KR20200047594A - A molded article having a molded article containing a semi-aromatic polyamide resin composition as a component - Google Patents

Abstract

The molded article of the present invention is a semi-aromatic polyamide resin (A) in which the sum of peak area, glass transition temperature and terminal amino group concentration and terminal carboxyl group concentration according to temperature crystallization measured by differential scanning calorimetry (DSC) satisfies specific requirements. ) A molded article (D) containing a semi-aromatic polyamide resin composition (C) containing 0 to 200 parts by mass of a reinforcing material (B) and having an equilibrium absorption rate of 80% to 95% RH of 3.0% or less with respect to 100 parts by mass, and glycine It is a molded article having a structure in which a thermosetting resin (E) containing a dill group is directly interposed, and is a molded article having high absorbent dimensional stability, heat resistance and adhesion.

Description

A molded article having a molded article containing a semi-aromatic polyamide resin composition as a component

The present invention relates to a molded article comprising a semi-aromatic polyamide resin composition excellent in absorbent dimensional stability and heat resistance, and a thermosetting resin containing a glycidyl group, having a high adhesive property and having a directly interposed structure. will be.

Polyamide resins have been used for medical, industrial materials, engineering plastics, etc., taking advantage of their excellent properties and ease of melt molding. In recent years, with the development of technology in each field, the use of the polyamide resin has been expanded, and is used in various applications ranging from automobile parts around the engine to electric and electronic parts represented by smartphones.

With the expansion of use, the method of joining parts together has attracted attention, while the shape and configuration of parts using polyamide resins are multifaceted. As the main example, there is a method of fastening with screws or screws, etc., but there are cases where physical fastening is difficult due to the efficiency of the product manufacturing process and the miniaturization of parts. As a new bonding method, various welding methods or thermosetting properties are used. Bonding by resin is advancing. Particularly in the electrical and electronic fields, sealing with thermosetting resins is generalized to prevent malfunction of devices due to a small amount of moisture or foreign matter that intrudes from the outside while the product is being refined, and these thermosetting resins are used in the polyamide resins used. High adhesion with and is strongly required.

In addition, in the polyamide resin, the effect on the product quality by absorption under the use environment is often a problem. Since the polyamide resin absorbs moisture in the atmosphere, its dimensions change, resulting in fluctuations in product dimensions, leading to poor assembly and poor operation. In addition, in the solder reflow process that is generalized in the electric and electronic fields, swelling (blister) of the product due to absorption occurs, leading to occurrence of product defects. PA6, PA66, modified PA6T, etc., which are widely used in the market, have a high saturation absorption rate of 6% or more of the resin, and thus the above-mentioned problems are likely to occur. Therefore, there is a need for a polyamide resin having low water absorption that is more difficult to absorb.

As described above, various polyamide resin compositions have been developed as market demands change. Patent Document 1 discloses a carbon fiber-reinforced polyamide resin composition excellent in metal adhesion, including a semi-aromatic polyamide, a carbon fiber, and an epoxy compound. However, in the technique described in the document, it is essential to include the epoxy compound in the resin composition, and since the heat resistance of the epoxy compound is low, the outgas increases during processing at a high temperature, and the formability of the molded article significantly decreases. Have difficulty.

In addition, Patent Document 2 discloses a semiaromatic polyamide resin mainly made of PA9T, which has excellent adhesion to other resins. In other words, in the technique described in this document, in other words, the amount of the terminal amino group of the semi-aromatic polyamide is 60 to 120 µ equivalent / g, and the ratio represented by (the amount of terminal amino groups) / (the amount of terminal carboxyl groups) is 6 or more. , In addition to the amount of terminal amino groups, by controlling the amount of terminal carboxyl groups in the range of 10 to 20 μ equivalent / g, high adhesion to other resins is obtained. However, in this document, a technique for expressing high adhesion in a polyamide resin having a high amount of terminal carboxyl groups is not disclosed.

Patent Document 3 discloses a molded article comprising a polyamide resin member, an adhesive layer in contact with the polyamide member, and a metal member. However, the technique described in this document is different from the technique of the present invention because a thermoplastic polyolefin elastomer or a thermoplastic polyether elastomer in which at least one of maleic acid and maleic anhydride is grafted to the adhesive layer is essential.

As described above, various inventions have been made to obtain high adhesiveness between a polyamide resin and other resins or materials, but there are various problems and limitations as a polyamide resin composition or an adhesive layer.

Patent Document 1: Japanese Patent Publication No. 2015-129271 Patent Document 2: International Publication WO2006 / 098434 Patent Document 3: Japanese Patent Publication No. 2017-140768

The present invention was devised in view of the present situation of the prior art, and its purpose is to directly interpose a molded article containing a semiaromatic polyamide resin composition and a thermosetting resin containing a glycidyl group with high adhesion. It is to provide a molded article having a structure, excellent absorbent dimensional stability, and heat resistance.

In order to achieve the above object, the present inventors, by using a resin composition containing a semi-aromatic polyamide resin having specific properties such as the amount of end groups, etc. in addition to the composition, and a thermosetting resin having a glycidyl group, have high absorption dimensions. It has come to provide a molded body having stability, heat resistance, and adhesiveness. Since this molded article is a molded article comprising a semi-aromatic polyamide resin composition and a thermosetting resin having a glycidyl group directly, it can also be referred to as a composite molded article. It was also found that the adhesiveness was improved by blending a specific ratio of a styrene-maleimide-based copolymer in the resin composition.

That is, this invention has the following structures.

(1) Containing 0 to 200 parts by mass of a reinforcing material (B) with respect to 100 parts by mass of the semi-aromatic polyamide resin (A) that satisfies the following requirements (a) to (c), and an equilibrium absorption rate of 80% at 95% RH 3.0 A molded article having a structure in which a molded article (D) comprising a semiaromatic polyamide resin composition (C) of% or less and a thermosetting resin (E) containing a glycidyl group are directly interposed.

(a) The peak area (ΔH _Tc2 ) according to the crystallization of temperature measured by differential scanning calorimetry (DSC) is 40 mJ / mg or less

(b) The glass transition temperature (Tg) is 120 ° C or less

(c) The sum (AEG + CEG) of the terminal amino group concentration (AEG) and the terminal carboxyl group concentration (CEG) is 70 eq / ton or more.

(2) The semi-aromatic polyamide resin composition (C) further contains 10 to 60 parts by mass of a styrene-maleimide-based copolymer (F) with respect to 100 parts by mass of the semi-aromatic polyamide resin (A) (1) The molded article described in.

(3) The semi-aromatic polyamide resin (A) contains 50 to 100 mol% of repeating units containing diamine having 6 to 12 carbons and terephthalic acid, and 0 to 0 of repeating units containing aminocarboxylic acid or lactam having 10 or more carbon atoms. The molded article according to (1) or (2), which is a semiaromatic polyamide resin containing 50 mol%.

(4) The semi-aromatic polyamide resin (A) contains 50 to 100 mol% of repeating units comprising hexamethylenediamine and terephthalic acid, and 0 to 50 mol% of repeating units containing aminoundecanoic acid or undecanactam. The molded article according to (1) or (2), which is an aromatic polyamide resin.

(5) The molded article according to any one of (1) to (4), wherein the thermosetting resin (E) containing a glycidyl group is a one-component thermosetting epoxy resin.

(6) A connector comprising the molded article according to any one of (1) to (5).

(7) A switch component comprising the molded article according to any one of (1) to (5).

(8) A camera component comprising the molded article according to any one of (1) to (5).

According to the present invention, a molded article comprising a semi-aromatic polyamide resin composition and a thermosetting resin having a glycidyl group, having high absorption dimensional stability, heat resistance, and adhesion, comprising the semi-aromatic polyamide resin composition It is possible to provide a composite molded article in which a thermosetting resin having a molded article and a glycidyl group is directly interposed. Here, intervening directly indicates that the bonding is directly performed.

