JP5292777B2 - Polyamide resin composition for hydraulic transfer printing moldings - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide resin composition that molds a molded article having excellent hydraulic transfer printability. <P>SOLUTION: The polyamide resin composition includes (A) 30-70 parts by mass of a crystalline polyamide resin, (B) 5-60 parts by mass of an inorganic reinforcing material, (C) 1-10 parts by mass of a resin that is compatible with a crystalline polyamide resin or dispersible in the resin and improves the contact angle of water on the crystalline polyamide resin and (D) 0.05-2 parts by mass of at least one of a higher fatty acid metal salt or a higher fatty acid derivative in which the contact angle &theta;<SB>w</SB>of water on the surface of a mirror surface molded article molded by using the composition and the contact angle &theta;<SB>y</SB>of diiodomethylene satisfy formula 1: 80&deg;&le;&theta;<SB>w</SB>&le;105&deg; and formula 2: 30&deg;&le;&theta;<SB>y</SB>&le;50&deg;. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a polyamide resin composition, and more particularly to an inorganic reinforced polyamide resin composition in which a molded product molded from the polyamide resin composition is excellent in decorating properties by a hydraulic transfer system.

In recent years, there has been a growing demand for high-quality and high-quality molded products by printing patterns and patterns on uneven molded products and plastic molded products with a three-dimensional curved surface. A hydraulic transfer printing method is known.
Hydraulic transfer printing is relatively easy in the case of an amorphous resin such as polycarbonate, polystyrene, and ABS, but is not as easy in the case of a crystalline resin such as polyolefin as in the case of an amorphous resin. As a method for improving the adhesion of a pattern or a pattern by the hydraulic transfer printing method, a pretreatment such as applying a primer to the surface of the molded product (Patent Document 1) or irradiating the surface of the molded product with ultraviolet rays (Patent Document 2). It has been proposed to do.
By the way, regarding polyamide resin, polyamide resin is a crystalline resin, has high water absorption, and inorganic reinforced polyamide resin to which inorganic reinforcing material such as glass fiber is added has an appearance of a molded product (mirror surface gloss, textured surface). There have been few attempts to perform hydraulic transfer printing so far, and there has been no desire to improve hydraulic transfer printability.
JP-A-9-1996 JP-A-10-277479

An object of the present invention is to provide an inorganic reinforced polyamide resin composition that can form a molded article excellent in hydraulic transfer printability and that can omit the pretreatment of the surface of the molded article. It is in.

The composition according to the present invention that has solved the above problems is the following composition.
1. (A) 30 to 70 parts by mass of crystalline polyamide resin, (B) 5 to 60 parts by mass of inorganic reinforcing material, (C) water contact of crystalline polyamide resin with resin that is compatible or dispersible in crystalline polyamide resin 1 to 10 parts by mass of a resin that enhances the corner, (D) a polyamide resin composition containing 0.05 to 2 parts by mass of at least one of a higher fatty acid metal salt and a higher fatty acid derivative, and using the composition hydraulic transfer printing moldings polyamide resin composition for a contact angle theta _w of water to the surface of the mirror molded article and satisfies the following formula 1 molded.
80 ° ≦ θ _w ≦ 105 ° ・ ・ ・ Equation 1
2. Hydraulic transfer printing molded product for the polyamide resin composition according to the 1 contact angle theta _y of methylene iodide to the surface of the mirror molded article satisfies the following Formula 2.
30 ° ≦ θ _y ≦ 50 ° Formula 2
3. 3. The polyamide for hydraulic transfer printing molded article according to 1 or 2 above, wherein the resin that is compatible or dispersible in the crystalline polyamide resin and increases the contact angle of the crystalline polyamide resin is a terpene phenol resin. Resin composition.
4). The polyamide resin composition for hydraulic transfer printing molded article according to any one of 1 to 3, wherein (B) the inorganic reinforcing material is at least one of glass fiber and plate-like crystal reinforcing material.
5. The hydraulic transfer printing molded article according to any one of 1 to 4 above, wherein the crystalline polyamide resin (A) is a blending ratio of 98 to 60 parts by mass of an aliphatic polyamide resin and 2 to 40 parts by mass of a semi-aromatic polyamide resin. Polyamide resin composition.

