JPH1025420A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin compsn. which has excellent adhesion to a substrate, adhesion to a printing ink or a coating, and secondary processability such as coating by incorporating a thermoplastic resin and a hydroxyl-contg. fatty acid or a deriv. thereof. SOLUTION: This thermoplastic resin compsn. comprises: a thermoplastic resin; and a hydroxyl-contg. fatty acid or a deriv. thereof. This resin compsn., when printed or applied to moldings having various shapes, develops high adhesion to an ink or a coating. In particular, the resin compsn., when brought into contact with water during use thereof, an org. solvent, such as an alcohol or kerosene, hardly causes a lowering in adhesion. This compsn., particularly in the case of a nonpolar polyolefin resin, has high adhesion to a substrate and excellent adhesion to an ink, a coating or the like. Further, by virtue of the adhesion, there is no need to enhance the molding temp. Therefore, it is possible to reduce the occurrence of an offensive odor and emission of smoke at the time of molding and a deterioration in heat sealing properties and mechanical strength.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is intended to maintain the mechanical properties such as the tensile strength, tear strength and impact resistance of thermoplastic resins and various properties such as moldability, and particularly to paper, synthetic resin films and aluminum. A resin composition having good adhesion to base materials such as inks and paints and excellent paintability of molded articles, especially various films; laminates; containers such as bottles and containers A thermoplastic resin composition having excellent secondary workability such as printability, paintability, and dyeability of molded products molded in the fields of extrusion molding, hollow molding, injection molding, etc. of industrial parts such as home appliances and automobiles. About things.

[0002]

2. Description of the Related Art Thermoplastic resins, especially polyolefin resins, are excellent in moisture resistance and easy to melt-mold such as extrusion, hollow, injection, etc., and are therefore used as single films, laminated films with various resins, and other resin films. , Paper, aluminum, and the like. In addition, it is used as a molding material for containers such as bottles and containers, and industrial parts such as home appliances and automobiles. For example, in the extrusion field, a film formed of a material obtained by mixing titanium dioxide, calcium carbonate, talc, etc. with a polyolefin resin is widely used for printing as synthetic paper, and a biaxially stretched polypropylene film is printed. And is widely used as a packaging material.

[0003]

In recent extrusion laminating resins, there is a demand for a secondary workability such as adhesion to a substrate and adhesion to inks and paints (printability). However, polyolefin resins are inherently non-polar and have the disadvantage that they are difficult to adhere to different materials, particularly polar materials. Therefore, in extrusion lamination in which a polyolefin resin is laminated in a molten state,
Simply extruding a molten polyolefin-based resin onto a substrate cannot provide sufficient adhesive strength. Therefore,
Extrusion lamination is performed at a high molding temperature of the molten resin. However, the thermal stability of the resin is poor, and a decomposition reaction occurs. In addition, there is a problem that the mechanical strength such as impact strength is reduced, and the odor remains in the product. As another method, there is an ozone treatment method in which ozone is sprayed on a resin extruded from a die to oxidize the surface (see JP-A-57-157724). Although the ozone treatment method has the advantage of being able to oxidize only the surface requiring bonding at a low temperature, ozone has problems of odor and corrosiveness, and its use is limited and the bonding strength is low. Not enough. In particular, the laminate thus manufactured has a problem that the adhesive strength is significantly reduced by absorbing moisture.

[0004] As a method of improving the adhesiveness to a substrate, a laminate laminate is prepared by interposing an anchor coat agent such as a urethane-based adhesive, a butadiene-based adhesive, or an imine-based adhesive between the substrate and the laminate resin. There is a way to get However, in this method, although high adhesive strength can be expressed, the polyolefin resin is sufficiently oxidized to effectively act the anchor coating agent, and the carbonyl group,
It is necessary to generate a polar group such as a hydroxyl group and a carboxyl group. For that purpose, it is necessary to raise the molding temperature of the molten resin, and there is also a problem that odor and smoke are generated during molding. In addition, a propylene-based polymer or a linear low-density polyethylene having a particularly high thermal decomposability among polyolefin-based resins cannot provide a necessary amount of a polar group. Therefore, even if an anchor coating agent is used, a polyester film using these resins,
In fact, it has been difficult to obtain a laminate having a high adhesive strength to a substrate such as a polyamide film.

As a method for improving the printability of containers such as laminated products, films and bottles, there is a method of subjecting a substrate or a product to a surface treatment such as a corona discharge treatment. Equipment is required, and there is a problem in economy.

[0006] Printing and painting are also performed on injection-molded articles such as home appliances, containers, and automobile parts. When used, water vapor in the air, organic solvents such as water, acids, alkalis, alcohols, and thinners, and kerosene are used. However, there is a problem that printing, painting and the like are peeled off by contact with petroleum and the like. In order to solve these problems, the surface of the molded article is subjected to a corona discharge treatment, a plasma treatment, a flame treatment, an ultraviolet treatment, a surface treatment using a halogen-based solvent or the like, or a surface treatment such as a primer coat. However, these processes require new equipment and are economically disadvantageous. Further, the method using an organic solvent such as a halogen-based solvent such as trichloroethane not only has problems such as contamination of the working environment and waste disposal, but also has insufficient bonding strength.

The present invention has been made in view of the above circumstances, and without impairing the excellent properties of a thermoplastic resin such as a polyolefin-based resin, it has been found that secondary properties such as adhesion to a substrate, adhesion to a printing ink or paint, and paintability can be improved. An object of the present invention is to provide a thermoplastic resin composition having excellent processability.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on these demands and found that a fatty acid having a specific hydroxyl group or a derivative thereof is blended with a thermoplastic resin such as a polyolefin resin. As a result, it has been found that the above object can be achieved, and the present invention has been completed. That is, the first aspect of the present invention is a thermoplastic resin composition comprising (A) a thermoplastic resin containing at least (B) a fatty acid having a hydroxyl group or a derivative thereof.