1 is a schematic view showing the shape of a test piece for evaluation of adhesive strength performed in Examples.
Fig. 2 is a schematic view showing a method for producing a test piece for evaluation of adhesive strength performed in Examples.

Hereinafter, the molded body of the present invention will be described.

The molded article of the present invention contains 0 to 200 parts by mass of the reinforcing material (B) and 100 parts by mass of the semi-aromatic polyamide resin (A) satisfying the following requirements (a) to (c), and 95% RH at 80 ° C. It is characterized by having a structure in which a molded article (D) containing a semi-aromatic polyamide resin composition (C) having an equilibrium absorption rate of 3.0% or less and a thermosetting resin (E) containing a glycidyl group are directly interposed.

(a) The peak area (ΔH _Tc2 ) according to the crystallization of temperature measured by differential scanning calorimetry (DSC) is 40 mJ / mg or less

(b) The glass transition temperature (Tg) is 120 ° C or less

(c) The sum (AEG + CEG) of the terminal amino group concentration (AEG) and the terminal carboxyl group concentration (CEG) is 70 eq / ton or more.

It is a preferable aspect that the semi-aromatic polyamide resin composition (C) further contains 10 to 60 parts by mass of a styrene-maleimide-based copolymer (F) with respect to 100 parts by mass of the semi-aromatic polyamide resin (A).

The semi-aromatic polyamide resin (A) used in the present invention is not particularly limited, and is a semi-aromatic polyamide having an acid amide bond (-CONH-) in the molecule and an aromatic ring (benzene ring).

Examples of semiaromatic polyamides include 6T-based polyamides (e.g., polyamide 6T6I containing terephthalic acid / isophthalic acid / hexamethylenediamine, polyamide 6T66 containing terephthalic acid / adipic acid / hexamethylenediamine, terephthalic acid / isophthalic acid) Polyamide 6T6I66 with / adipic acid / hexamethylenediamine, polyamide 6T / M-5T with terephthalic acid / hexamethylenediamine / 2-methyl-1,5-pentamethylenediamine, terephthalic acid / hexamethylenediamine / ε -Polyamide 6T6 with caprolactam, polyamide 6T / 4T with terephthalic acid / hexamethylenediamine / tetramethylenediamine), 9T-based polyamide (terephthalic acid / 1,9-nonanediamine / 2-methyl-1,8 -Octanediamine), 10T-based polyamide (terephthalic acid / 1,10-decanediamine), 12T-based polyamide (terephthalic acid / 1,12-dodecanediamine), sebacic acid / polyamide containing paraxylenediamine, etc. Can.

The semi-aromatic polyamide resin (A) used in the present invention needs to have a peak area (ΔH _Tc2 ) of 40 mJ / mg or less due to crystallization at a temperature measured by the method described in the section of Examples below. Moreover, it is preferable that it is 35 mJ / mg or less, and it is more preferable that it is 30 mJ / mg or less. When ΔH _Tc2 exceeds the above upper limit, the adhesiveness with the thermosetting resin (E) decreases, and there is a possibility that the required strength as a molded body may not be achieved, which is not preferable. The lower limit of ΔH _Tc2 is 5 mJ / mg, more preferably 10 mJ / mg or more. If it is below the lower limit, there is a possibility that the molding cycle time becomes long and production efficiency decreases. In addition, when the obtained molded body is subjected to secondary processing under a high temperature environment, there is a possibility of dimensional change or deformation, which is not preferable.

The semi-aromatic polyamide resin (A) used in the present invention needs to have a glass transition temperature (Tg) of 120 ° C. or less as measured by the method described in the following Examples. Moreover, it is preferable that it is 110 degrees C or less, and it is more preferable that it is 100 degrees C or less. When Tg exceeds the above upper limit, the mobility of the molecular chain is extremely limited at the curing treatment temperature of the thermosetting resin (E), and the adhesiveness with the thermosetting resin (E) decreases, so that the required strength as a molded body can be achieved. This is not desirable because it is possible. The lower limit of Tg is 50 ° C or higher, preferably 60 ° C or higher, and more preferably 70 ° C or higher. When the temperature is below the lower limit, the molded body may soften depending on the use environment, which may cause deformation or malfunction of the product, which is not preferable.

In the semi-aromatic polyamide resin (A) used in the present invention, the sum of the terminal amino group concentration (AEG) and the terminal carboxyl group concentration (CEG) (AEG + CEG) needs to be 70 eq / ton or more. Moreover, it is preferable that it is 80 eq / ton or more, and it is more preferable that it is 100 eq / ton or more. When (AEG + CEG) is less than the above lower limit, the adhesiveness with the thermosetting resin (E) decreases, and there is a possibility that the strength required as a molded body may not be achieved, which is not preferable. The upper limit of (AEG + CEG) is preferably 200 eq / ton or less, more preferably 180 eq / ton or less, and even more preferably 160 eq / ton. When the above upper limit is exceeded, the reaction between the end groups due to heat during processing may occur, which may cause problems in retention stability, which is not preferable.

The semi-aromatic polyamide resin (A) used in the present invention preferably has a terminal amino group concentration (AEG) of 2 eq / ton or more, more preferably 10 eq / ton or more, and even more preferably 15 eq / ton or more. , 20 eq / ton or more is particularly preferred. Even if the terminal amino group concentration is below the lower limit, the semi-aromatic polyamide resin (A) used in the present invention has excellent adhesion to the thermosetting resin (E), so that the molded article of the present invention has sufficient adhesive strength, but the terminal amino group concentration It is preferable to make it more than the said lower limit, since higher adhesive strength can be obtained.

The semi-aromatic polyamide resin (A) used in the present invention preferably has a terminal carboxyl group concentration (CEG) of 20 eq / ton or more, more preferably 30 eq / ton or more, and even more preferably 40 eq / ton or more. . It is preferable because the adhesiveness with the thermosetting resin (E) can be enhanced by setting the terminal carboxyl group concentration to be more than the above lower limit.

The semi-aromatic polyamide resin (A) used in the present invention preferably has a larger CEG than AEG. CEG / AEG is preferably 2 or more, and more preferably 5 or more.

The semi-aromatic polyamide resin (A) used in the present invention preferably has a DSC melting peak temperature (Tm) of 280 ° C. or higher located at the lowest temperature measured by the method described in the section of Examples below. Moreover, it is more preferable that it is 290 degreeC or more, and it is still more preferable that it is 300 degreeC or more. When Tm is less than the lower limit, when the molded article of the present invention is processed in a solder reflow step, it is not preferable because there is a possibility that the molded article may melt or deform. The upper limit of Tm is preferably 340 ° C or lower, more preferably 330 ° C or lower, and even more preferably 320 ° C or lower. When Tm exceeds the above upper limit, the processing temperature during molding is very high, which is not preferable because of the possibility of decomposition of the resin due to heat.

The semi-aromatic polyamide resin (A) used in the present invention is preferably the following semi-aromatic polyamide resin from the viewpoints of ΔH _Tc2 , Tg, and Tm.

In the semi-aromatic polyamide resin (A), 50 to 100 mol% of repeating units containing diamine having 6 to 12 carbons and terephthalic acid, 0 to 50 mol% of repeating units containing aminocarboxylic acid or lactam having 10 or more carbon atoms It is preferably a semi-aromatic polyamide resin containing 50 to 98 mol% of repeating units comprising diamine having 6 to 12 carbons and terephthalic acid, and 2 to 50 repeating units containing aminocarboxylic acid or lactam having 10 or more carbon atoms. It is more preferable that it is a semi-aromatic polyamide resin containing mol%, and 55 to 98 mol% of repeating units comprising diamine having 6 to 12 carbons and terephthalic acid, and repeating units containing aminocarboxylic acid or lactam having 10 or more carbon atoms. It is more preferable that it is a semi-aromatic polyamide resin containing 2 to 45 mol%.

