JP2013072047A - Primer resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-chlorine resin composition having good adhesion to a nylon base material.SOLUTION: The resin composition for a nylon base material contains a block copolymer (C) comprising a polymer block (A) composed mainly of olefinic monomer units and a polymer block (B) composed of 2-25 mol% of a vinyl monomer unit having a carboxyl group and 98-75 mol% of another vinyl monomer unit copolymerizable with the above vinyl monomer, wherein the weight ratio of the polymer block (A) to the polymer block (B), (A)/(B) is 70/30 to 40/60.

Description

  The present invention relates to a resin composition used for the purpose of protecting or making up a nylon-based substrate. More specifically, the present invention relates to a resin composition for paints, printing inks, adhesives, or primers that is excellent in adhesion and other physical properties to a sheet, film, or molded product molded with a nylon resin.

Nylon resin has 1) high crystallinity, so it has excellent resistance to organic solvents such as gasoline and oil, 2) it has an amide group, so it has excellent toughness, impact resistance and flexibility. 3) Food It has excellent hygienic properties such as automobile parts (gasoline tanks, etc.), electrical and electronic equipment parts (connectors, housings, etc.), containers and food films, daily goods, toys, building materials, clothing fibers, Widely used in bearings, liners, rollers, insulating parts, food processing machine parts, packaging machine parts, etc. Along with the expansion of applications, protection or cosmetic properties of various sheets, films, molded articles (nylon-based substrates) using this nylon resin are required. However, conventional printing inks and adhesives have a problem that poor adhesion to a nylon base material occurs.
To solve this problem, a method of applying a primer (priming agent) mainly composed of chlorinated polyolefin using printing or an adhesive as a pretreatment for coating is disclosed (Patent Document 1, Patent Document 2). .

JP-A-57-036128 JP-B 63-036624

However, although the resin composition mainly composed of chlorinated polyolefin has excellent adhesion to nylon-based substrates, it has a problem of stability of chlorinated polyolefin due to dehydrochlorination. There is a tendency to be avoided. For this reason, non-chlorine resin compositions having good adhesion to nylon base materials, particularly non-chlorine primer resin compositions are demanded.
Then, an object of this invention is to provide the non-chlorine-type resin composition with favorable adhesiveness with a nylon-type base material.

That is, the present invention provides the following [1] to [2].

[1] A resin composition for a nylon base material, wherein the resin composition is a polymer block (A) mainly composed of an olefin monomer unit and a vinyl monomer unit having a carboxyl group. The polymer block (B) is composed of 2 to 25 mol% and a polymer block (B) composed of 98 to 75 mol% of other vinyl monomers copolymerizable with the vinyl monomer. And a block copolymer (C) in which the weight ratio of the polymer block (B) is (A) / (B) = 70/30 to 40/60 object.

[2] The nylon base material according to [1], wherein the block copolymer (C) is contained in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the total resin composition. Resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, the non-chlorine-type resin composition with favorable adhesiveness with a nylon-type base material can be provided.

  In the present invention, the nylon base material is a polyamide resin containing an aliphatic skeleton processed into a sheet, film, or molded product. The polyamide resin containing an aliphatic skeleton includes nylon 6, nylon 11, and nylon 12. Nylon 66, nylon 610, nylon 6T, nylon 6I, nylon 9T, nylon M5T, nylon 612, nylon 46, and the like.

  In the present invention, an inorganic substance such as glass fiber may be contained for the purpose of improving the mechanical strength, rigidity, and heat distortion temperature of the nylon base material.

  The block copolymer (C) in the present invention is composed of a polymer block (A) and a polymer block (B) described below. For example, an AB type diblock copolymer and an ABA type triblock copolymer are used. And a BAB type triblock copolymer. Among these, AB type diblock copolymer is preferable.

  The polymer block (A) is a polymer block mainly composed of olefin monomer units. That is, it is a polymer block composed of a polymer mainly composed of olefin monomer units. The content of the olefin monomer unit in the polymer block (A) is preferably in the range of 50 to 100 mol% based on the total number of moles of all structural units of the polymer block (A). It is more preferably in the range of 70 to 100 mol%, and still more preferably in the range of 80 to 100 mol%.