A second aspect of the present invention is a thermoplastic resin composition for lamination containing (A) a thermoplastic resin containing at least (B) a fatty acid having a hydroxyl group or a derivative thereof.

A third aspect of the present invention is a thermoplastic resin composition for coating comprising (A) a thermoplastic resin containing at least (B) a fatty acid having a hydroxyl group or a derivative thereof.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The thermoplastic resin as the component (A) of the present invention includes a polyolefin resin, a polyamide resin, a polyester resin,
General-purpose thermoplastic resins such as saponified ethylene-vinyl acetate copolymer, polystyrene resin, ABS resin, polyphenylene ether resin, and polycarbonate resin, engineering plastics, and mixtures thereof are included. Among these, a polyolefin-based resin is particularly preferable in terms of mechanical strength, processability, economy, and the like.

The polyolefin resin is a homo- or copolymer of ethylene or an α-olefin having 3 to 16 carbon atoms, and specific examples thereof include high-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene. , Low-density polyethylene polymerized by high-pressure radical polymerization, ethylene-vinyl acetate copolymer, ethylene-
Ethylene polymers such as ethyl acrylate copolymer; propylene homopolymer, propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-4-methyl-1-pentene copolymer, propylene-1- Examples include random or block copolymers of propylene and other α-olefins such as hexene copolymers; homopolymers or mutual copolymers of other α-olefins such as 1-butene and mixtures thereof.

[0013] Among the above, the density 0.93-0.97g
/ Cm ³ high / medium density polyethylene, density 0.91-0.9
4 g / cm ³ linear low density polyethylene, density 0.86 to
A homopolymer or copolymer of 0.91 g / cm ³ of ultra-low density polyethylene and propylene can be generally obtained by homopolymerization or copolymerization using a Ziegler catalyst, a Phillips catalyst, a metallocene catalyst or the like.
Generally, it is produced by a medium / low pressure method, but it is also produced by a high pressure method, and is produced by any method such as a gas phase method, a solution method, and a slurry method. In the present invention, any of these methods may be used.

The low-density polyethylene obtained by the high-pressure radical polymerization method is generally obtained by polymerizing under a high pressure of 1000 to 3500 atm in the presence of a radical generator such as a peroxide. It is characterized by having many long chain branches in the range of 0.94 g / cm ³ . Also,
Ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers and other copolymers of ethylene with polar group monomers such as vinyl esters or (meth) acrylates are also produced by the high-pressure radical polymerization method, In the present invention, any of these may be used.

[0015] The melt flow rate (MFR; polypropylene is 230
° C, polyethylene is measured at 190 ° C under a load of 2.16 kg, and the unit is g / 10 minutes).
The range is from 1 to 300, preferably from 0.1 to 100. These polyolefin resins may be used alone or in combination of two or more.

The fatty acid having a hydroxyl group as the component (B) in the present invention or a derivative thereof will be described. In the component (B) of the present invention, as the fatty acid having a hydroxyl group, 9-hydroxypelargonic acid, hydroxypivalic acid, 2-hydroxycapric acid, 2-hydroxylauric acid, 2-hydroxymyristic acid, 2-hydroxypalmitic acid, Examples include 2-hydroxystearic acid, 16-hydroxypalmitic acid, ricinoleic acid, 12-hydroxystearic acid, 9,10-dihydroxystearic acid, and the like, and mixtures thereof. The component (B) may be obtained by subjecting an unsaturated fatty acid to a hydration reaction, an oxidation reaction, an epoxidation and a ring opening reaction thereof.

The derivatives of the fatty acid having a hydroxyl group which can be used as the component (B) of the present invention include the above fatty acids and higher alcohols such as octyl alcohol, caprylic alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol and stearyl alcohol; Ethylene glycol, glycerin, diglycerin, polyglycerin, trimethylolpropane, pentaerythritol,
Esters with polyhydric alcohols such as sorbitol and sorbitan are mentioned.

The fatty acid having a hydroxyl group may be a product obtained by condensing a hydroxyl group and a carboxyl group, for example, a compound represented by the following formula (1).
Examples thereof include poly (12-hydroxystearic acid).

[0019] ^{H - {(O-R 1} -CO) l - (O-R 2 -CO) m} n -OH ··· (1)

Here, R ¹ and R ² are a hydrocarbon group constituting a fatty acid having a hydroxyl group or a substituted hydrocarbon group, which may be the same or different. l and m are integers, n is an integer of 1 or more, and l and m are simultaneously 0
is not. Further, when l = 0, either m or n is 2 or more, and when m = 0, either l or n is 2 or more.

Further, oils and fats or waxes containing the above-mentioned components can also be used, such as castor oil containing triglyceride ricinoleate and triglyceride 9,10-dihydroxystearate as a main component, and hydrogenated hydrogenated products thereof. Castor oil, ergot oil, carnauba wax, lanolinic acid and the like. Further, by subjecting the oil or fat containing the precursor of the above component to a chemical reaction, it is also possible to obtain the target component, for example, oleic acid, linoleic acid,
Examples thereof include oxidation products and hydration products of fats and oils such as linolenic acid, and reaction products of epoxidized soybean oil and epoxidized linseed oil with carboxylic acids and amines. Among these components (B), oils and fats having a hydroxyl group or wax are preferable, and castor oil and hardened castor oil are particularly preferable.