When the proportion of the repeating units containing diamine having 6 to 12 carbon atoms and terephthalic acid in the semi-aromatic polyamide resin (A) is less than 50 mol%, the molding cycle time due to the decrease in ΔH _Tc2 becomes longer, and the Tm decreases. In the solder reflow process due to the melting or deformation of the molded body, there is a possibility of problems due to softening of the molded body in the use environment due to a decrease in Tg, which is not preferable. On the other hand, since the ΔH _Tc2 , Tg, and Tm of the _semiaromatic polyamide resin (A) can be appropriately improved, the proportion of repeating units containing diamine having 6 to 12 carbon atoms and terephthalic acid in the semiaromatic polyamide resin (A) It is more preferable to make 55 mol% or more (45 mol% or less of a repeating unit containing aminocarboxylic acid or lactam having 10 or more carbon atoms), and 60 mol% or more (containing aminocarboxylic acid or lactam having 10 or more carbon atoms). It is more preferable that the repeating unit is 40 mol% or less).

As the diamine component having 6 to 12 carbon atoms constituting the semi-aromatic polyamide resin (A), 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, and 1,9-nonamethylene Diamine, 2-methyl-1,8-octamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, and 1,12-dodecamethylenediamine. These may be used alone or in plural.

As an aminocarboxylic acid having 10 or more carbon atoms or a lactam having 10 or more carbon atoms constituting the semi-aromatic polyamide resin (A), an aminocarboxylic acid having 11 to 18 carbon atoms or lactam is preferable. Among them, 11-aminoundecanoic acid, undecanlactam, 12-aminododecanoic acid, and 12-lauryllactam are preferred.

In the semi-aromatic polyamide resin (A) used in the present invention, other components can be copolymerized at 50% mol or less in the constituent units. Other diamine components that can be copolymerized include 1,13-tridecamethylenediamine, 1,16-hexadecamethylenediamine, 1,18-octadecamethylenediamine, 2,2,4 (or 2,4,4) -trimethylhexa Aliphatic diamines such as methylenediamine, piperazine, cyclohexanediamine, bis (3-methyl-4-aminohexyl) methane, bis- (4,4'-aminocyclohexyl) methane, alicyclic diamines such as isophoronediamine, And aromatic diamines such as metaxylylenediamine, paraxylylenediamine, paraphenylenediamine, and metaphenylenediamine, and their hydrogenated products.

As other copolymerizable acid components, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 2,2'- Aromatic dicarboxylic acids such as diphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sulfonic acid sodium isophthalic acid, and 5-hydroxyisophthalic acid, fumaric acid, maleic acid, succinic acid, and itaconic acid , Adipic acid, azelaic acid, sebacic acid, 1,11-undecanic acid, 1,12-dodecanic acid, 1,14-tetradecanic acid, 1,18-octadecaneic acid, 1,4 -Aliphatic acids such as cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, and dimer acid And alicyclic dicarboxylic acid.

Moreover, epsilon-caprolactam etc. are mentioned as another component which can be copolymerized.

Among the above components, from the viewpoint of ΔH _Tc2 , Tg and Tm, it is preferable to copolymerize one or more kinds of aminocarboxylic acids having 11 to 18 carbon atoms or lactams having 11 to 18 carbon atoms as the copolymerization component.

The semi-aromatic polyamide resin (A) used in the present invention is 50 to 100 mol% of repeating units comprising hexamethylenediamine and terephthalic acid, and 0 to 50 mol% of repeating units comprising aminoundecanoic acid or undecanactam. It is preferably a semi-aromatic polyamide resin containing a half containing 50 to 98 mol% of repeating units comprising hexamethylenediamine and terephthalic acid and 2 to 50 mol% of repeating units comprising aminoundecanoic acid or undecanactam. It is more preferable that it is an aromatic polyamide resin, and semi-aromatic poly containing 55 to 80 mol% of repeating units containing hexamethylenediamine and terephthalic acid and 20 to 45 mol% of repeating units containing aminoundecanoic acid or undecanactam. It is more preferable that it is an amide resin, and 60 to 70 mol% of a repeating unit containing hexamethylenediamine and terephthalic acid, aminoundecanoic acid or undecanelactam is used. Is a repeating unit should the semi-aromatic polyamide resin containing 30 to 40% by mole is particularly preferable.

When the ratio of the repeating units containing hexamethylenediamine and terephthalic acid in the semi-aromatic polyamide resin (A) is less than 50 mol%, the molding cycle time is prolonged due to the decrease in ΔH _Tc2 , and soldering due to the decrease in Tm. There is a possibility that a problem occurs due to melting or deformation of the molded body in the reflow process, and softening of the molded body in the use environment due to a decrease in Tg. On the other hand, by controlling the proportion of repeating units containing hexamethylenediamine and terephthalic acid in the semi-aromatic polyamide resin (A) to 55 to 80 mol%, controlling the crystallinity and molecular mobility of the semi-aromatic polyamide resin (A) It is more preferable because ΔH _Tc2 , Tg, and Tm can be appropriately improved. In addition, by setting the ratio of the repeating units containing hexamethylenediamine and terephthalic acid in the semi-aromatic polyamide resin (A) to 60 to 70 mol%, Tm can be in the range of 300 ° C to 320 ° C, making molding easy. In addition to this, ΔH _Tc2 is more preferably 10 to 35 mJ / mg, Tg to 70 to 100 ° C, and high adhesion to the thermosetting resin (E) can be obtained.

Examples of the catalyst used when producing the semi-aromatic polyamide resin (A) include phosphoric acid, phosphorous acid, hypophosphorous acid, or metal salts, ammonium salts and esters thereof. Specific examples of the metal species of the metal salt include potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony. Examples of the ester include ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, and phenyl ester. Moreover, it is preferable to add alkali compounds, such as sodium hydroxide, potassium hydroxide, and magnesium hydroxide, from a viewpoint of improving melt retention stability.

The relative viscosity (RV) measured at 20 ° C in 96% concentrated sulfuric acid of the semi-aromatic polyamide resin (A) is preferably 0.4 to 4.0, more preferably 1.0 to 3.0, and even more preferably 1.5 to 2.5. As a method of making the relative viscosity of the polyamide within a certain range, means for adjusting the molecular weight may be mentioned.

In the semi-aromatic polyamide resin (A), the amount and molecular weight of the end groups of the polyamide can be adjusted by a method of polycondensing by adjusting the molar ratio of the amino group and the carboxyl group or by adding a terminal sealant.

Examples of the timing for adding the terminal sealant include injection of raw materials, starting of polymerization, late polymerization, or termination of polymerization. The terminal sealant is not particularly limited as long as it is a monofunctional compound having reactivity with an amino group or a carboxyl group at the polyamide terminal, but an acid anhydride such as monocarboxylic acid or monoamine or phthalic anhydride, monoisocyanate, monoacid halide, Monoesters, monoalcohols, etc. can be used. Examples of the terminal sealing agent include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, capronic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid. , Aromatic monocarboxylic acids such as alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid, Acid anhydrides such as maleic anhydride, phthalic anhydride and hexahydrophthalic anhydride, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropyl Aliphatic monoamines such as amine and dibutylamine, alicyclic monoamines such as cyclohexylamine and dicyclohexylamine, aromatic mothers such as aniline, toluidine, diphenylamine, and naphthylamine There may be mentioned amines or the like.

The semi-aromatic polyamide resin (A) can be produced by a conventionally known method, and can be easily synthesized by, for example, co-condensing a raw material monomer. The order of the co-polymerization reaction is not particularly limited, and all the raw material monomers may be reacted at once, or some of the raw material monomers may be reacted first, followed by the remaining raw material monomers. In addition, the polymerization method is not particularly limited, and may proceed from raw material injection to polymer production in a continuous process, and once the oligomer is produced, polymerization is performed by an extruder or the like in another process, or the oligomer is solidified. A method such as high molecular weight polymerization may be used. By adjusting the injection ratio of the raw material monomer, the ratio of each constituent unit in the synthesized copolymerized polyamide can be controlled.