  According to the inorganic reinforced polyamide resin composition of the present invention, although it is generally an inorganic reinforced polyamide resin composition having poor paintability, the surface of the molded product is further provided with wrinkles or irregularities. Even a molded product having a curved surface can provide a molded product excellent in hydraulic transfer printability. Moreover, the pretreatment of the surface of the molded product can be omitted during the hydraulic transfer printing.

Hereinafter, the present invention will be described in detail.
The polyamide resin composition for hydraulic transfer printing molded article of the present invention is compatible with (A) 30 to 70 parts by mass of crystalline polyamide resin, (B) 5 to 60 parts by mass of inorganic reinforcing material, and (C) crystalline polyamide resin. 1 to 10 parts by mass of a resin capable of increasing the contact angle of water of a crystalline polyamide resin with a dispersible resin, and 0.05 to 2 parts by mass of (D) at least one of a higher fatty acid metal salt and a higher fatty acid derivative. comprising a polyamide resin composition, and the contact angle theta _w of water to the surface of the shaped mirror molded article and satisfies the following formula 1 using the composition.
80 ° ≦ θ _w ≦ 105 ° ・ ・ ・ Equation 1
The contact angle theta _w of water to the surface of the mirror-molded article is preferably 85 ° or more, more preferably 90 ° or more.
In the case of hydraulic transfer printing, if the surface of the molded product is a mirror surface, even if the printability is relatively good, the molded product surface is given a texture or irregularities or has a curved surface, The hydraulic transfer printability may become extremely inferior. In such a case, the higher the contact angle theta _w of water is preferred, tends to become exceeds 105 °, is poor adhesion between the molded article and the transfer ink.
Furthermore, it is preferable that the contact angle θ _y of methylene iodide with respect to the surface of the mirror surface molded product satisfies the following formula 2.
30 ° ≦ θ _y ≦ 50 ° ・ ・ ・ ・ Formula 2
The contact angle θ _y of methylene iodide is more preferably 30 ° ≦ θ _y ≦ 40 °. When θ _y is 50 ° or more, the adhesion between the transfer ink and the molded product is poor. A larger θ _y improves the adhesion between the transfer ink and the molded product, but it is difficult to make θ _y 30 ° or less and θ _w to be in the range of Equation 1.

Further, the polyamide resin composition of the present invention, the contact angle theta _y of 2 methylene iodide to the contact angle theta _w and specular surface of the molded article of the water to the mirror surface of the molded article of the composition, using the formula Owens-Wendt In the surface free energy of the surface of the molded product obtained in this way, γ _sh (hydrogen bond strength component term in the surface energy of the molded product surface) and γ _sd (dispersion force component term in the surface energy of the molded product surface) are expressed by the following equations Is preferably satisfied.
γ _sh ≦ 10 mN / m Equation 3
45 mN / m ≧ γ _sd ≧ 35 mN / m Equation 4

By satisfying Equation 3 and Equation 4, hydraulic transfer printing can be performed stably. Further, γ _sh is more preferably 5 or less.

Nylon 6 or nylon 66 is preferably used as the crystalline polyamide resin (A) used in the present invention. As long as the effects of the present invention are not impaired, aliphatic polyamides such as nylon 46, nylon 612, nylon 610, nylon 11 and nylon 12, poly (metaxylylene adipamide), poly (hexamethylene terephthalamide), poly ( And semi-aromatic polyamides such as hexamethyleneisophthalamide).
The crystallinity in the present invention means that the amount of crystal melting when the resin is heated at 160 ° C. for 1 hour and then heated at 20 ° C./min in a nitrogen atmosphere with a differential scanning calorimeter (DSC) is 3 J / It exceeds g.

The degree of polymerization of the polyamide is not particularly limited, but the relative viscosity (hereinafter referred to as ηr) measured at 25 ° C. in a 98% sulfuric acid concentration of 1% according to JIS K6810 is 1.8 to 3.5, preferably 2. It is 0-3.3, More preferably, it is 2.3-3.2. If ηr is less than 1.8, sufficient mechanical properties such as toughness and rigidity cannot be obtained, and if it is 3.5 or more, the fluidity is lowered and the moldability is deteriorated.
The component (A) in the present invention has a relative viscosity of 2.3 or more as measured by 96% H ₂ SO _{4 of a} molding material that is usually used, but the relative viscosity when used in the present invention is 1.7. A range of ~ 2.2 is preferred. Particularly preferred is a range of 1.9 to 2.1. In addition, if it is less than 1.7, toughness will fall and it is unpreferable, and if it exceeds 2.2, since fluidity | liquidity will fall and the target molded article external appearance will not be obtained, it is unpreferable.