Other examples of the derivative of a fatty acid having a hydroxyl group which can be used as the component (B) of the present invention include amides or imides of the above fatty acids and lithium, sodium, potassium, calcium, magnesium, zinc and the like of the above fatty acids. Metal salts.

Examples of the amide compound include ricinoleamide, N, N-ethylenebis- (ricinoleamide), N, N-hexamethylenebis- (ricinoleamide), N, N-xylylenebis- (ricinoleamide), 12-hydroxy Stearic acid amide, N, N-ethylenebis- (12-hydroxystearic acid amide), N, N-hexamethylenebis- (12-hydroxystearic acid amide), N, N-xylylenebis- (12-hydroxystearic acid amide), 9,10 -Hydroxystearic acid amide, N, N-ethylenebis- (9,10-hydroxystearic acid amide), N, N
-Hexamethylenebis- (9,10-hydroxystearic acid amide), N, N-xylylenebis- (9,10-hydroxystearic acid amide), and mixtures thereof.

In the present invention, the mixing ratio of the component (B) is
When the component (A) is contained in an amount of 0.01 to 20 parts by weight relative to 100 parts by weight, or when the composition contains the component (C) described later, the sum of the components (A) and (C) is 100 parts by weight. And preferably 0.1 to 15 parts by weight. When the blending ratio of the component (B) is less than 0.01 parts by weight, the adhesiveness to the substrate,
Printability and paintability are insufficient, and if it exceeds 20 parts by weight, mechanical properties such as extrudability and rigidity are reduced, and problems such as smoke, smell, and burns may occur during molding, which is not preferable. .

The composition of the present invention has a melt flow rate (M
FR) varies depending on the purpose, application, and the like, and is not particularly limited, and is usually selected from a range of 0.01 to 500 g / 10 min. Further, in general extrusion molding, injection molding, blow molding and the like, it is selected in the range of 0.01 to 300 g / 10 minutes, but in the field of fibers, 500 g / 10 minutes or more may be required. is there.

In the present invention, by blending an elastomer as the component (C) with the component (A),
In addition to improving thermal and mechanical properties such as low-temperature heat sealability, hot tack, impact resistance, etc., it further improves adhesion with anchor coating agents, adhesion with inks and paints, and paintability. be able to.

As the elastomer of the component (C), ethylene-α-olefin copolymer elastomer, isoprene-isobutylene copolymer elastomer, styrene-based copolymer elastomer, 1,2-polybutadiene, 1,4-
Examples thereof include diene-based elastomers such as polybutadiene, polychloroprene and polyisoprene, and mixtures thereof. Among them, at least one of ethylene-α-olefin copolymer elastomer, isoprene-isobutylene copolymer elastomer, and styrene-based copolymer elastomer is used. Examples of the ethylene-α-olefin copolymer elastomer include an ethylene-propylene copolymer elastomer, an ethylene-butene copolymer elastomer, an ethylene-propylene-diene copolymer elastomer, and a mixture thereof.

Examples of the diene component of the ethylene-propylene-diene copolymer elastomer include 1,4-pentadiene, 1,4-hexadiene, cyclohexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene. MF of these (C) elastomer components
R (JIS K7210, measured at 230 ° C, 2, 16Kg load)
Is not particularly limited, but is usually 0.001 to 200 g / 10
Min, preferably 0.1 to 100 g / 10 min.

The amount of the elastomer (C) of the present invention is as follows:
95% by weight of the total of the components (A) and (C)
Or less, preferably 80% by weight or less, more preferably 6% by weight or less.
It is selected in the range of 0% by weight or less. In particular, in the field of home electric appliances, automobile parts and the like, selection is made in consideration of various physical properties such as impact resistance and paintability.

The composition of the present invention may optionally contain various fillers (D) such as various inorganic or organic fillers.
May be added. In particular, in applications such as synthetic paper, titanium dioxide as a light shielding agent, or a filler such as calcium carbonate or talc is preferably used for the purpose of improving scratch resistance, rigidity, pencil writing properties and the like. Also, in various structural material applications, talc, glass fiber, and the like are preferably used for the purpose of improving rigidity and the like. The amount of these fillers is not particularly limited, but is generally 100 parts by weight of component (A) (if component (C) is present, the total amount of component (A) and component (C) is 100 parts by weight. ), Up to 200 parts by weight, preferably up to 100 parts by weight.

The thermoplastic resin composition of the present invention contains at least the above components (A) and (B), and is particularly a thermoplastic resin composition for extrusion lamination or coating. When a non-polar polyolefin resin is selected as the component (A), the thermoplastic resin composition further contains (E1) a hydroxyl group, (E)
2) It is preferable to introduce at least one functional group of a carboxyl group, a carboxylic anhydride group, an (E3) amino group, and an (E4) epoxy group. By introducing the component (E), the adhesiveness, printability of the thermoplastic resin composition,
Secondary workability such as paintability is improved. As a method for introducing these functional groups, for example, a method of directly graft-modifying the component (A) with the functional group-containing compound, a random copolymer of an olefin and a monomer having the functional group, a block copolymer, or A method of blending a polymer or compound such as a polyolefin resin graft-modified with a monomer having the functional group, a graft copolymer graft-modified with the component (C), a functional group-containing oligomer, a functional group-containing WAX, or the like. . Of these, a method of using a functional group-containing olefin polymer alone or a combination of an unmodified polyolefin resin and the functional group-containing olefin polymer is preferable. The concentration of the functional group (E) is 0.001 to 50 as the functional group unit in the whole composition.
%, Preferably 0.005 to 40% by weight, more preferably 0.01 to 35% by weight.