  An olefin monomer unit means a unit derived from an olefin monomer. Examples of the olefin monomer unit include ethylene; propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, and 1-hexene. Α-olefins such as 1-octene, 1-decene and 1-octadecene; 2-butenes; conjugated dienes such as isobutylene, butadiene, isoprene and cyclopentadiene; vinylcyclohexanes; derived from olefinic monomers such as β-pinene The polymer block (A) can contain one or more of these olefinic monomer units.

  The polymer block (A) preferably contains units derived from ethylene and propylene. Among these, a polymer block composed of units derived from propylene; a copolymer block composed of units derived from propylene and units derived from other α-olefins other than propylene is more preferable. The propylene content in the polymer block (A) is within the range of 70 to 100 mol%, more preferably 80 mol% to 100 mol, based on the total number of moles of all structural units of the polymer block (A). % Is preferred. The other α-olefin is preferably ethylene or butene.

  When the olefin monomer unit is a unit derived from a conjugated diene such as butadiene, isoprene or cyclopentadiene, the remaining unsaturated bond may be hydrogenated.

  The polymer constituting the polymer block (A) is mainly composed of the olefin monomer units described above. Therefore, in addition to the olefinic monomer unit, a unit other than the olefinic monomer may be included. For example, the unit derived from the vinyl monomer copolymerizable with the above-mentioned olefin monomer can be contained in a proportion in the range of 0 to 50 mol% as necessary. The content of the monomer unit is preferably in the range of 0 to 30 mol%, and more preferably in the range of 0 to 20 mol%.

  Examples of the vinyl monomer copolymerizable with the olefin monomer include (meth) acrylonitrile; vinyl esters such as vinyl acetate and vinyl bivalinate; methyl (meth) acrylate, ethyl (meth) acrylate, (Meth) acrylic acid esters such as butyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; (meth) acrylamide; N-vinyl-2-pyrrolidone, etc. 1 type (s) or 2 or more types can be used. Among these, methyl acrylate, ethyl acrylate, and vinyl acetate are preferable.

  The polymer mainly composed of the olefin monomer units constituting the polymer block (A) may be modified. The modification can be performed on the polymer by various known methods such as epoxidation; hydroxylation; anhydrous carboxylic oxidation; carboxylic oxidation.

  The polymer block (A) may be obtained by degrading a polymer mainly composed of the above-described olefin monomer units. Thereby, a double bond can be introduce | transduced into the terminal of the polymer mainly consisting of the olefin-type monomer unit which comprises a polymer block (A), and the molecular weight of a polymer block (A) can be adjusted. Degradation methods include a method in which a polymer mainly composed of olefinic monomer units is thermally decomposed in an oxygen-free atmosphere at 400 to 500 ° C., and a polymer mainly composed of olefinic monomer units is subjected to an oxygen-free atmosphere. Among them, a method of decomposing in the presence of an organic peroxide can be mentioned, and any method may be used.

  Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl 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- Butyl peroxyisobutyrate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisopropyl carbonate, cumyl peroxy octoate Etc.

  The polymer block (B) is a polymer block comprising a vinyl monomer having a carboxyl group, a carboxylic anhydride group or a sulfonic acid group and another vinyl monomer copolymerizable with the vinyl monomer. It is. That is, it is a polymer block composed of a vinyl monomer having the substituent and a polymer of another vinyl monomer copolymerizable with the vinyl monomer.

  The polymer block (B) contains 2 to 25 mol% of vinyl monomer units having a carboxyl group, a carboxylic anhydride group or a sulfonic acid group based on the number of moles of all structural units of the polymer block (B). contains. By setting it within this range, it is preferable from the viewpoint of adhesion to the top coat.

  Examples of the vinyl monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid, etc., and one or more of these are used. be able to. Among these, acrylic acid and methacrylic acid are preferable.

  Examples of vinyl monomers having a carboxylic anhydride group (group represented by the formula: —CO—O—CO—) include, for example, maleic anhydride, itaconic anhydride, citraconic anhydride, butenyl succinic anhydride, and tetrahydro anhydride. A phthalic acid etc. can be mentioned, Among these, 1 type (s) or 2 or more types can be used. Of these, maleic anhydride is preferred.