The crystalline polyamide resin in the present invention can be appropriately mixed and used as necessary in order to improve moldability. There are blends of medium-viscosity resins and low-viscosity resins for improving fluidity, and blends of aliphatic polyamide resins and semi-aromatic polyamide resins for preventing silver generation.
In the case of a blend of a medium viscosity resin and a low viscosity resin, in the case of a blend of 90-20 parts by weight of a medium viscosity resin, 10-80 parts by weight of a low viscosity resin, a blend of an aliphatic polyamide resin and a semi-aromatic polyamide resin Is preferably a blending ratio of 98 to 60 parts by mass of the aliphatic polyamide resin and 2 to 40 parts by mass of the semi-aromatic polyamide resin.

  (B) Inorganic reinforcing material in the present invention includes plate-like talc, mica, unfired clay, amorphous and spherical calcium carbonate, silica, glass beads, and commonly used wollastonite And whisker such as acicular wollastonite, glass fiber, carbon fiber, aluminum borate, potassium titanate, milled fiber, which is a short glass fiber having an average particle size of about 4 to 20 μm and a cut length of about 35 to 80 μm, Although not particularly limited, glass fiber is the best in terms of talc, strength, and rigidity in terms of appearance of molded products, and glass fiber in terms of strength, rigidity, and surface gloss of molded products. And talc and / or mica, which are plate-like crystal reinforcing materials, are the most excellent. Examples of mica include phlogopite, sericite, and the like, but sericite is preferred from the viewpoint of the degree of freedom in coloring of the resin (coloring property).

  The compounding quantity of an inorganic reinforcement material is 5-60 mass parts with respect to all the compositions, Preferably it is 20-50 mass parts, More preferably, it is 30-50 mass parts. When the amount is less than 5 parts by mass, the strength and rigidity are lowered. On the other hand, when the amount exceeds 60 parts by mass, a good molded product appearance cannot be obtained, and the strength is also lowered.

  In the present invention, (C) a resin that is compatible or dispersible in the crystalline polyamide resin and that increases the water contact angle of the crystalline polyamide resin is higher in the water contact angle than the crystalline polyamide resin. There is no particular limitation as long as the resin can be blended in the resin, and when molded, the surface of the molded body can increase the contact angle as compared with the case of the crystalline polyamide resin, but it is not limited, but a polar group such as phenolic resin, hydroxyl group or carboxyl group And a fluorine-containing polymer, an olefin resin having a polar group such as a hydroxyl group or a carboxyl group, an acrylate ester resin, a styrene resin, or a silicon resin.

As the phenolic resin, terpene phenol resin, phenol or a phenol substituent derivative (precursor a) and an oligomer obtained by condensation of an aliphatic hydrocarbon having two double bonds (precursor b) are compatible. This is preferable.
As the substituent derivative of phenol as the precursor a, those having 1 to 3 substituents selected from an alkyl group, a halogen atom and a hydroxyl group on the benzene nucleus of the phenol are preferably used. Specific examples thereof include cresol, xylenol, ethylphenol, butylphenol, t-butylphenol, nonylphenol, 3,4,5-trimethylphenol, chlorophenol, bromophenol, chlorocresol, hydroquinone, resorcinol, orcinol. The precursor b is an aliphatic hydrocarbon having two double bonds and may have a cyclic structure.
Examples of the precursor b include butadiene, isoprene, pentadiene, hexadiene, as monocyclic compounds, cyclohexadiene, vinyl cyclohexene, cycloheptadiene, cyclooctadiene, monocyclic represented by molecular formula C ₁₀ H ₁₆ Bicyclic compounds such as monoterpenes (dipentene, limonene, terpinolene, terpinene, ferrandylene) and the like, and bicyclic sesquiterpenes (kadinene, serine, caryophyllene) represented by the molecular formula of 2,5-norbornadiene, tetrahydroindene, C15H24 Etc.), and the like. Examples of tricyclic compounds include dicyclopentadiene.
Among them, terpene phenol resins having a molecular weight of 300 or more are preferable from the viewpoint of miscibility and heat stability, and dipentene-phenol copolymers and α-pinene-phenol copolymers are particularly preferable.