When the concentration of the functional group of (E) is 0.001
If the amount is less than 50% by weight, no improvement in adhesion, coating property, dyeing property, etc. of the substrate, ink, paint, etc. is observed. It is not preferable because there is a possibility that the property may be lowered or the quality of the substrate may be deteriorated.

The graft-modified component (A) and / or component (C) has a weight average molecular weight of 500 to 50,000.
0, preferably 2,000 to 400,000, more preferably 5,000 to 300,000, is a polyolefin-based resin and / or a modified elastomer. Is further improved.

The method for graft modification of the thermoplastic resin component (A) or the component (C) is not particularly limited, but generally a known method by graft modification can be used. That is, a compound having a functional group such as a hydroxyl group-containing compound, an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride, or a monomer thereof is prepared by combining (A) a thermoplastic resin or (C) an elastomer with a radical generator. It is generally manufactured by acting in a molten or solution state. Further, a solid phase grafting method in which a treatment is carried out with a modifier after contact treatment with an organic peroxide or irradiation with an electron beam or γ ray or the like at or below the melting point of the thermoplastic resin (A) is also possible. Such a method is generally performed at -20 ° C to 200 ° C.
It is performed in the range.

The type of radical generator is not particularly limited, but organic peroxides are generally used. Specific examples thereof include di-t-butyl peroxide, dicumyl peroxide, and t-butyl cumyl peroxide. Dialkyl peroxides such as oxides, diacyl peroxides such as i-butyl peroxide, peroxydicarbonates such as dii-propylperoxydicarbonate, peroxyesters such as t-butylperoxypivalate, Ketone peroxides such as methyl ethyl ketone peroxide, peroxyketals such as 1,1-bis-t-butylperoxycyclohexane, and hydroperoxides such as t-butyl hydroperoxide are exemplified. is not.

The above-mentioned composition used in the present invention can be used by dry blending each component with a Henschel mixer or the like or by melt-kneading. In the case of melt-kneading, a known method, for example, a method of kneading using an open roll, a Banbury mixer, a kneader, an extruder, or the like may be appropriately used. The kneading temperature is usually from 130 ° C to 300 ° C, preferably from 170 ° C to 2 ° C.
60 ° C.

Hydroxy group-containing monomers (E1) include hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerol mono or di (meth) acrylate, trimethylolpropane or di or tri (meth) acrylate, ethylene glycol monoallyl ether, propylene glycol monoallyl ether, polyethylene glycol Examples include, but are not limited to, monoallyl ether, o-, m- and p-hydroxymethylstyrene and mixtures thereof.

Similarly, (E2) monomers containing a carboxyl group or a carboxylic anhydride group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, furanic acid, vinyl acetic acid and pentenoic acid; maleic acid, croton Unsaturated dicarboxylic acids such as acid, fumaric acid, itaconic acid, tetrahydrophthalic acid and norbornene-5,6-dicarboxylic acid; and esters of these unsaturated monocarboxylic acids or anhydrides of dicarboxylic acids and mixtures thereof. Can be

(E3) As the amino group-containing monomer,
Examples thereof include aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and cyclohexylaminoethyl (meth) acrylate.

(E4) Epoxy group-containing monomers include glycidyl acrylate, glycidyl methacrylate,
Itaconic acid monoglycidyl ester, butenetricarboxylic acid monoglycidyl ester, butenetricarboxylic acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester; glycidyl esters such as α-chloroallyl, maleic acid, crotonic acid, fumaric acid; vinyl glycidyl ether, allyl Glycidyl ethers such as glycidyl ether, glycidyloxyethyl vinyl ether, and styrene-p-glycidyl ether; and p-glycidyl styrene, etc., and particularly preferred are glycidyl methacrylate and allyl glycidyl ether.

Further, specific examples of the functional group-containing olefin polymer are shown below. (E1) Examples of the hydroxyl group-containing olefin polymer include random copolymers such as ethylene-hydroxyethyl acrylate, ethylene-hydroxyethyl methacrylate, ethylene-hydroxypropyl acrylate, and ethylene-hydroxypropyl methacrylate; polyethylene, polypropylene, and ethylene-propylene copolymers Modified graft copolymers in which the above functional groups are grafted to an olefin polymer such as rubber are exemplified. Specifically, hydroxyethyl (meth) acrylate-g-polyethylene,
Hydroxypropyl (meth) acrylate-g-polyethylene, hydroxyethyl (meth) acrylate-g-polypropylene, hydroxypropyl (meth) acrylate-
Modified graft copolymers such as g-polypropylene, hydroxyethyl (meth) acrylate-g-ethylene-propylene copolymer rubber, hydroxypropyl (meth) acrylate-g-ethylene-propylene copolymer rubber, and the like. .

(E2) As the olefin containing a carboxyl group or a carboxylic anhydride group, ethylene- (meth)
For random copolymers such as acrylic acid copolymer, ethylene-maleic anhydride copolymer, ethylene-styrene-maleic anhydride copolymer; for olefin polymers such as polyethylene, polypropylene and ethylene-propylene copolymer rubber And (meth) acrylic acid, maleic anhydride, crotonic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid,
Modified graft copolymers obtained by grafting a monomer containing a carboxyl group or a carboxylic anhydride group such as norbornene-5,6-dicarboxylic acid are exemplified.