The reinforcing material (B) used in the present invention is blended in order to improve the moldability of the semi-aromatic polyamide resin composition (C) and the strength of the molded article (D) containing the semi-aromatic polyamide resin composition (C). It is preferable to use at least one selected from a mold reinforcement and a needle reinforcement. Examples of the fibrous reinforcing material include glass fibers, carbon fibers, boron fibers, ceramic fibers, and metal fibers. Examples of the needle reinforcing materials include potassium titanate whiskers, aluminum borate whiskers, zinc oxide whiskers, calcium carbonate whiskers, and magnesium sulfate. Whiskers, wollastonite, and the like. As the glass fiber, it is possible to use a chopped strand or continuous filament fiber having a length of 0.1 mm to 100 mm. As the cross-sectional shape of the glass fiber, glass fibers having a circular cross section and a non-circular cross section can be used. The diameter of the circular cross-section glass fiber is 20 µm or less, preferably 15 µm or less, and more preferably 10 µm or less. In addition, glass fibers having a non-circular cross section are preferred from the viewpoint of physical properties and fluidity. The glass fiber having a non-circular cross-section includes those that are approximately elliptical, approximately elliptical and approximately cocoon in a cross section perpendicular to the longitudinal direction of the fiber length, and preferably have a flatness of 1.5 to 8. Here, the flatness is assumed to be a rectangle having the smallest area circumscribed in a section perpendicular to the longitudinal direction of the glass fiber, and the length of the long side of this rectangle is the long diameter, and the length of the short side is the short diameter. It is rain. The thickness of the glass fiber is not particularly limited, but the short diameter is about 1 to 20 μm and the long diameter is about 2 to 100 μm. Moreover, the glass fiber is a fiber bundle, and it is preferable to use a chopped strand type cut into fibers of about 1 to 20 mm in length. Further, in order to improve the affinity with the polyamide resin, the fibrous reinforcing material is preferably treated with an organic treatment or a coupling agent, or in combination with a coupling agent during melt compounding. As the coupling agent, a silane coupling agent, Either a titanate-based coupling agent or an aluminum-based coupling agent may be used, but among them, an aminosilane coupling agent and an epoxysilane coupling agent are particularly preferable.

The reinforcing material (B) used in the present invention needs to be 0 to 200 parts by mass relative to 100 parts by mass of the semiaromatic polyamide resin (A). Moreover, 10-200 mass parts is preferable, 10-180 mass parts is more preferable, and 15-160 mass parts is more preferable. When the proportion of the reinforcing material (B) exceeds the above upper limit, the adhesion decreases because the proportion of the semi-aromatic polyamide resin (A) directly contacting the thermosetting resin (E) decreases upon adhesion to the thermosetting resin (E). There is a possibility to do so, which is not preferable. On the other hand, the lower limit of the ratio of the reinforcing material (B) is 0 parts by mass, although some products may exhibit sufficient strength of the molded body even if the reinforcing material (B) is not used. It is preferable to make it into mass parts or more, and it is more preferable to make it into 15 mass parts or more.

The styrene-maleimide-based copolymer (F) used in the present invention is preferably 10 to 60 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide resin (A). Moreover, 12-50 mass parts is preferable, and 15-40 mass parts is more preferable. When the ratio of the styrene-maleimide-based copolymer (F) is less than the above lower limit, there is a possibility that the adhesiveness may decrease upon adhesion with the thermosetting resin (E), which is not preferable. When the ratio of the styrene-maleimide-based copolymer (F) exceeds the above upper limit, the fluidity during injection molding decreases, and there is a possibility that the appearance of the molded body decreases, which is not preferable.

The styrene-maleimide-based copolymer (F) used in the present invention is a copolymer containing a styrene-based monomer and a maleimide-based monomer as constituent components. Maleic anhydride may be copolymerized in the styrene-maleimide-based copolymer (F) for the purpose of improving the compatibility with the semi-aromatic polyamide resin (A). The ratio of the constituent components of the styrene-maleimide-based copolymer (F) is not particularly limited, but examples of specific constituent components include 25 to 40 mol% of styrene-based monomers, 50 to 70 mol% of N-phenylmaleimide, and maleic anhydride. And 5 to 15 mol%. As a commercial product, Denka IP MS-NIP by Tenka Corporation is mentioned.

The semi-aromatic polyamide resin composition (C) used in the present invention is not only for suppressing the dimensional change in the actual use environment of the molded article obtained by the present invention, but also in the solder reflow process used in the mounting of electrical and electronic components. In order to suppress the generation of the emitter, it is necessary that the equilibrium absorption rate at 80 ° C 95% RH measured by the method described in the Examples section below is 3.0% (3.0% by mass) or less. Further, it is preferable that the equilibrium absorption rate at 80 ° C of 95% RH is 2.5% or less. When the 80% 95% RH equilibrium absorption rate exceeds the above upper limit, the absorbed dimensional change of the resulting molded article may be large, causing problems during product assembly or product operation, or blistering in the solder reflow process, leading to product failure. This is not desirable. The lower limit of the 80% 95% RH equilibrium absorption rate is 0%, but about 1.0% is preferable due to the properties of the semi-aromatic polyamide resin (A) used in the present invention.

Various additives used in the conventional polyamide resin composition can be used for the semi-aromatic polyamide resin composition (C) used in the present invention. Examples of the additives include stabilizers, impact modifiers, mold release agents, slidability modifiers, colorants, plasticizers, crystal nucleating agents, polyamides other than semiaromatic polyamide resins (A), and thermoplastic resins other than polyamides. The possible blending amounts of these components in the semi-aromatic polyamide resin composition (C) are as described below, but the total of these components is preferably 30% by mass or less, and 20% by mass or less, in the semi-aromatic polyamide resin composition (C). % Or less is more preferable, 10 mass% or less is more preferable, and 5 mass% or less is particularly preferable.

In the present invention, the semi-aromatic polyamide resin composition (C) also includes a case in which only the semi-aromatic polyamide resin (A) is included, and in this case, it is also referred to as a semi-aromatic polyamide resin composition (C) for convenience.

As the stabilizer, organic antioxidants such as hindered phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants or thermal stabilizers, light stabilizers such as hindered amine-based, benzophenone-based, imidazole-based, ultraviolet absorbers, and metal inactivators And copper compounds. As the copper compound, cuprous chloride, cupric bromide, cupric iodide, cupric chloride, cupric bromide, cupric bromide, cupric iodine, cupric phosphate, cupric pyrophosphate, cupric sulfide, cupric nitrate , Copper salts of organic carboxylic acids such as copper acetate, and the like. Moreover, it is preferable to contain a halogenated alkali metal compound as a component other than a copper compound, and as the halogenated alkali metal compound, lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride , Potassium bromide, potassium iodide, and the like. These additives may be used alone or in combination of various types. The optimum amount of the stabilizer may be selected by selecting an optimal amount, and it is possible to add up to 5 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide resin (A).

In addition, the semi-aromatic polyamide resin composition (C) used in the present invention may be polymer blended with a polyamide having a composition different from the semi-aromatic polyamide resin (A). The addition amount of the polyamide having a composition different from that of the semi-aromatic polyamide resin (A) may be selected as an optimum amount, and it is possible to add up to 50 parts by mass with respect to 100 parts by mass of the semi-aromatic polyamide resin (A).