Examples of the polymer containing a polar group such as a hydroxyl group or a carboxyl group and a fluorine group include (1) a copolymer containing, as essential components, fluoroolefin, cyclohexyl vinyl ether, alkyl vinyl ether, and hydroxyalkyl vinyl ether. Typical examples of the fluoroolefin are perhaloolefins such as chlorotrifluoroethylene and tetrafluoroethylene. The molar ratio of the copolymer is 40 to 60% fluoroolefin, 5 to 45% cyclohexyl vinyl ether, 5 to 45% alkyl vinyl ether, and 3 to 15% hydroxyalkyl vinyl ether (Japanese Patent Laid-Open No. 57-34107).
(2) Perfluoroolefin, vinylidene fluoride, and vinyl ester are essential constituents, and their molar ratio is 20 to 80% perfluoroolefin, 5 to 80% vinylidene fluoride, and 3 to 45% vinyl ester. Hydroxyl group-containing fluoropolymer obtained by hydrolyzing a copolymer (Japanese Patent Laid-Open No. 59-174657).
(3) A fluoropolymer obtained by reacting the hydroxyl group-containing fluoropolymer described in the above (1) or (2) with a dibasic acid anhydride for esterification and converting at least one part of the hydroxyl group into a carboxyl group (special No. 58-136605).
Examples of polar group-containing ester resins such as hydroxyl groups or carboxyl groups, and styrene resins include (meth) acrylic acid (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc. Examples include acrylic acid esters, monomers having a hydroxyl group such as vinyl alcohol and hydroxyalkyl vinyl ether, and copolymers such as styrene, such as (meth) acryl / styrene polyol resins having a hydroxyl group and a carboxyl group.

In the present invention, (C) the resin that is compatible or dispersible with the crystalline polyamide resin and increases the water contact angle of the crystalline polyamide resin has an affinity for polyamide by having polar groups such as hydroxyl groups and carboxyl groups. It is considered that the contact angle of water of the crystalline polyamide resin can be increased by the action of the resin skeleton molecules.
In the present invention, the reason why it is possible to suppress the occurrence of transfer failure at the time of hydraulic transfer printing is not clear at the present time, but at the time of hydraulic transfer printing, the infiltration of water between the hydraulic transfer sheet and the molded article to be transferred can be suppressed. This is presumably because the transfer onto the transfer molded body is not hindered.

  (C) As addition amount of a component, it is the range of 1-10 mass parts, A preferable range is 2-9 mass parts, A especially preferable range is 5-8 mass parts. When the addition amount is less than 1 part by mass, the effect of improving the hydraulic transfer printability is small. On the other hand, when it exceeds 10 parts by mass, mechanical and thermal characteristics are deteriorated and the surface of the molded product is peeled off. Absent. Further, when the component (C) is a terpene phenol resin, the molecular weight is preferably 300 or more, particularly preferably 500 or more, and when the molecular weight is less than 300, the thermal stability is poor and decomposition or scattering during processing is not preferable.

  The (D) higher fatty acid metal salt and higher fatty acid derivative in the present invention are a metal salt and derivative of a higher fatty acid having 10 to 40 carbon atoms, and the metal is a metal of Groups I to III of the periodic table. Of these, fatty acid metal salts obtained from fatty acids having 10 to 25 carbon atoms, particularly 12 to 22 carbon atoms, and metals of Groups I to III of the periodic table are preferably used. Examples of fatty acids include stearic acid, palmitic acid, oleic acid, alginic acid, behenic acid, montanic acid, etc., and examples of metals include zinc, calcium, lithium, aluminum, barium, potassium, magnesium, etc. be able to. As examples of the fatty acid metal salt, for example, zinc stearate, calcium stearate, lithium stearate, aluminum stearate, barium stearate, magnesium stearate, calcium montanate and the like are preferably used.