  Examples of the vinyl monomer having a sulfonic acid group include 4-styrene sulfonic acid, 2-methyl-2-propene-1-sulfonic acid, allyl sulfonic acid, and 2-acrylamido-2-methylpropane-1. -A sulfonic acid etc. can be mentioned and 1 type, or 2 or more types of these can be used. It is also possible to use vinyl monomers whose sulfonic acid group is a metal salt such as sodium or potassium or various ammonium salts.

  The polymer block (B) is composed of units of other vinyl monomers copolymerizable with the above-mentioned vinyl monomers having a carboxyl group, a carboxylic anhydride group or a sulfonic acid group. 75 to 98 mol% based on the number of moles of all structural units. The other vinyl monomer means a vinyl monomer other than a vinyl monomer having a carboxyl group, a carboxylic anhydride group or a sulfonic acid group, and includes styrene, p-styrene sulfonic acid and its Styrene monomers such as sodium salt and potassium salt; (meth) acrylonitrile; vinyl esters such as vinyl acetate and vinyl bivalinate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, iso-propyl (Meth) acrylates such as (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. , (Meth) acrylamide, N-vinyl-2-pi Such as pyrrolidone are exemplified, can be used alone or two or more of them. Among these, methyl (meth) acrylate, ethyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, styrene, and vinyl acetate are preferable.

  As the combination of monomers constituting the polymer block (B) in the present invention, a vinyl monomer having a carboxyl group and a (meth) acrylic acid ester are preferable. For example, acrylic acid, methyl acrylate, ethyl acrylate, iso -(Meth) acrylates such as butyl acrylate and tert-butyl acrylate.

  In the present invention, (meth) acrylate refers to acrylate and methacrylate.

  The weight average molecular weight of the polymer block (A) is preferably in the range of 1,000 to 100,000, and more preferably in the range of 5,000 to 70,000. As a weight average molecular weight of a polymer block (B), it is preferable to exist in the range of 1,000-100,000, and it is more preferable to exist in the range of 5,000-70,000.

  The weight average molecular weight of the block copolymer (C) is preferably in the range of 5,000 to 100,000, and more preferably in the range of 10,000 to 70,000. When the weight average molecular weight of the block copolymer (C) exceeds 100,000, the solution viscosity when mixed with the active energy ray-curable compound (D) becomes high or becomes difficult to dissolve and the solution properties become unstable. This causes problems such as becoming and lowering the coatability. When the weight average molecular weight of the block copolymer (C) is less than 5,000, the cohesive force is insufficient, and the adhesion to the polyolefin substrate cannot be exhibited. In addition, the weight average molecular weight as used in the field of this invention is the value calculated | required from the standard polystyrene calibration curve by the gel permeation chromatography (GPC) method.

  The block copolymer (C) in this invention should just be comprised from the polymer block (A) and the polymer block (B), and the manufacturing method is not specifically limited. For example, it can be produced by radical polymerization of the monomer component constituting the polymer block (B) in the presence of the polymer block (A) having a mercapto group at the terminal. According to this method, the block copolymer (C) having the target weight average molecular weight and molecular weight distribution can be produced simply and efficiently. In addition, according to this method, as a polymer block (A), it is possible to use those obtained by degrading various polyolefins including commercial products as described above, compared to the case of producing a block copolymer by living polymerization, The structure and melting point of the polymer block (A) can be freely selected.

  The polymer block (A) having a mercapto group at the terminal can be produced by various methods. For example, a double bond is introduced at the end of a polymer mainly composed of olefinic monomer units, and thioacetic acid, thiobenzoic acid, thiopropionic acid, thiobutyric acid or thiovaleric acid is introduced through this double bond. After the addition, it can be produced by a method of treating with an acid or alkali, a method of using ethylene sulfide as a terminator when producing a polymer mainly composed of olefinic monomer units by an anionic polymerization method.

  The radical polymerization of the monomer component constituting the polymer block (B) in the presence of the polymer block (A) having a mercapto group at the terminal can be advanced by a known method. For example, a solution in which a polymer block (A) having a mercapto group at a terminal is dissolved in an organic solvent such as toluene, then a monomer component constituting the polymer block (B) is added, and a radical generator is added with stirring. Law. Further, for example, the polymer block (A) having a mercapto group at the terminal is melted in a solvent-free manner by heating to the melting point or higher, and then the monomer component constituting the polymer block (B) is added and stirred. Examples include a melting method in which a lower radical generator is added.