(E3) Examples of the amino group-containing olefin polymer include ethylene-aminoethyl (meth) acrylate, ethylene-dimethylaminoethyl (meth) acrylate, ethylene-diethylaminoethyl (meth) acrylate, and ethylene-cyclohexylaminoethyl (meth). A) random copolymers such as acrylates; and modified graft copolymers obtained by grafting the above functional groups to olefin polymers such as polyethylene, polypropylene and ethylene-propylene copolymer rubber.

(E4) Epoxy group-containing olefin polymers include ethylene-glycidyl acrylate copolymer,
Ethylene-glycidyl methacrylate copolymer, ethylene-vinyl acetate-glycidyl acrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-ethyl acrylate-glycidyl acrylate copolymer, ethylene-acrylic acid Random copolymers such as ethyl-glycidyl methacrylate copolymer; polyethylene,
Modified graft copolymers in which the above functional groups are grafted on olefin polymers such as polypropylene and ethylene-propylene copolymer rubber are exemplified.

The thermoplastic resin composition thus obtained can be formed into a molded product by extrusion molding as a film or sheet, or as a laminated film or sheet laminated on a substrate. Further, it can be formed into a molded product such as an industrial part or a container by a usual molding method such as injection molding, hollow molding, press molding or the like.

The resin composition thus obtained can give a strong adhesive force to a substrate when the resin composition is laminated on a heterogeneous substrate by, for example, an extrusion laminating method which is one of the fields of extrusion molding. The substrate to be used is not particularly limited. However, resin films such as paper, cellophane, polyester, polyamide, saponified ethylene-vinyl acetate copolymer, sheets, nonwoven fabrics and resin films on which metal or ceramics are deposited, polyvinylidene chloride Various materials such as a resin film coated with the same are used. The resin temperature during extrusion lamination is 220 to 360 ° C, preferably 2 to 360 ° C.
It is in the range of 50-330 ° C. In particular, materials having high thermal decomposability, such as propylene-based polymers and linear low-density polyethylene, generally cannot be molded at 310 ° C. or higher, so that the adhesive strength cannot be improved. By using a plastic resin composition, a remarkable effect is exerted for imparting adhesion between these materials and a substrate. The same applies when laminated on resin films, sheets, nonwoven fabrics, resin films on which metals or ceramics are deposited, resin films coated with polyvinylidene chloride, etc., such as polyester resins, polyamide resins, saponified ethylene-vinyl acetate copolymers. It shows a high adhesive effect.

When bonding to the base material by extrusion lamination, corona treatment, anchor coat treatment, ozone treatment, etc. can be used in combination. Among them, the anchor coat treatment is particularly effective. The anchor coating agent is not particularly limited, and a general imine-based, butadiene-based, titanate-based, urethane-based or the like is used, and a urethane-based agent is particularly preferred.

The thermoplastic resin composition thus obtained exhibits high performance in adhesiveness to ink or paint when printing or painting on molded articles of various shapes. In particular, it has a feature that the adhesiveness hardly decreases even when it comes into contact with an organic solvent such as water, alcohol, and kerosene during use. The printing method can be performed by a conventional method such as gravure printing, flexographic printing, and offset printing. The type of ink used for printing is not particularly limited.

An acrylic vehicle as a vehicle component of the ink,
Examples include urethane-based, epoxy-based, alkyd resin-based, and polyamide-based systems. As a coating method, a commonly used method can be used, and examples include a method of applying with a spray gun, a method of brush coating, and a method of using a roll coater. Examples of the paint include acrylic paints, urethane paints, melamine paints, epoxy paints and the like, and these are all preferably used. When printing or painting, surface treatments such as corona treatment, anchor coat treatment, ozone treatment, and flame treatment may be used in combination.

Further, in the case of injection molded articles such as cabinets and containers for home appliances which require heat resistance and impact resistance using the thermoplastic resin composition of the present invention, at least the thermoplastic resin (A) By containing the component (B) and further comprising a functional group-containing compound (C), (D) or (E), a polymer, or the like, it is possible to improve the secondary workability such as the coating property and the dyeing property. In particular, the functional group-containing compound or the functional group-containing polymer of (E) is used as the component (A) for the polyolefin resin, polyamide resin, polyester resin, polystyrene resin, ABS resin, polyphenylene ether (PPE) resin, polyoxymethylene (POM). )
An engineering plastic such as a resin is used in combination with the component (B), and is used as a modifier or a compatibilizer for the two components (A) to improve the mechanical properties, chemical resistance and other physical properties of these engineering plastics. It is desirable to simultaneously improve both the secondary workability such as printability and dyeability. Specific examples of the combination of these two components (A) include:
A mixture of a polyolefin resin and a polyamide resin, a mixture of a polyamide resin and a polyphenylene ether resin, and the like are given.

In order to further improve the printability and the paintability, a catalyst component such as dibutyltin malate (referred to as component (F)) may be added for use. The thermoplastic resin composition of the present invention may contain various conventional additives such as a plasticizer, a lubricant, various stabilizers, an antiblocking agent, an antistatic agent, a dye, and a pigment.

[0052]

EXAMPLES (A) Used in Examples and Comparative Examples described later.
To (F) indicate the type of each component. As the component (E), the component (A) or the component (C) was used after modification. The component (A) is each thermoplastic resin shown in Table 1.

[Table 1] <Synthesis of the above HEMA-g-RPP> MFR is 0.5 g / 10 minutes,
100 parts by weight of a propylene-ethylene random copolymer having an ethylene content of 4% by weight, and 1 part by weight of 2,5-bis (t-butylperoxy) -2,5-dimethylhexane were dry-blended using a Henschel mixer, 40mm
Graft modification was performed by kneading at 180 ° C. using a twin screw extruder in the same direction. The graft ratio was 1.1% by weight and the weight average molecular weight was 120,000.

