less than 30 minutes Δ: 30 minutes or more to less than 1 hour ○: 1 hour or more to less than 2 hours ◎: 2 hours or more

<Test 4: Moisture resistance>
The test piece was immersed in warm water at 40 ° C. for 10 days, and then the swollen state (blister) on the surface of the coating film was visually observed and evaluated according to ASTM (American Society for Testing and Material) D714-87. That is, the size of the blister is evaluated by a numerical value of 1 to 10 (the smaller the blister, the smaller the numerical value. Note that up to 8 can be visually confirmed), and the number of blisters is F, M, MD, Evaluation was based on the alphabet of D (small: F (Few) <M (Medium) <MD (Medium Sense) <D (Dense): many).
Furthermore, after cutting with a cutter knife into 100 grids reaching the substrate at intervals of 2 mm on the coating film, and applying cellophane adhesive tape on it, it peels in the direction of 180 °, and the coating film remains. Judged by.

<Test 5: Storage stability test>
The dispersion resin composition was placed in a 250 ml glass lidded container and stored in a blow dryer at 50 ° C. for 1 month, and the change in viscosity before and after storage was evaluated.

  Table 1 shows the results of baking at 30 ° C., Table 2 shows the results of baking at 80 ° C., and Table 3 shows the results of storage stability.

  From the above results, it can be seen that the dispersion resin composition provided by the present invention is excellent in adhesion, solvent resistance, and moisture resistance even in a baking process at a low temperature of 80 ° C. from a baking process close to room temperature of 30 ° C.

  The dispersion resin composition neutralized with a basic substance other than ammonia at the time of aqueous formation is reduced in both solvent resistance and moisture resistance in a low-temperature baking treatment.

  On the other hand, the dispersion resin composition neutralized with ammonia is improved in adhesion, water resistance, solvent resistance, and blister resistance despite containing a surfactant. It was confirmed that the sex improved dramatically.

  Therefore, the dispersion resin composition using ammonia as a neutralizing agent in the case of making the aqueous solution of the present invention exhibits excellent physical properties with respect to a nonpolar substrate even by low-temperature baking.

Claims (6)

A dispersion resin composition comprising the following components (a) to (d):
(A) The raw material polyolefin resin having a melting point of 60 ° C. to 165 ° C. measured by a differential scanning calorimeter is an unsaturated carboxylic acid comprising (i) chlorine, (ii) an unsaturated carboxylic acid, its anhydride, and an unsaturated carboxylic acid derivative. One or more compounds selected from the group of acid compounds, and (iii) a modified polyolefin resin modified with one or more polarity-imparting agents selected from radically polymerizable monomers (b) ammonia (c) surfactants (d) water   The dispersion resin composition according to claim 1, wherein the melting point of the modified polyolefin resin (a) by a differential scanning calorimeter is 20 ° C to 100 ° C.   The polarity imparting agent is (ii) one or more compounds selected from an unsaturated carboxylic acid compound group consisting of an unsaturated carboxylic acid, an anhydride thereof and an unsaturated carboxylic acid derivative, and (iii) a radical polymerizable monomer. Item 3. The dispersed resin composition according to Item 1 or 2.   The polar imparting agent is at least one unsaturated carboxylic acid anhydride selected from itaconic anhydride and maleic anhydride, methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, and lauryl (meth). The dispersion resin composition according to any one of claims 1 to 3, which is a combination with one or more (meth) acrylates selected from acrylates.   The primer, ink, and adhesive agent containing the dispersion resin composition as described in any one of Claims 1-4.   The primer containing the dispersion resin composition as described in any one of Claims 1-4 used on the conditions whose drying temperature is 100 degrees C or less.