A thermoplastic resin other than polyamide may be added to the semi-aromatic polyamide resin composition (C) used in the present invention. Examples of the polymer other than polyamide include polyphenylene sulfide (PPS), liquid crystal polymer (LCP), aramid resin, polyether ether ketone (PEEK), polyether ketone (PEK), polyetherimide (PEI), thermoplastic polyimide, Polyamideimide (PAI), polyether ketone ketone (PEKK), polyphenylene ether (PPE), polyethersulfone (PES), polysulfone (PSU), polyarylate (PAR), polyethylene terephthalate, polybutylene Terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycarbonate (PC), polyoxymethylene (POM), polypropylene (PP), polyethylene (PE), polymethylpentene (TPX), polystyrene (PS), polymeta Methyl acrylate, acrylonitrile-styrene copolymer (AS), and acrylonitrile-butadiene-styrene copolymer (ABS). These thermoplastic resins may be blended in a molten state by melt kneading, but may be dispersed in the polyamide resin composition of the present invention in the form of fibers and particles. The optimum amount of the thermoplastic resin may be selected, and it is possible to add up to 50 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide resin (A).

Examples of the impact modifier include ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, and ethylene-methacrylic acid ester copolymer Polyolefin resins such as copolymers and ethylene vinyl acetate copolymers, styrene-butadiene-styrene block copolymers (SBS), styrene-ethylene-butylene-styrene block copolymers (SEBS), and styrene-isoprene-styrene copolymers (SIS) , Polyester polymers such as acrylic ester copolymers, polybutylene terephthalate or polybutylene naphthalate as a hard segment, and polytetramethylene glycol or polycaprolactone or a polycarbonate diol as a soft segment. , Polyamide elastomer, urethane elastomer, acrylic elastomer, silicone rubber, fire And plastic particles having a core shell structure composed of two types of polymers and other rubbers. The addition amount of the impact modifier may be selected by selecting the optimum amount, and it is possible to add up to 30 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide resin (A).

When adding a thermoplastic resin and an impact modifier other than the aromatic polyamide resin (A) to the semi-aromatic polyamide resin composition (C) used in the present invention, it is preferable that a reactive group capable of reacting with the polyamide is copolymerized. , As a reactive group, it is a group which can react with the amino group, carboxyl group, and main chain amide group which are terminal groups of a polyamide resin. Specifically, a carboxylic acid group, an acid anhydride group, an epoxy group, an oxazoline group, an amino group, an isocyanate group, and the like are exemplified, but among these, the acid anhydride group is most excellent in reactivity.

Examples of the release agent include long-chain fatty acids or esters or metal salts thereof, amide-based compounds, polyethylene wax, silicone, and polyethylene oxide. The long-chain fatty acid is particularly preferably 12 or more carbon atoms, and examples thereof include stearic acid, 12-hydroxystearic acid, behenic acid and montanic acid. Partial or total carboxylic acids may be esterified with monoglycol or polyglycol. Alternatively, a metal salt may be formed. Examples of the amide-based compound include ethylene bisterephthalamide and methylenebisstearylamide. These mold release agents may be used alone or as a mixture. The amount of the release agent to be added may be selected as an optimal amount, and it is possible to add up to 5 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide resin (A).

The semi-aromatic polyamide resin composition (C) used in the present invention can be produced by blending each of the above-described constituent components by a conventionally known method. For example, each component is added during the polycondensation reaction of the semi-aromatic polyamide resin (A), dry blend of the semi-aromatic polyamide resin (A) and other components, or by using a twin screw extruder. And melt kneading.

The semi-aromatic polyamide resin composition (C) used in the present invention can be formed into a molded article (D) by a known molding method such as injection molding.

The thermosetting resin (E) used in the present invention is a thermosetting resin characterized by containing a glycidyl group in its chemical structure, and one or more components having a glycidyl group may be included. The thermosetting resin containing a glycidyl group in the chemical structure means a resin in which the glycidyl group is bonded as part of the chemical structure of the resin. As a thermosetting resin containing a glycidyl group in a chemical structure, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, cyclic aliphatic type epoxy resin, long chain aliphatic type epoxy resin, glycidyl ester type epoxy resin , Glycidylamine-type epoxy resins, flame retardant epoxy resins, hydantoin-based epoxy resins, isocyanurate-based epoxy resins, and the like. Among these, bisphenol A-type epoxy resins and bisphenol F-type epoxy resins are preferred from the viewpoints of adhesiveness, processability, and versatility with the semi-aromatic polyamide resin (A).

The thermosetting resin (E) used in the present invention contains various curing agent components for the purpose of advancing the curing reaction. Examples of curing agents include aliphatic polyamines, aromatic amines, modified amines, polyamideamines, secondary amines, tertiary amines, imidazole compounds, polymercaptan compounds, acid anhydrides, boron trifluoride-amine complexes, dicyandiamides, and organic acid hydrazides. Can be lifted. Examples of the aliphatic polyamine include diethylenetriamine, triethylenetriamine, tetraethylenepentamine, dipropriendiamine, diethylaminopropylamine, N-aminoethylpiperazine, mensendiamine, isophoronediamine, and 1,3-bis And aminocyclohexane. Examples of aromatic amines include m-xylenediamine, metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. Piperidine is an example of a secondary amine. Examples of tertiary amines include N, N-dimethylpiperazine, triethylenediamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, and 2,4,6-tris (dimethylaminomethyl) phenol. Examples of the imidazole compound include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-aminoethyl-2-undecylimidazolium trimellitate, and epoxy-imidazole adduct. . Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, maleic anhydride, tetrahydrophthalic anhydride, endomethylene Tetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl anhydrous succinic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexenedicarboxylic anhydride, alkyl Styrene-maleic anhydride copolymer, chlorendic anhydride, and polyazelaic anhydride. The curing agent may be included in one type or multiple types. As the thermosetting resin (E) used in the present invention, commercially available single-liquid and two-liquid thermosetting epoxy resins for adhesion and sealing can be used. Moreover, among them, a one-component thermosetting epoxy resin is preferred.

The thermosetting resin (E) used in the present invention may be subjected to a thermosetting treatment at a temperature suitable for each of the thermosetting resins. It is preferable that the heat curing treatment is possible at 23 to 140 ° C, and that the heat curing treatment is possible at 40 to 120 ° C. It is preferable, and it is more preferable that it is heat-curable at 60-100 degreeC. When the temperature at which the heat-curable resin (E) is heat-curable is below the lower limit, there is a possibility that a problem in which the heat-curing reaction does not sufficiently proceed may occur. When the temperature at which the thermosetting resin (E) is heat-curable exceeds the upper limit, crystallization or softening of the semi-aromatic polyamide resin composition (C) may occur due to heat applied during the curing reaction, which may cause problems in the dimensions of the resulting molded body. There is this.

The adhesive strength of the molded article (D) containing the semi-aromatic polyamide resin composition (C) obtained in the present invention and the thermosetting resin (E) is measured by the method described in the Examples section below. The adhesive strength is an item related to the durability of the molded article obtained in the present invention. In the present invention, the adhesive strength can achieve 1.5 MPa or more. Further, the adhesive strength is preferably 2.0 MPa or more, more preferably 2.5 MPa or more, and even more preferably 3.0 MPa or more. When the adhesive strength is less than the lower limit, peeling of the adhesive surface between the molded article (D) containing the semi-aromatic polyamide resin (C) and the thermosetting resin (E) simply occurs, and it is possible that the strength and sealing properties of the molded body cannot be satisfied. There is this. The fracture state at the time of measuring the adhesive strength is more preferably a fracture state of the base material in which the test piece itself is broken. The semi-aromatic polyamide resin composition (C) contains a styrene-maleimide-based copolymer (F) in a predetermined amount, whereby the adhesive strength to the extent of causing base material destruction can be achieved.

The molded article obtained in the present invention is a molded article formed by assembling a molded article (D) containing a semi-aromatic polyamide resin composition (C) and a thermosetting resin (E) containing a glycidyl group in a chemical structure. A method of granulating by injecting or applying a thermosetting resin (E) to a molded article (D) containing an aromatic polyamide resin composition (C) is preferred.

The molded article (D) obtained in the present invention can be formed into a composite molded body by adhering to a homogeneous material or a dissimilar material through a thermosetting resin (E). Although it does not specifically limit as a dissimilar material, For example, resin other than a semi-aromatic polyamide resin (A), a metal material is mentioned.