  The radical generator for performing the radical polymerization can be appropriately selected from known ones. In particular, azo initiators are preferable. For example, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl-2, 2′-azobis (2-methylpropionate), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis ( N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), etc., and those having an appropriate half-life temperature depending on the temperature at which radical polymerization is performed You can choose.

  In the present invention, the block copolymer (C) is such that the weight ratio of the polymer block (A) to the polymer block (B) is polymer block (A) / polymer block (B) = 70 / 30-40. / 60 is required. A weight ratio within this range is preferred from the standpoint of solvent solubility and compatibility with other resins.

The composition of the present invention can be used by dissolving in an organic solvent. The solution concentration may be appropriately selected depending on the use, but the coating concentration is preferably 5 to 60% by weight because the coating workability is impaired if the solution concentration is too high or too low. The solvent to be used is preferably an aromatic solvent such as toluene or xylene. In addition, an ester solvent such as ethyl acetate or butyl acetate, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, or an aliphatic solvent such as n-hexane or heptane. Solvent, cycloaliphatic solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane can be used. Furthermore, in order to increase the storage stability of the resin solution, alcohols such as methanol, ethanol and isopropyl alcohol, propylene glycol ethers such as propylene glycol methyl ether, propylene glycol ethyl ether and propylene glycol tertiary butyl ether are used alone or in combination. It is preferable to add 1 to 20% by weight with respect to the solvent by mixing more than one species.
The resin composition of the present invention can be obtained by mixing the block copolymer (C) and an organic solvent by a known method. Moreover, after heating and stirring a composition for a fixed time at 90 degrees C or less, the solution property can be improved by cooling.
The resin composition according to the present invention can be used as a paint, printing ink, adhesive, and primer that can be applied to nylon films, sheets, and molded articles. The coating may be used as it is, but a solvent, a pigment, and other additives may be added as long as the effects of the present invention are not impaired. Further, the composition exhibits a well-balanced coating film property by itself, but if necessary, cyclized rubber, petroleum resin, coumarone indene resin, acrylic resin, alkyd resin and the like may be further added. Absent.

  EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to this. In the following reference examples, the melting point was measured as follows.

(Measuring method of melting point)
The melting point is measured by a differential scanning calorimeter (DSC). The measurement of melting | fusing point Tm can be performed on the following conditions, for example. 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 addition, Tm in a reference example to be described later is measured under the above-described conditions.

(Chlorine content)
It measured according to JIS-K7229.

Example 1
Production of Block Copolymer (Melting Point 75 ° C. Polyolefin Block / Ethyl Acrylate-Acrylic Acid Block Copolymer) (1) Olefin Polymer (Propylene copolymer having 92 mol% of propylene component and 8 mol% of ethylene component) A polyolefin having a double bond at the terminal is supplied to a twin-screw extruder, melt-kneaded at 420 ° C., and thermally decomposed. Were manufactured respectively.
(2) 100 parts by weight of the polyolefin having a double bond at the end obtained in (1) above, 300 parts by weight of xylene and 10 parts by weight of thioacetic acid were placed in the reactor, and the inside was sufficiently purged with nitrogen. 2,2′-Azobisisobutyronitrile (0.2 part by weight) was added and reacted at 90 ° C. for 2 hours to produce a polyolefin having a terminal thioacetyl group.
(3) 100 parts by weight of the polyolefin having a thioacetyl group at the terminal obtained in the above (2) is dissolved in a mixed solvent of 200 parts by weight of xylene and 20 parts by weight of n-butanol, and 4% n- A polyolefin having a terminal mercapto group was produced by adding 10 parts by weight of a butanol solution and reacting in nitrogen at 110 ° C. for 1 hour.
(4) 100 parts by weight of a polyolefin having a mercapto group at the end obtained in (3) above is dissolved in 250 parts by weight of toluene, 85 parts by weight of ethyl acrylate and 5 parts by weight of acrylic acid are added thereto, and in nitrogen, At 90 ° C., 2,2′-azobis (2,4-dimethylvaleronitrile) was added so that the polymerization rate was 10 to 20% per hour, and the reaction was stopped when the polymerization rate reached 95%. . After cooling the reaction solution, the solvent is removed, and an AB type diblock copolymer (hereinafter referred to as “block copolymer (2)”) composed of a polyolefin block (A) and an ethyl acrylate-acrylic acid block (B). Obtained). The weight average molecular weight of the polymer block (A) of the obtained block copolymer (2) is 21000, the weight average molecular weight of the polymer block (B) is 19000, and the weight average molecular weight of the block copolymer (2) is 40000. The melting point of the polymer block (A) was 75 ° C.