Component (B): B1: 9,10-dihydroxystearic acid B2: Hardened castor oil (hydroxyl value: 168 mg KOH / g, saponification value: 18)
1 mgKOH / g, iodine value: 2.0, melting point 85 ° C)

Component (C): C1: ethylene-propylene copolymer elastomer (M
FR: 1.0 g / 10 min, ethylene content: 65% by weight) C2: Hydrogenated styrene-butadiene-styrene trifloc copolymer elastomer (styrene content: 29% by weight, MFR: 2.0 g / 10)
E13: HEMA-modified ethylene-propylene copolymer elastomer (hereinafter referred to as HEMA-g-EPR) <Synthesis of HEMA-g-EPR> Ethylene-propylene copolymer elastomer (ethylene content: 65% by weight, MFR :
4.0 g / 10 min) 100 parts by weight, HEMA 3 parts by weight,
After 0.5 parts by weight of 2,5-bis (t-butylperoxy) -2,5-dimethylhexane was dry-blended with a Henschel mixer, the mixture was mixed with a 40 mm co-rotating twin-screw extruder.
The mixture was kneaded at 0 ° C. to perform graft modification. The graft ratio was 0.85% by weight, and the MFR was 0.8 g / 10 minutes.

Component (D): D1: anatase-type titanium dioxide (Tochem Proctact Co., Ltd.)
D2: Calcium carbonate (S-SS, manufactured by Ishihara Sangyo Co., Ltd.)
S) D3: Talc (Hayashi Kasei Co., Ltd., Micron White 50)
00SA)

Component (F): F: DBTM (dibutyltin malate, manufactured by Sankyoki Gosei Co., Ltd.)

[1. Evaluation of Adhesion to Substrate] With respect to each of the thermoplastic resin compositions of Examples 1 to 8 and Comparative Examples 1 and 2 shown below, the adhesion at the time of laminating was examined.

Example 1 10 kg of the polyolefin resin A4 as the component (A) and 0.3 kg of the fatty acid having a hydroxyl group or the derivative B1 as the component (B) were mixed with a Henschel mixer, and then mixed with a Henschel mixer. 40mm
The composition was obtained by kneading at 240 ° C. using a coaxial twin screw extruder with a φ vent. 50 m using this composition
Using a biaxially stretched polyethylene terephthalate (PET) film as a base material, a resin temperature of 280 ° C. and an air gap of 110 m using a laminating machine having an extruder of mφ
m, and lamination was performed at a take-off speed of 50 m / min. In addition, the laminated resin film thickness was set to 20 μm. At this time, an anchor coating agent (two-liquid urethane-based “Seikadyne 3600A, B”) was applied in-line on the PET film in a laminating machine so that the thickness after evaporation of the solvent was 2 μm. After the lamination, the laminate was subjected to an aging treatment at 40 ° C. for one day to complete the curing of the anchor coat agent. The obtained laminate is cut into strips having a width of 15 mm in the flow direction of the laminate, and peeled at the interface between the base material and the laminate resin layer (90 ° peeling, peeling speed 300 mm /
Min) to determine the adhesive strength. As a result, 700 g / 15
mm width, indicating high adhesiveness. Further, in order to examine the solvent resistance, the samples were immersed in ethyl acetate, ethanol, salad oil, and kerosene at 23 ° C. for 30 minutes, respectively, and the peel strength (g / 15 mm) was examined. As a result, 600 g, 6
50 g, 700 g, and 700 g showed excellent adhesion with almost no decrease.

Example 2 Evaluation was made in the same manner as in Example 1 except that B1 in Example 1 was changed to B2. As a result, the adhesive strength was as high as 900 g / 15 mm width. Also,
After immersing this sample in ethyl acetate, ethanol, salad oil, and kerosene, the peel strength was examined.
g, 800 g, and 800 g.

Example 3 As the component (A), A7,
A composition was obtained by the same blending ratio and method as in Example 1 except that B2 was used as the component (B). Extrusion lamination was performed on the biaxially stretched polyamide 6 as a substrate in the same manner as in Example 1. Example 1 adhesion strength with substrate
It was 850 g / 15 mm wide when measured by the same method as in Example 1 and had high adhesiveness. After this sample was immersed in ethyl acetate, ethanol, salad oil, and kerosene, and the peel strength was examined, excellent adhesiveness was exhibited at 800 g / 15 mm width or more.

Example 4 A6 was added at 7 k as the component (A).
g, 3 kg of C1 as the component (C) (30% by weight of the component (C) with respect to the total amount of (A) + (C)), and (B)
A laminate was obtained in the same manner as in Example 1 by mixing 0.1 kg of B2 as a component. When the adhesive strength to the substrate was measured by the same method as in Example 1, the adhesive strength was 1000 g / 15 mm wide, indicating high adhesiveness. After this sample was immersed in ethyl acetate, ethanol, salad oil, and kerosene, the peel strength was examined.

[Example 5] 7 k of A6 was used as the component (A).
g, 3 kg of C2 as the component (C) (30% by weight of the component (C) based on the total amount of (A) + (C)), and (B)
A laminate was obtained in the same manner as in Example 1 by mixing 0.1 kg of B2 as a component. When the adhesive strength to the substrate was measured by the same method as in Example 1, the adhesive strength was 1000 g / 15 mm wide, indicating high adhesiveness. After this sample was immersed in ethyl acetate, ethanol, salad oil, and kerosene, the peel strength was examined.