  Commercially available higher fatty acid derivatives include Clariant Japan's Montanic Acid Dihydric Alcohol Ester “Licowax E”, Clariant Japan ’s Partially Saponified Montanic Acid Dihydric Alcohol Ester “Licowax OP” Montanic acid esters and derivatives thereof such as “,” and ethylene glycol esters of melicic acid and derivatives thereof are preferably used.

  As a compounding quantity of a fatty-acid metal salt and a higher fatty acid derivative, it is 0.01-2 mass parts with respect to a resin composition, Preferably it is 0.01-1.0 mass part. When the amount is less than 0.01 parts by mass, good screwing stability cannot be obtained, and a problem easily occurs in the releasability from the mold. If it exceeds 2 parts by mass, poor appearance due to volatile components at the time of molding tends to occur, and it is not economically preferable.

  The polyamide resin composition of the present invention preferably has a melt flow index (275 ° C. × 2160 g load) at a moisture content of 0.05% or less of 2.0 g / 10 min or more. When the melt index is less than 2.0 g / 10 minutes, a good molded product appearance cannot be obtained. In order to obtain an inorganic reinforced polyamide resin composition having a melt flow index of 2.0 g / 10 min or more, a crystalline polyamide having a relative viscosity of 2.3 or more, which is usually used, has poor fluidity and is extremely low to It is preferable to employ a prescription such as using a low-viscosity (relative viscosity 1.7-2.2) crystalline polyamide resin or adding a polyamido molecular chain cleaving agent during compound processing.

  As the polyamide thinning agent (molecular chain cleaving agent), aliphatic dicarboxylic acid, aromatic dicarboxylic acid and the like are effective. Specifically, oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebatin Examples of the acid include phthalic acid, terephthalic acid, and the like. Moreover, the addition amount is about 0.1 to 3 parts by mass with respect to a total of 100 parts by mass of the components (A), (B) and (C) of the present invention, and the melt flow index of the present invention (275 ° C. × 2160 g) 2 0.0 g / 10 min or more. However, the effect of the molecular chain cleaving agent varies depending on the compound processing conditions. Naturally, the higher the processing temperature and the longer the polymer residence time during compounding, the better the effect, and the normal compound processing temperature is in the range of 240 to 300 ° C. The polymer residence time during compounding is generally within 15 to 60 seconds.

  The inorganic reinforced polyamide resin composition of the present invention further includes additives such as stabilizers against deterioration due to oxidation, heat or ultraviolet rays, nucleating agents, plasticizers, mold release agents, flame retardants, antistatic agents, lubricants, colorants. Further, an impact modifier such as an elastomer may be added.

Stabilizers against degradation such as oxidative degradation, thermal degradation or UV degradation include hindered phenols, hydroquinones, phosphites and their substituted antioxidants, resorcinols, salicylates, benzotriazoles, benzophenones In addition, a heat-resistant stabilizer such as an ultraviolet absorber such as a hindered amine or a copper halide or an iodine compound is preferable.
Examples of the copper compound used as the heat resistance stabilizer include copper chloride, copper bromide, copper iodide, copper phosphate, copper ammonium complex, copper stearate, copper montanate, copper adipate, copper propionate, and copper isophthalate. , Copper terephthalate, copper benzoate, copper pyrophosphate, copper acetate, copper ammonia, and the like. Preferably, copper bromide, copper chloride, copper iodide, and copper acetate are used. The compounding quantity of a copper compound is 0.01-1 mass part with respect to 100 mass parts of polyamide resins, Preferably it is 0.01-0.5 mass part. When the amount is less than 0.01 part by mass, sufficient heat resistance cannot be obtained, and when the amount is more than 1 part by mass, discoloration of the polyamide due to water absorption becomes significant.

  Examples of the iodine compound used in the present invention include sodium iodide, potassium iodide, magnesium iodide, ammonium iodide, iodine and the like, preferably potassium iodide. The compounding quantity of this iodine compound is 0.01-1 mass part with respect to 100 mass parts of polyamide resins, Preferably it is 0.3-0.8 mass part. If the amount is less than 0.01 parts by mass, sufficient heat resistance cannot be obtained, but as the amount increases, bleed-out tends to occur at the time of water absorption, and corrosion to metals, particularly corrosion of metals inserted into molded products by insert molding, is likely to occur. Become. Also, care must be taken because the amount of gas generated when the composition melts increases and the smoothness of the surface of the molded article may deteriorate due to the generation of silver.