(Example 2)
Production of Block Copolymer (Melting Point 75 ° C. Polyolefin Block / Ethyl Acrylate-Acrylic Acid Block Copolymer) (1) Olefin Polymer (Propylene copolymer having 92 mol% of propylene component and 8 mol% of ethylene component) A polyolefin having a double bond at the terminal is supplied to a twin-screw extruder, melt-kneaded at 420 ° C., and thermally decomposed. Were manufactured respectively.
(2) 100 parts by weight of the polyolefin having a double bond at the end obtained in (1) above, 300 parts by weight of xylene and 10 parts by weight of thioacetic acid were placed in the reactor, and the inside was sufficiently purged with nitrogen. 2,2′-Azobisisobutyronitrile (0.2 part by weight) was added and reacted at 90 ° C. for 2 hours to produce a polyolefin having a terminal thioacetyl group.
(3) 100 parts by weight of the polyolefin having a thioacetyl group at the terminal obtained in the above (2) is dissolved in a mixed solvent of 200 parts by weight of xylene and 20 parts by weight of n-butanol, and 4% n- A polyolefin having a terminal mercapto group was produced by adding 10 parts by weight of a butanol solution and reacting in nitrogen at 110 ° C. for 1 hour.
(4) 100 parts by weight of a polyolefin having a mercapto group at the terminal obtained in the above (3) is dissolved in 250 parts by weight of toluene, and 85 parts by weight of ethyl acrylate and 2.0 parts by weight of acrylic acid are added to the mixture. Inside, at 90 ° C., 2,2-azobis (2,4-dimethylvaleronitrile) was added so that the polymerization rate was 10-20% per hour, and the reaction was stopped when the polymerization rate reached 95%. did. After cooling the reaction solution, the solvent is removed, and an AB type diblock copolymer (hereinafter referred to as “block copolymer (2)”) composed of a polyolefin block (A) and an ethyl acrylate-acrylic acid block (B). Obtained). The weight average molecular weight of the polymer block (A) of the obtained block copolymer (2) is 21,000, the weight average molecular weight of the polymer block (B) is 18000, and the weight average molecular weight of the block copolymer (2) is 39000. The melting point of the polymer block (A) was 75 ° C.

(Example 3)
Production of Block Copolymer (Melting Point 75 ° C. Polyolefin Block / Ethyl Acrylate-Acrylic Acid Block Copolymer) (1) Olefin Polymer (Propylene copolymer having 92 mol% of propylene component and 8 mol% of ethylene component) A polyolefin having a double bond at the terminal is supplied to a twin-screw extruder, melt-kneaded at 420 ° C., and thermally decomposed. Were manufactured respectively.
(2) 100 parts by weight of the polyolefin having a double bond at the end obtained in (1) above, 300 parts by weight of xylene and 10 parts by weight of thioacetic acid were placed in the reactor, and the inside was sufficiently purged with nitrogen. 2,2′-Azobisisobutyronitrile (0.2 part by weight) was added and reacted at 90 ° C. for 2 hours to produce a polyolefin having a terminal thioacetyl group.
(3) 100 parts by weight of the polyolefin having a thioacetyl group at the terminal obtained in the above (2) is dissolved in a mixed solvent of 200 parts by weight of xylene and 20 parts by weight of n-butanol, and 4% n- A polyolefin having a terminal mercapto group was produced by adding 10 parts by weight of a butanol solution and reacting in nitrogen at 110 ° C. for 1 hour.
(4) 100 parts by weight of a polyolefin having a mercapto group at the end obtained in (3) above is dissolved in 250 parts by weight of toluene, 85 parts by weight of ethyl acrylate and 20 parts by weight of acrylic acid are added to this, and in nitrogen, At 90 ° C., 2,2′-azobis (2,4-dimethylvaleronitrile) was added so that the polymerization rate was 10 to 20% per hour, and the reaction was stopped when the polymerization rate reached 95%. . After cooling the reaction solution, the solvent is removed, and an AB type diblock copolymer (hereinafter referred to as “block copolymer (2)”) composed of a polyolefin block (A) and an ethyl acrylate-acrylic acid block (B). Obtained). The weight average molecular weight of the polymer block (A) of the obtained block copolymer (2) is 21000, the weight average molecular weight of the polymer block (B) is 16000, and the weight average molecular weight of the block copolymer (2) is 37000. The melting point of the polymer block (A) was 75 ° C.