The molded article of the present invention, in addition to the composition, by using a semi-aromatic polyamide resin composition containing a semi-aromatic polyamide resin having specific properties such as the amount of end groups, and a thermosetting resin having a glycidyl group, high absorption dimensional stability , It is possible to provide a molded body (composite molded body) having heat resistance and adhesiveness and highly satisfying user needs. It becomes a more preferable aspect by containing a predetermined amount of a styrene-maleimide-type copolymer (F) in a semi-aromatic polyamide resin composition.

The molded article of the present invention can be widely used in automobile parts and electric and electronic parts, and is not limited to use, but is particularly preferably used for various connectors, switches, and camera parts. Connectors, switches, camera parts, etc., often have a small sized molded product, and if dimensional changes due to absorption occur, there is a possibility of poor contact with the terminal. When the molded body is mounted in a solder reflow process, there is a possibility that blisters are generated on the surface of the molded body due to absorption. When the molded body is used for a camera part, there is a possibility that the optical axis shifts due to the dimensional change due to absorption, resulting in problems in operation as a camera.

In addition, in connectors, switches, and camera parts, a molded body is often sealed using a thermosetting resin for the purpose of preventing intrusion of moisture and foreign matter from the outside. When the adhesiveness with the thermosetting resin is low, the sealing property is insufficient, and there is a possibility that it may lead to a problem of the product due to the influence of moisture and foreign matter intruding from the outside.

Example

Hereinafter, the present invention will be described more specifically by examples, but the present invention is not limited to these examples. In addition, the measurement value described in the Example was measured by the following method.

(1) Terminal amino group concentration, terminal carboxyl group concentration

The semi-aromatic polyamide resin (A) was dissolved in a solvent of heavy chloroform (CDCl ₃ ) / hexafluoroisopropanol (HFIP) = 1/1, and after adding formic acid, the concentration of each terminal group was adjusted by ¹ H-NMR. Measured.

(2) Peak area according to crystallization of temperature (ΔH _Tc2 )

The semi-aromatic polyamide resin dried under reduced pressure at 105 ° C. for 15 hours was weighed 10 mg in an aluminum pan (manufactured by SIA Inano Technology, part number 170421S), and covered with an aluminum cover (manufactured by SIA Inano Technology, part number 170420). After preparing the measurement sample in a sealed state, using a high-sensitivity differential scanning calorimeter DSC7020 (manufactured by SIA Inano Technology), the temperature was raised from room temperature to 20 ° C / min, maintained at 350 ° C for 3 minutes, and then the measurement sample pan Was taken out, immersed in liquid nitrogen and quenched. Thereafter, the sample was taken out from liquid nitrogen, left at room temperature for 30 minutes, and then again heated to 20 ° C / min from room temperature using a highly sensitive differential scanning calorimeter DSC7020 (manufactured by ESIA Innotechnology), and 350 ° C After holding for 3 minutes, the mixture was cooled to 30 ° C at 10 ° C / min. The peak area of heat dissipation resulting from cold crystallization at low temperature was defined as (ΔH _Tc2 ).

(3) Melting point (Tm)

The semi-aromatic polyamide resin dried under reduced pressure at 105 ° C. for 15 hours was weighed 10 mg in an aluminum pan (manufactured by SIA Inano Technology, part number 170421S), and covered with an aluminum sheath (manufactured by SIA Inano Technology, part number 170420). After preparing a measurement sample in a sealed state, using a highly sensitive differential scanning calorimeter DSC7020 (manufactured by SIA Inano Technology), the temperature was raised from room temperature to 20 ° C / min, maintained at 350 ° C for 3 minutes, and then the measurement sample pan Was taken out, immersed in liquid nitrogen and quenched. Thereafter, the sample was taken out from liquid nitrogen, left at room temperature for 30 minutes, and then heated again at a temperature of 20 ° C / min from room temperature using a highly sensitive differential scanning calorimeter DSC7020 (manufactured by ESIA InnoTechnologies Co., Ltd.), 350 ° C For 3 minutes. The peak temperature of heat absorption by melting at elevated temperature was defined as the melting point (Tm).

(4) Glass transition temperature (Tg)

The semi-aromatic polyamide resin dried under reduced pressure at 105 ° C. for 15 hours was weighed 10 mg in an aluminum pan (manufactured by SIA Inano Technology, part number 170421S), and covered with an aluminum sheath (manufactured by SIA Inano Technology, part number 170420). After preparing a measurement sample in a sealed state, using a highly sensitive differential scanning calorimeter DSC7020 (manufactured by SIA Inano Technology), the temperature was raised from room temperature to 20 ° C / min, maintained at 350 ° C for 3 minutes, and then the measurement sample pan Was taken out, immersed in liquid nitrogen and quenched. Thereafter, the sample was taken out from liquid nitrogen, left at room temperature for 30 minutes, and then heated again at a temperature of 20 ° C / min from room temperature using a highly sensitive differential scanning calorimeter DSC7020 (manufactured by ESIA InnoTechnologies Co., Ltd.), 350 ° C For 3 minutes. The inflection point of the baseline at the time of heating was taken as the glass transition temperature (Tg).

(5) 80 ° C 95% RH equilibrium absorption rate

Using an injection molding machine EC-100 manufactured by Toshiba Kikai, the cylinder temperature is set to + 20 ° C for the resin and the mold temperature is 140 ° C, and injection molding is performed on a flat plate having a length of 100 mm, a width of 100 mm, and a thickness of 1 mm. An evaluation test piece was produced. The specimen was annealed for 2 hours in an atmosphere of 150 ° C, and then the mass was measured, and the mass at this time was used as the mass at the time of drying. In addition, after the annealing-treated test piece was allowed to stand for 1000 hours in an atmosphere of 85 ° C and 95% RH (relative humidity), the mass was measured, and the mass at this time was taken as the mass during saturated absorption. From the mass at the time of saturated absorption and drying measured by the above-described method, an equilibrium absorption rate of 80% 95% RH was obtained by the following equation.

80 ° C 95% RH equilibrium absorption rate (%) = {(mass upon saturated absorption-mass upon drying) / mass upon drying} × 100

(6) 80 ° C 95% RH equilibrium absorption dimensional change rate

Using an injection molding machine EC-100 manufactured by Toshiba Kikai, the cylinder temperature is set to + 20 ° C for the resin and the mold temperature is 140 ° C, and injection molding is performed on a flat plate having a length of 100 mm, a width of 100 mm, and a thickness of 1 mm. An evaluation test piece was produced. After annealing this test piece for 2 hours in an atmosphere of 150 ° C, dimensions in the parallel direction and the right angle direction to the film gate were measured with a nose at a position of 50 mm from the end, respectively, and the average dimension was obtained from the following equation. In addition, the average dimension at this time was made into the average dimension at the time of drying.

Average dimension (mm) = (dimension in parallel direction + dimension in right angle direction) / 2

In addition, after the annealing-treated test piece was allowed to stand for 1000 hours in an atmosphere of 85 ° C. and 95% RH (relative humidity), the average size was determined by the method described above, and the average size at this time was taken as the average size at the time of equilibrium absorption. From the average dimension at the time of equilibrium absorption and drying measured by the above-described method, the rate of change of the equilibrium absorption dimension at 80 ° C 95% RH was obtained by the following equation.

80 ° C 95% RH Equilibrium absorption dimensional change rate (%) = {(average dimension at equilibrium absorption-average dimension at drying) / average dimension at drying} × 100

(7) Adhesion strength

Using the injection molding machine EC-100 manufactured by Toshiba Kikai, the cylinder temperature was set to + 20 ° C of the resin and the mold temperature to 140 ° C, and the test specimen for evaluation described in FIG. 1 was produced by injection molding. The upper view of FIG. 1 is a view of the upper surface seen from above, and the lower view is a view of the side seen horizontally. After uniformly applying 0.04 g of a thermosetting resin to the adhesive surface (area 310 mm2: total area of the arrow tip in the upper figure of FIG. 2) of the produced evaluation test piece, bonding the test piece of the same shape so that the adhesive surface is a pair In the fixed state (lower view in FIG. 2), heat treatment was performed for 60 minutes in an atmosphere at 100 ° C to prepare a test piece for evaluation of adhesive strength. After the produced test piece was allowed to stand at room temperature for 24 hours, it was evaluated at a tensile speed of 5 mm / min using a precision universal testing machine AG-IS manufactured by Shimadzu Corporation, and the adhesive strength was obtained by the following formula.