  As a method for obtaining the composition of the present invention, the above-described components (A) to (D) and others are mixed in an arbitrary mixing order at the above mixing ratio, and then melt-kneaded. Any method known to those skilled in the art can be used as the melt kneading method, and a single screw extruder, a twin screw extruder, a kneader, a twin screw roll, or the like can be used. Among these, it is preferable to use a twin-screw extruder, and glass fibers, milled fibers, and acicular wollastonite, which are inorganic reinforcing materials that are easily damaged during extrusion, are preferably introduced from the side of the twin-screw extruder. It is not limited.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the present invention, unless otherwise specified, all “parts” represent parts by mass. In addition, evaluation of each obtained composition was measured with the following method.

(1) Relative viscosity (sulfuric acid solution method): JIS K-6810 was measured using a Ubbelohde viscometer tube at 20 ° C. and a polymer concentration of 1 g / dl using 96% H ₂ SO ₄ as a solvent.
(2) Moisture content (Karl Fischer method): Measured according to JIS K-6810.
(3) Molding mirror surface finish of test molded body and textured 100 × 150 × 2 mmt mold are used, Toshiba Corporation injection molding machine IS-100, resin temperature = 280 ° C., mold temperature = 80 ° C. Thus, a molded article for test was obtained.
In addition, the embossment has a depth of 7 μm and a pitch of 70 μm and has recesses formed therein.
Further, the obtained molded body for surface texture test was subjected to a load at the center with the end of the molded body fixed using a bending tester (Tensilon UCT500 manufactured by Orient Corporation) to form a loose curved surface of R700. .
(4) Contact angle measurement:
Using a contact angle meter manufactured by Kyowa Interface Science Co., Ltd., the contact angles θ _w and θ _y of water and methylene iodide on the surface of the test molded body were measured under conditions of normal temperature and normal humidity (20 ° C., 60% RH).
Further, from these measured values, the hydrogen bonding force component term γ _sh and the dispersion force component term γ _sd in the surface energy were also calculated by the above formulas 3 and 4.
(5) Hydraulic transfer sheet The surface of a base film made of a water-soluble film (Nippon Synthetic Film Co., Ltd .: Hi-Selon) with a thickness of 40 μm is coated with the following printing color ink from a line width of 2 mm and the center of the line. A transfer printing layer having a grid pattern with a distance of 5 mm to the center of the adjacent line was formed by a gravure printing method to obtain a hydraulic transfer sheet.
Colored ink: 10.0 parts by mass of diketopyrrolopyrrole, 22.8 parts by mass of vinylidene fluoride resin, 7.1 parts by mass of acrylic polyol resin, 3.0 parts by mass of fluoro wax (dispersant) by tetrafluoroethylene resin, Methyl ethyl ketone (true solvent) 10.0 parts by mass, slow dry solvent 47.1 parts by mass, slow dry solvent (toluene: 24.5 parts by mass, ethyl acetate: 10.0 parts by mass, butyl acetate: 12.6 parts by mass)

(6) Water pressure transfer test After applying the active agent of the following mixed composition (i) to 13 g / m ² by spray coating method on the printing layer surface for transfer in the water pressure transfer sheet, the water surface at a water temperature of 30 ° C. Floating so that the surface of the transfer printing layer coated with the activator is the upper surface, and after 1 minute, the test molded body was pushed in from above, and the transfer sheet was spread and adhered to the surface of the molded body .
Next, the test molded body with the water pressure transfer sheet spread and adhered to the surface is pulled out from the water, showered with warm water at 40 ° C. for 30 minutes, and then showered with fresh water to remove the base film from the water pressure transfer sheet. Then, through a drying process, a test molded body having a cross-patterned transfer layer by hydraulic transfer was obtained.
Mixing composition of activator (i)
26 parts by mass of butyl cellosolve acetate, 26 parts by mass of butyl carbitol acetate, 8 parts by mass of butyl methacrylate polymer, 20 parts by mass of dibutyl phthalate, 20 parts by mass of barium sulfate (powder).