Example 6 A laminate was obtained in the same manner as in Example 1 except that the component (A) was changed to A5. When the adhesive strength to the substrate was measured by the same method as in Example 1, it was 1100 g / 15 mm width and had high adhesiveness. This sample was immersed in ethyl acetate, ethanol, salad oil, and kerosene, and the peel strength was examined. All samples showed excellent adhesion at 950 g / 15 mm width or more.

Example 7 One component of E12 was used as the component (A).
A laminate was obtained in the same manner as in Example 1 by mixing 0 kg and 0.1 kg of B2 as the component (B). When the adhesive strength with the substrate was measured by the same method as in Example 1, it was 130.
The width was 0 g / 15 mm, and higher adhesive strength was obtained by using the modified product. After this sample was immersed in ethyl acetate, ethanol, salad oil, and kerosene, and the peel strength was examined, all samples showed excellent adhesion at 1100 g / 15 mm width or more.

Example 8 7 k of A6 was used as the component (A).
g, 3 kg of E13 as the component (C) ((A) + (C)
Example 1 was prepared by blending 0.1 kg of B2 as the component (B) and 30% by weight of the component (C) based on the total amount of
A laminate was obtained in the same manner as described above. When the adhesive strength with the substrate was measured by the same method as in Example 1, it was 1150 g / 15 m.
m width, and had high adhesiveness. After immersing this sample in ethyl acetate, ethanol, salad oil, kerosene,
When the peel strength was examined, excellent adhesiveness was exhibited at all of the widths of 1000 g / 15 mm or more.

Comparative Example 1 A laminate was obtained in the same manner as in Example 1 except that the component (B) was omitted. Adhesion strength with substrate is 20g / 1
Hardly adhered with a width of 5 mm. The solvent resistance was peeled off from the substrate during immersion in all the solvents.

Comparative Example 2 A laminate was obtained in the same manner as in Example 2 except that the component (B) was omitted. Adhesive strength with substrate is 30g / 1
Hardly adhered with a width of 5 mm. Solvent resistance peeled off from the substrate during immersion in all solvents.

Table 2 summarizes the above results.

[Table 2] In the table, the blending amounts of the components (A) and (C) are as follows:
+ (C), and the blending amount of the component (B) indicates parts by weight when (A) + (C) is 100 parts by weight.

[2. Evaluation of Adhesiveness to Ink] The adhesiveness to the ink was examined for each of the thermoplastic resin compositions of Examples 9 to 13 and Comparative Examples 3 and 4 shown below. Example 9 Polyolefin Resin A as Component (A)
1 kg and 0.3 kg of a hydroxyl group-containing fatty acid or its derivative B1, which is the component (B), are mixed in a Henschel mixer, and kneaded at 240 ° C. using a vented co-axial twin screw extruder having a screw diameter of 40 mmφ. A composition was obtained. Then, a casting film having a thickness of 80 μm was formed by a T-die forming machine having a 30 mmφ extruder.
The resin temperature was 240 ° C., and the take-off speed was 10 m / min. A printing machine (RI Co., Ltd., RI
Printing was carried out using a tester RI-3), a cellophane tape was stuck on the printed surface, and then peeled. When only the cellophane tape was peeled off, the ink was partially adhered to the cellophane tape, and when almost all the surface of the ink was peeled, x was evaluated. A urethane-based ink was used (Lamipack Super, manufactured by Toyo Ink Mfg. Co., Ltd.). After printing, the ink did not peel off at all even when the cellophane tape was peeled off. Further, in order to examine the solvent resistance, various solvents shown in Table 3 were used.
After immersion at 3 ° C. for 30 minutes, evaluation was made by the cellophane tape method. Similarly, the cellophane tape was not peeled off after immersion in the solvent.

Example 10 A3 was used as the component (A).
kg, 3 kg of C1 as a component (C) ((A) + (C))
Example 9 was prepared by blending (C) component (30% by weight) with respect to the total amount of (B) and 0.1 kg of B2 as component (B).
A film was obtained in the same manner as described above. Even if the cellophane tape was peeled off after printing, the ink did not come off at all. Similarly, the cellophane tape was not peeled off after immersion in the solvent.

Example 11 Table 3 shows the results of the evaluation performed in the same manner as in Example 10 except that B1 in Example 10 was replaced with B2.

Example 12 As component (A), A1
3 kg of E11 and 3 kg of C11 as the component (C)
g (30% by weight of component (C) based on the total amount of (A) + (C)) and 0.1 kg of B2 as component (B) were blended to obtain a film in the same manner as in Example 9. Was. Even if the cellophane tape was peeled off after printing, the ink did not come off at all. Similarly, the cellophane tape was not peeled off after immersion in the solvent.

Example 13 A1 was replaced by 7
kg and E11, 3 kg, and B2 as a component (B) in an amount of 0.1 kg.
0.5 kg (5% by weight based on the total amount of A1 + E11), 0.5 kg (5% by weight based on the total amount of A1 + E11), and 3 kg (5% by weight based on the total amount of A1 + E11). 30 for total amount
% By weight) to obtain a film in the same manner as in Example 8. Even if the cellophane tape was peeled off after printing, the ink did not come off at all. Similarly, the cellophane tape was not peeled off after immersion in the solvent.

Comparative Example 3 A laminate was obtained in the same manner as in Example 13 except that B2 was omitted. When the cellophane tape was peeled off after printing, the ink was peeled off except for about 1/3 of the cellophane tape contact surface. The cellophane tape was completely peeled off after immersion in the solvent.