Adhesion strength (MPa) = test force at breakage of test piece / adhesive area (310 mm2)

(8) Adhesive breaking mode

The fracture state when the adhesive strength was evaluated by the method described above was classified using the following index.

Base material: No breakage occurs at the interface between the adhesive (thermosetting resin) part or the resin composition test piece and the adhesive, and the test piece itself breaks

Interface: Breakage at the interface of the adhesive (thermosetting resin) portion or the resin composition test piece and the adhesive

(9) Solder reflow resistance

Using the injection molding machine EC-100 manufactured by Toshiba Kikai, the cylinder temperature was set to + 20 ° C for the resin and the mold temperature to 140 ° C, and a test piece for UL combustion test with a length of 127 mm, a width of 12.6 mm, and a thickness of 0.8 mm was used. By injection molding, a test piece was produced. The test piece was left in an atmosphere of 85 ° C and 85% RH (relative humidity) for 72 hours. The test piece was air-reflowed (AIS-20-82C manufactured by A-Tech), heated up from room temperature to 150 ° C over 60 seconds, preliminarily heated, and then preheated to 190 ° C at a rate of 0.5 ° C / min. Was conducted. Thereafter, the temperature was raised to a predetermined set temperature at a rate of 100 ° C / min, and held at a predetermined temperature for 10 seconds, followed by cooling. The set temperature was increased from 240 ° C to 5 ° C intervals, and the highest set temperature at which no swelling or deformation of the surface occurred was used as the reflow heat resistance temperature, and was used as an index of solder heat resistance.

○: Reflow heat-resistant temperature is 260 ° C or higher

×: Reflow heat resistance temperature is less than 260 ° C

This example was made using a semi-aromatic polyamide resin (A) synthesized as illustrated below.

<Synthesis Example 1>

7.54 kg of 1,6-hexamethylenediamine, 10.79 kg of terephthalic acid, 7.04 kg of 11-aminoundecanoic acid, 9 g of sodium diphosphate as a catalyst, 40 g of acetic acid as a terminator, and 17.52 kg of ion-exchanged water in a 50 liter autoclave , It was pressurized with N ₂ from normal pressure to 0.05 MPa, and pressure was released to return to normal pressure. This operation was performed three times, and after N ₂ substitution, the mixture was uniformly dissolved at 135 ° C. and 0.3 MPa under stirring. Thereafter, the dissolved solution was continuously supplied by a liquid feeding pump, heated to 240 ° C by a heating pipe, and heated for 1 hour. Thereafter, the reaction mixture was supplied to a pressurized reaction can, heated to 290 ° C., and a portion of water was discharged to maintain the pressure inside the can at 3 MPa, thereby obtaining a low-order condensate. Thereafter, the low-order condensate was directly supplied to a twin-screw extruder (screw diameter of 37 mm, L / D = 60) while maintaining the molten state, and the resin temperature was 335 ° C., while the water was extracted from the three vents under melting. The polycondensation proceeded to obtain a semiaromatic polyamide resin (A-1). In the obtained semi-aromatic polyamide resin (A-1), the structural unit containing 1,6-hexamethylenediamine and terephthalic acid was 65.1 mol%, and the structural unit containing 11-aminoundecanoic acid was 34.9 mol%, The relative viscosity was 2.1, melting point of 314 ° C, and AEG = 20 eq / ton and CEG = 140 eq / ton analyzed by ¹ H-NMR.

<Synthesis Example 2>

8.57 kg 1,6-hexamethylenediamine, 12.24 kg terephthalic acid, 7.99 kg 11-aminoundecanoic acid, 9 g sodium diphosphate as catalyst, 150 g acetic acid as terminal blocker and 16.20 kg ion-exchanged water in a 50 liter autoclave It was put in, and it was pressurized with N ₂ from normal pressure to 0.05 MPa, released pressure, and returned to normal pressure. This operation was performed three times, and after N ₂ substitution, the mixture was uniformly dissolved at 135 ° C. and 0.3 MPa under stirring. Thereafter, the dissolved solution was continuously supplied by a liquid feeding pump, heated to 240 ° C by a heating pipe, and heated for 1 hour. Thereafter, the reaction mixture was supplied to the pressurized reaction can, heated to 290 ° C., and a portion of water was discharged to maintain the internal pressure of the can at 3 MPa, thereby obtaining a low-order condensate. Thereafter, the low-order condensate was taken out into a container at atmospheric temperature, normal pressure, and then dried under an environment of 70 ° C and a vacuum of 50 Torr using a vacuum dryer. After drying, the low-order condensate was reacted for 6 hours in an environment at 210 ° C and a vacuum of 50 Torr using a blender (capacity 0.1 m 3) to obtain a semiaromatic polyamide resin (A-2). The obtained semi-aromatic polyamide resin (A-2) is composed of 65.3 mol% of structural units containing 1,6-hexamethylenediamine and terephthalic acid, and 34.7 mol% of structural units containing 11-aminoundecanoic acid. The relative viscosity was 2.03, the melting point of 313 ° C, and AEG = 2 eq / ton and CEG = 111 eq / ton analyzed by ¹ H-NMR.

<Synthesis Example 3>

13.22 kg of 1,6-hexamethylenediamine, 12.25 kg of terephthalic acid, 7.99 kg of 11-aminoundecanoic acid, 9 g of sodium diphosphate as a catalyst, 395 g of acetic acid as a terminal blocker and 12.68 kg of ion-exchanged water into a 50 liter autoclave It was put in, and it was pressurized with N ₂ from normal pressure to 0.05 MPa, released pressure, and returned to normal pressure. This operation was performed three times, and after N ₂ substitution, the mixture was uniformly dissolved at 135 ° C. and 0.3 MPa under stirring. Thereafter, the dissolved solution was continuously supplied by a liquid feeding pump, heated to 240 ° C by a heating pipe, and heated for 1 hour. Thereafter, the reaction mixture was supplied to the pressurized reaction can, heated to 290 ° C., and a portion of water was discharged to maintain the internal pressure of the can at 3 MPa, thereby obtaining a low-order condensate. Thereafter, the low-order condensate was taken out into a container at atmospheric temperature, normal pressure, and then dried under an environment of 70 ° C and a vacuum of 50 Torr using a vacuum dryer. After drying, the low-order condensate was reacted for 6 hours in an environment at 210 ° C. and a vacuum of 50 Torr using a blender (capacity 0.1 m 3) to obtain a semiaromatic polyamide resin (A-3). In the obtained semi-aromatic polyamide resin (A-3), the structural unit containing 1,6-hexamethylenediamine and terephthalic acid was 64.8 mol%, and the structural unit containing 11-aminoundecanoic acid was 35.2 mol%, The relative viscosity was 1.84, melting point of 314 ° C, and AEG = 29 eq / ton and CEG = 30 eq / ton analyzed by ¹ H-NMR.

<Synthesis Example 4>

According to the method described in Example 1 of Japanese Patent Application Laid-open No. Hei 7-228689, a terephthalic acid unit, a 1,9-nonanediamine unit and a 2-methyl-1,8-octanediamine unit (1,9-nonanediamine unit) A semi-aromatic polyamide resin containing a molar ratio of: 2-methyl-1,8-octanediamine unit of 85:15) was synthesized (terminal blockade using benzoic acid). The obtained semi-aromatic polyamide resin (A-4) was AEG = 13 eq / ton and CEG = 50 eq / ton analyzed by relative viscosity 2.1, melting point 286 ° C, and ¹ H-NMR.