(7) Evaluation of hydraulic transferability Using the above-described hydraulic transfer sheet, the transfer state of the grid pattern to the test molded body by hydraulic transfer was evaluated.
○: No transfer failure is observed at all (cross-cut pattern is clearly transferred).
(Triangle | delta): Transfer defect is recognized slightly (a transfer defect part exists in a part of grid pattern).
X: Transfer defects are remarkably recognized (transfer defective portions are present in a part of the grid pattern).

Examples 1-6, Comparative Example 1
After adjusting the mixture which added 0.02 mass part of copper iodide and 0.15 mass part of potassium iodide to the compound composition shown in Table 1 as a heat-resistant stabilizer, it is a polyamide resin composition using a 35 (phi) twin screw extruder. Product pellets were produced. The resin temperature at that time was 230 to 290 ° C., and the screw rotation speed was 70 to 120 rpm. The pelletized resin composition extruded from the extruder was dried to a moisture content of 0.05% or less, and then a test molded body was molded for evaluation. The results are shown in Table 1.

In Table 1, the raw materials used are as follows.
Medium viscosity nylon 6: manufactured by Toyobo Co., Ltd., Toyobo nylon T-800, melting point 222 ° C., ηr2.5.
Low viscosity nylon 6: manufactured by Toyobo Co., Ltd., Toyobo nylon T-840, melting point 222 ° C., ηr2.2.
MXD6: poly (metaxylylene adipamide), relative viscosity (ηr) = 2.1.
-Terpene phenol resin * 1: YS Polystar S145 manufactured by Yasuhara Chemical Co., Ltd.
Polar group and fluorine-containing polymer * 2: fluoroolefin-cyclohexyl vinyl ether-hydroxyethyl vinyl ether copolymer.
Acrylic / styrene polymer * 3: butyl methacrylate-hydroxyethyl vinyl ether-styrene copolymer.
Glass fiber: Nippon Glass Fiber Co., Ltd., RES03-TP57E.
-Talc: KST-W, manufactured by Katsumitsu Mining Co., Ltd.
Wollastonite: FPW # 800 manufactured by Kinsei Maitech Co., Ltd.

The polyamide resin composition of the present invention is a polyamide resin composition that can form a molded article excellent in hydraulic transfer printability, and is an inorganic reinforced polyamide resin composition that can omit the pretreatment of the surface of the molded article. For this reason, it is possible to provide polyamide resin-based molded products and parts having excellent design properties for automobiles and electrical products, which contribute to the industry.

Claims (5)

(A) 30 to 70 parts by mass of crystalline polyamide resin, (B) 5 to 60 parts by mass of inorganic reinforcing material, (C) water contact of crystalline polyamide resin with resin that is compatible or dispersible in crystalline polyamide resin 1 to 10 parts by mass of a resin that enhances the corner, (D) a polyamide resin composition containing 0.05 to 2 parts by mass of at least one of a higher fatty acid metal salt and a higher fatty acid derivative, and using the composition hydraulic transfer printing moldings polyamide resin composition for a contact angle theta _w of water to the surface of the mirror molded article and satisfies the following formula 1 molded.
80 ° ≦ θ _w ≦ 105 ° Formula 1 2. The polyamide resin composition for hydraulic transfer printing molded article according to claim 1, wherein a contact angle θ _y of methylene iodide with respect to the surface of the mirror molded article satisfies the following formula 2.
30 ° ≦ θ _y ≦ 50 ° Formula 2   The hydraulic transfer printing molded article according to claim 1 or 2, wherein the resin that is compatible or dispersible with the crystalline polyamide resin (C) and that increases the contact angle of the crystalline polyamide resin is a terpene phenol resin. Polyamide resin composition.   The polyamide resin composition for hydraulic transfer printing molded article according to any one of claims 1 to 3, wherein the (B) inorganic reinforcing material is at least one of glass fiber and plate crystal reinforcing material. The hydraulic transfer printing molded article according to any one of claims 1 to 4, wherein the (A) crystalline polyamide resin is a blending ratio of 98 to 60 parts by mass of an aliphatic polyamide resin and 2 to 40 parts by mass of a semi-aromatic polyamide resin. Polyamide resin composition.