(Reference Example 1)
In a twin-screw extruder, 500 g of a propylene random copolymer (propylene: about 97% -ethylene: about 3%) produced by using a metallocene catalyst as a polymerization catalyst (manufactured by Nippon Polychem Co., Ltd., Tm = 125 ° C.), 30 g of maleic anhydride, 15 g of mill peroxide was added. The residence time is 10 minutes and the barrel temperature is 180 ° C. (1st to 7th barrels). The deaeration is performed at the 7th barrel, unreacted maleic anhydride is removed, and maleic anhydride-modified propylene-based random A copolymer was obtained. 500 g of this resin was put into a glass-lined reaction kettle, 5 L of chloroform was added, and gaseous chlorine was blown from the bottom of the reaction kettle while irradiating ultraviolet rays under a pressure of 2 kg / cm 2. In the middle, chloroform was removed as a solvent by using an evaporator, and a 20% by weight solution of a chlorinated propylene random copolymer substituted with toluene and modified with maleic anhydride was obtained. The obtained chlorinated propylene random copolymer had a chlorine content of 20.8%, and the maleic anhydride content with respect to the chlorinated propylene random copolymer was 5.0% by weight.

(Reference Example 2)
In the same manner as in Reference Example 1, a chlorinated propylene random copolymer having a chlorine content of 25.1% and a maleic anhydride content of 5.1% by weight was obtained.

<Nylon substrate adhesion test>
The 15% toluene solutions of Examples 1 to 3 and Comparative Example 1 were spray-coated on a nylon plate so that the dry film thickness was 10 μm or more and 15 μm or less, and dried at 80 ° C. for 30 minutes. After standing overnight, a cross-cut adhesion test was performed.
-Adhesion evaluation 100 grids reaching the substrate at intervals of 2 mm were formed on the coated surface, and a cellophane adhesive tape was stuck on it and peeled in the direction of 180 degrees, and the degree of remaining coating was determined. The results are shown in (Table 1).

<Primer test>
The 10% toluene solutions of Examples 1 to 3 and Comparative Example 1 were spray-coated on a nylon plate so that the dry film thickness was 10 μm or more and 15 μm or less, and allowed to stand at room temperature for 10 minutes. Next, the base (undercoat) paint (solvent type) containing the pigment component is spray-coated, left at room temperature for 10 minutes, and then the clear (top coat) containing the clear resin component and the curing agent. A paint (solvent type) was applied and allowed to stand at room temperature for 10 minutes, and then baked at 80 ° C. for 30 minutes. After the test piece was allowed to stand at room temperature for 3 days, a test similar to the above adhesion test was performed. The results are shown in (Table 1).

Claims (2)

A resin composition for a nylon base material, wherein the resin composition is a polymer block (A) mainly composed of olefin monomer units and vinyl monomer units 2 to 25 having a carboxyl group. And a polymer block (B) composed of 98 to 75 mol% of other vinyl monomer units copolymerizable with the vinyl monomer. The polymer block (A) and the polymer A resin composition for a nylon-based substrate, comprising a block copolymer (C) in which the weight ratio of the block (B) is (A) / (B) = 70/30 to 40/60.   2. The resin composition for a nylon-based substrate according to claim 1, wherein the block copolymer (C) is contained in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the total resin composition. .