<Synthesis Example 5>

According to the method described in Comparative Example 3 of WO2006 / 098434, terephthalic acid units, 1,9-nonanediamine units and 2-methyl-1,8-octanediamine units (1,9-nonanediamine units: 2-methyl A semi-aromatic polyamide resin containing a molar ratio of -1,8-octanediamine units of 80:20) was synthesized (terminal blockade using benzoic acid). The obtained semi-aromatic polyamide resin (A-5) had a relative viscosity of 2.1, a melting point of 282 ° C, and AEG = 80 eq / ton and CEG = 46 eq / ton analyzed by ¹ H-NMR.

This example was made using a semi-aromatic polyamide resin composition (C) prepared as illustrated below.

The components and mass ratios (parts by mass) described in Tables 1 and 2 were melt-kneaded at the melting point of each polyamide material at + 20 ° C using a twin screw extruder STS-35 manufactured by Coperion Co., Ltd. The semiaromatic polyamide resin compositions (C) of Comparative Examples 1 to 5 were obtained. The raw materials used in preparing the polyamide resin composition by the method described above using the semi-aromatic polyamide resin composition (C) are as follows. The release agent and stabilizer used as other additives were used in a mass ratio of 1: 5.

Semiaromatic polyamide resin (A-1): Semiaromatic polyamide resin produced based on Synthesis Example 1 described above

Semiaromatic polyamide resin (A-2): Semiaromatic polyamide resin prepared based on Synthesis Example 2 described above

Semiaromatic polyamide resin (A-3): Semiaromatic polyamide resin prepared based on Synthesis Example 3 described above

Semiaromatic polyamide resin (A-4): Semiaromatic polyamide resin prepared based on Synthesis Example 4 described above

Semiaromatic polyamide resin (A-5): Semiaromatic polyamide resin prepared based on Synthesis Example 5 described above

Semiaromatic polyamide resin (A-6): PA10T (Vicnyl (R) 700 manufactured by KINGFA SCI. & TECH. CO., LTD.)

Reinforcement (B): Glass fiber (manufactured by Nippon Denki Glass Co., Ltd., T-275H)

Styrene-maleimide copolymer (F): Styrene-N-phenylmaleimide-maleic anhydride copolymer (manufactured by Denka Corporation, Denka IP MS-NIP)

Release agent: magnesium stearate

Stabilizer: pentaerythryl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox1010 manufactured by Chiba Speciality Chemicals)

This example is made using a molded article (D) and a thermosetting resin (E) comprising a semiaromatic polyamide resin composition (C) prepared as described above.

<Examples 1 to 9 and Comparative Examples 1 to 5>

Using the semi-aromatic polyamide resin composition (C) and thermosetting resin (E) shown in Tables 1 and 2, Examples 1 to 9 and Comparative Examples 1 to 5 were performed by the methods described above.

Thermosetting resin (E-1): One-component thermosetting epoxy resin (2222P manufactured by Three Bond)

Thermosetting resin (E-2): One-component thermosetting epoxy resin (AH-3031T manufactured by Takaoka Chemical)

As can be seen from Tables 1 and 2, Examples 1 to 3 can not only express high adhesiveness with the thermosetting resin (E), but also have a small rate of change in dimensional equilibrium absorption at 80 ° C 95% RH and solder reflow resistance. It can be seen that it has excellent properties such as satisfaction. In addition, in Example 4, AEG = 2 eq / ton was low, and the adhesion with the thermosetting resin (E) slightly decreased compared to Examples 1 to 3, but the adhesive strength was 2.9 MPa, and practically sufficient properties were obtained. have. In Example 5, although the thermosetting resin (E) was changed, it was found that sufficient adhesive strength was obtained and excellent properties were obtained. On the other hand, Comparative Example 1 uses a semi-aromatic polyamide resin made of the same monomers as Examples 1 to 3, but the value of (AEG + CEG) is low to 59 eq / ton, and adhesion to the thermosetting resin (E) This is insufficient. In Comparative Examples 2 and 3, semi-aromatic polyamide resins (PA9T / M8T) made of monomers different from Examples 1 to 5 were used. In Comparative Example 2, the value of (AEG + CEG) was 63 eq / ton. In addition to being low, since ΔH _Tc2 is large and Tg is high, adhesiveness with the thermosetting resin (E) is insufficient. In Comparative Example 3, the value of (AEG + CEG) is appropriate at 126 eq / ton, but since ΔH _Tc2 is large and Tg is high, adhesion to the thermosetting resin (E) is insufficient. In Comparative Example 4, a semi-aromatic polyamide resin (PA10T) made of monomers different from Examples 1 to 5 was used, and in addition to the low (AEG + CEG) value of 44 eq / ton, ΔH _Tc2 was large. , Since Tg is high, the adhesiveness with the thermosetting resin (E) is insufficient. In Comparative Example 5, the thermosetting resin (E) was changed. As in Comparative Example 3, the value of (AEG + CEG) is appropriate at 126 eq / ton, but since ΔH _Tc2 is large and Tg is high, the thermosetting resin (E) ) Has insufficient adhesion.

Moreover, in Examples 6-9, since adhesive strength is high and an adhesive failure mode is also a base material, it turns out that it has excellent adhesiveness with thermosetting resin (D). In addition, the 80% 95% RH equilibrium absorption rate, the 80 ° C 95% RH equilibrium absorption dimensional change rate is low, and the dimensional stability at the time of absorption is excellent.

The molded article of the present invention, in addition to the composition, by using a semi-aromatic polyamide resin composition containing a semi-aromatic polyamide resin having specific physical properties such as the amount of end groups, and a thermosetting resin having a glycidyl group, high absorption dimensions A molded article (composite molded article) having stability, heat resistance, and adhesiveness and highly satisfying the user's needs can be industrially advantageously produced.

Claims (8)

With respect to 100 parts by mass of the semi-aromatic polyamide resin (A) that satisfies the following requirements (a) to (c), it contains 0 to 200 parts by mass of the reinforcing material (B), and the equilibrium absorption rate at 80 ° C 95% RH is 3.0% or less. A molded article having a structure in which a molded article (D) comprising a semiaromatic polyamide resin composition (C) and a thermosetting resin (E) containing a glycidyl group are directly interposed:
(a) the peak area (ΔH _Tc2 ) according to the crystallization of temperature measured by differential scanning calorimetry (DSC) is 40 mJ / mg or less,
(b) the glass transition temperature (Tg) is 120 ° C or less,
(c) The sum (AEG + CEG) of the terminal amino group concentration (AEG) and the terminal carboxyl group concentration (CEG) is 70 eq / ton or more. The semi-aromatic polyamide resin composition (C) according to claim 1, further comprising 10 to 60 parts by mass of a styrene-maleimide-based copolymer (F) with respect to 100 parts by mass of the semi-aromatic polyamide resin (A). Molded body. The semi-aromatic polyamide resin (A) according to claim 1 or 2, wherein the repeating unit containing diamine having 6 to 12 carbons and terephthalic acid is 50 to 100 mol% and aminocarboxylic acid or lactam having 10 or more carbon atoms. A molded article which is a semiaromatic polyamide resin containing 0 to 50 mol% of repeating units. The semi-aromatic polyamide resin (A) according to claim 1 or 2, wherein the repeating unit comprising hexamethylenediamine and terephthalic acid is 50 to 100 mol%, and the repeating unit comprising aminoundecanoic acid or undecanelactam is 0. A molded article which is a semiaromatic polyamide resin containing ∼50 mol%. The molded article according to any one of claims 1 to 4, wherein the thermosetting resin (E) containing a glycidyl group is a one-component thermosetting epoxy resin. A connector comprising the molded body according to any one of claims 1 to 5. A switch component comprising the molded body according to any one of claims 1 to 5. A camera component comprising the molded body according to any one of claims 1 to 5.

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