Comparative Example 4 A laminate was produced in the same manner as in Example 13 except that B was changed to 0.1 kg (1 part by weight based on 100 parts by weight of the total of A1 + E11) except for B2. I got When the cellophane tape was peeled off after printing, the ink was peeled off except for about 2/3 of the cellophane tape contact surface. The cellophane tape was completely peeled off after immersion in the solvent.

These are summarized in Table 3.

[Table 3] In the table, the blending amounts of the components (A) and (C) are as follows:
+ (C), and (B), (F) and (D) are 10% of (A) + (C).
The parts by weight when 0 parts by weight are shown.

[3. Evaluation of Adhesion to Paint] Adhesion to paint was examined for each of the thermoplastic resin compositions of Examples 14 and 15 and Comparative Example 5 shown below. Example 14 8 kg of E11 as the component (A)
As component (C), 2 kg of E13 (20% by weight of component (C) based on the total amount of (A) + (C)), and as component (B) 0.5 kg of B2 ((A) + (C)) 2 kg of D3 as the component (D) (20 parts by weight of the component (D) with respect to 100 parts by weight of the total of (A) + (C)) based on 100 parts by weight of the total amount. Thus, a composition was obtained in the same manner as in Example 1. Using the obtained thermoplastic resin composition, injection molding was performed at a temperature of 200 ° C. and a mold temperature of 30 ° C. by injection molding.
A flat test piece of 00 mm x 100 mm and a thickness of 2 mm was obtained. The test piece was coated with a roll coater and a coating so that the thickness after drying was 30 μm, and dried at 80 ° C. for 1 hour. As the paint, a two-component urethane paint (manufactured by Fujikura Kasei Co., Ltd., Leclac) was used. Then, 100 grids were inserted into the test piece at an interval of 2 mm, a cellophane tape was stuck on the grid, and then peeled. As a result, a sample in which the paint did not peel at all was evaluated as Δ, a sample in which less than half of the grids were peeled was evaluated as Δ, and a sample in which half or more of the grids were peeled was evaluated as ×. As a result, no peeling of the paint was observed. further,
To test the solvent resistance, test specimens were exposed to various solvents at 23 ° C and 3 ° C.
After soaking for 0 minutes, those that did not peel were rated as ○, and those that peeled were rated as x. As a result, no peeling was observed even when the cellophane tape was immersed in the solvent.

Example 15 As component (A), A3 was replaced with 7
1 kg of E11 and 2 kg of C1 as component (C)
g (20% by weight of component (C) based on the total amount of (A) + (C)), and 0.5 kg of B2 as component (B) ((A) +
(B) 5 parts by weight with respect to 100 parts by weight of the total amount of (C); 0.5 parts by weight),
A composition was obtained in the same manner as in Example 1, except that 2 kg of D3 was used as the component (D) (20 parts by weight of the component (D) with respect to 100 parts by weight of the total amount of (A) + (C)). In the same manner as in Example 14, the test piece obtained by injection molding was applied, and a cross-cut peel test was performed using a cellophane tape. As a result, no peeling of the paint was observed. No peeling was observed even when the cellophane tape was peeled after immersion in the solvent.

Comparative Example 5 A test piece was obtained in the same manner as in Example 15 except that the component (B) was omitted. In the cross-cut peeling test after coating in the same manner as in Example 14, peeling was observed in about half of the cross-cuts. After immersion in the solvent, it was completely peeled off with all the solvents.

These are summarized in Table 4.

[Table 4] In the table, the blending amounts of the components (A) and (C) are as follows:
+ (C), and (B), (F) and (D) are 10% of (A) + (C).
The parts by weight when 0 parts by weight are shown.

[0081]

The thermoplastic resin composition of the present invention has a high adhesiveness to a substrate and an excellent adhesiveness to inks, paints and the like, especially for a nonpolar polyolefin resin. In addition, because of its high adhesiveness, it is not necessary to raise the molding temperature, and it is possible to reduce the generation of offensive odor and smoke during molding, the reduction of heat sealing properties and the decrease in mechanical strength. Further, since surface treatment of the surface of the molded article with a halogen-based solvent or the like can be omitted, cost can be reduced,
Problems such as work environment and waste disposal can be solved. Therefore, the present invention provides extremely high value for use in packaging materials, industrial materials, and various structural parts.

Claims (10)

[Claims] 1. A thermoplastic resin composition comprising (A) a thermoplastic resin and (B) a fatty acid having a hydroxyl group or a derivative thereof. 2. The thermoplastic resin composition according to claim 1, further comprising (C) an elastomer and / or (D) a filler. 3. The thermoplastic resin composition according to claim 3, wherein (E) at least one functional group of a hydroxyl group, a carboxyl group, a carboxylic anhydride group, an amino group, and an epoxy group is contained in the thermoplastic resin composition.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is blended by weight. 4. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyolefin resin. 5. The thermoplastic resin composition according to claim 4, wherein the polyolefin resin is a polypropylene resin and / or a polyethylene resin. 6. The thermoplastic resin composition according to claim 1, wherein the (B) fatty acid having a hydroxyl group or its derivative is a fat or wax having a hydroxyl group. 7. The fat or wax having a hydroxyl group,
7. The thermoplastic resin composition according to claim 6, which is castor oil or hardened castor oil. 8. The method according to claim 1, wherein 0.01 to 20 parts by weight of (B) the fatty acid having a hydroxyl group or a derivative thereof is compounded based on 100 parts by weight of the thermoplastic resin (A). The thermoplastic resin composition according to claim 1. 9. A thermoplastic resin composition for laminate comprising the thermoplastic resin composition according to claim 1. 10. A thermoplastic resin composition to be coated, comprising the thermoplastic resin composition according to claim 1.