WO2019059357A1

WO2019059357A1 - Compact including, as constituent, molded article formed of semiaromatic polyamide resin composition

Info

Publication number: WO2019059357A1
Application number: PCT/JP2018/035096
Authority: WO
Inventors: 誠玉津島; 順一中尾
Original assignee: 東洋紡株式会社
Priority date: 2017-09-25
Filing date: 2018-09-21
Publication date: 2019-03-28
Also published as: KR102615918B1; KR20200047594A; JPWO2019059357A1; JP7200927B2; CN111133038B; CN111133038A

Abstract

This compact has a structure in which a molded article (D) and a heat-curable resin (E) that contains a glycidyl group are directly interfaced. The molded article (D) comprises a semiaromatic polyamide resin composition (C) that has an equilibrium water absorption ratio of 3.0% or less at 80°C and 95% RH, and that contains 0–200 parts by mass of a reinforcing material (B) relative to 100 parts by mass of a semiaromatic polyamide resin (A) for which the peak area associated with cooling crystallization measured by differential scanning calorimetry (DSC), the glass transition temperature, and the sum of the terminal amino group concentration and the terminal carboxyl group concentration satisfy designated conditions. The compact has high water absorption dimensional stability, heat resistance, and adhesiveness.

Description

Molded article having a molded article comprising a semi-aromatic polyamide resin composition as a component

The present invention has a structure in which a molded article made of a semiaromatic polyamide resin composition excellent in water absorption dimensional stability and heat resistance and a thermosetting resin containing glycidyl group have high adhesiveness and are directly intervened. It is related with the molded object which it has.

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

BACKGROUND OF THE INVENTION With the expansion of applications, a method of joining parts has been attracting attention, in the wide variety of shapes and configurations of parts in which polyamide resin is used. As a best example, there is a method of fastening with screws or screws, but with the streamlining of product manufacturing process and miniaturization of parts, there are cases where physical fastening becomes difficult, and various new joining methods are available. The welding method and bonding with thermosetting resin are being promoted. In the field of electrical and electronic equipment in particular, sealing with a thermosetting resin is becoming common in order to prevent malfunction of equipment due to a trace amount of moisture and foreign matter entering from the outside while the product is being refined. High adhesion to these thermosetting resins is strongly demanded for such polyamide resins.

In the case of polyamide resins, the influence of water absorption in the environment of use on product quality often becomes a problem. The polyamide resin changes its dimensions when it absorbs water in the air, and therefore, the product dimensions change, leading to a defective assembly or operation of the product. Moreover, in the solder reflow process generally used in the field of electric and electronic equipment, blisters of the product due to water absorption occur, leading to the occurrence of product defects. In the case of PA6, PA66, modified PA6T, etc. widely used in the market, the saturated water absorption rate of the resin is as high as 6% or more, and the above problem is likely to occur. Therefore, a low water absorption polyamide resin that is less likely to absorb water is required.

Various polyamide resin compositions have been developed with the changes in market requirements as described above. Patent Document 1 discloses a carbon fiber reinforced polyamide resin composition which is excellent in metal adhesion and is composed of a semiaromatic polyamide, a carbon fiber, and an epoxy compound. However, it is essential that the technique described in the document contains an epoxy compound in the resin composition, and the low heat resistance of the epoxy compound increases outgassing at the time of processing at high temperature, and the appearance of the molded article There is a problem with processability such as a marked decrease.

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

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

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

JP, 2015-129271, A International Publication WO 2006/098434 JP, 2017-140768, A

The present invention has been made in view of the current state of the prior art, and its object is to improve the adhesion between a molded article made of a semi-aromatic polyamide resin composition and a thermosetting resin containing glycidyl group. An object of the present invention is to provide a molded article excellent in water absorption dimensional stability and heat resistance, which has a structure directly interposed while having the resin.

In order to achieve the above object, the present inventor uses a resin composition containing a semiaromatic polyamide resin having specific physical properties such as the amount of end groups in addition to the composition, and a thermosetting resin having a glycidyl group It came to provide the molded object which has high water absorption dimensional stability, heat resistance, and adhesiveness by carrying out. This molded body can also be understood as a composite molded body, since it is a molded body in which a molded article made of a semi-aromatic polyamide resin composition and a thermosetting resin having a glycidyl group are directly interposed. It has also been found that the adhesiveness is improved by further blending a styrene-maleimide copolymer in a specific ratio into the resin composition.

That is, the present invention has the following constitution.
(1) 100 parts by mass of a semiaromatic polyamide resin (A) satisfying the following requirements (a) to (c), containing 0 to 200 parts by mass of a reinforcing material (B), 80 ° C. 95% RH equilibrium A molded article having a structure in which a molded article (D) comprising a semi-aromatic polyamide resin composition (C) having a water absorption coefficient of 3.0% or less and a thermosetting resin (E) containing glycidyl group are directly interposed .
(A) Peak area (ΔH _Tc2 ) associated with temperature-decreasing crystallization measured by differential scanning calorimetry (DSC) is 40 mJ / mg or less (b) Glass transition temperature (Tg) is 120 ° C. or less (c) Terminal amino group concentration (c) Sum of (AEG) and terminal carboxyl group concentration (CEG) (AEG + CEG) is 70 eq / ton or more (2) The semi-aromatic polyamide resin composition (C) is based on 100 parts by mass of the semi-aromatic polyamide resin (A), The molded article according to (1), further comprising 10 to 60 parts by mass of a styrene-maleimide copolymer (F).
(3) The semi-aromatic polyamide resin (A) contains 50 to 100 mol% of a repeating unit consisting of a diamine having 6 to 12 carbon atoms and terephthalic acid, and no repeating unit consisting of an 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) Semi-aromatic polyamide resin (A) containing 50 to 100 mol% of repeating units consisting of hexamethylene diamine and terephthalic acid and 0 to 50 mol% of repeating units consisting of aminoundecanoic acid or undecanelactam The molded object as described in (1) or (2) which is a 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 body according to any one of (1) to (5).
(7) A switch part comprising the molded body according to any one of (1) to (5).
(8) A camera part comprising the molded body according to any one of (1) to (5).

According to the present invention, the semi-aromatic polyamide resin having high water absorption dimensional stability, heat resistance and adhesiveness, comprising a molded article comprising a semi-aromatic polyamide resin composition and a thermosetting resin having a glycidyl group It is possible to provide a composite molded article in which molded articles made of the composition and a thermosetting resin having a glycidyl group are directly intervened. Here, "directly intercalated" means that they are directly adhered.

It is the schematic which shows the test piece shape for adhesive strength evaluation implemented in an Example. It is the schematic which shows the test piece production method of adhesive strength evaluation implemented in an Example.

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

The molded article of the present invention contains 0 to 200 parts by mass of a reinforcing material (B) with respect to 100 parts by mass of a semiaromatic polyamide resin (A) satisfying the following requirements (a) to (c), Structure in which a molded article (D) comprising a semi-aromatic polyamide resin composition (C) having a 95% RH equilibrium water absorption of 3.0% or less and a thermosetting resin (E) containing glycidyl group are directly intervened It is characterized by having.
(A) Peak area (ΔH _Tc2 ) associated with temperature-decreasing crystallization measured by differential scanning calorimetry (DSC) is 40 mJ / mg or less (b) Glass transition temperature (Tg) is 120 ° C. or less (c) Terminal amino group concentration (c) The sum of (AEG) and terminal carboxyl group concentration (CEG) (AEG + CEG) is 70 eq / ton or more. The semiaromatic polyamide resin composition (C) further contains styrene based on 100 parts by mass of the semiaromatic polyamide resin (A). It is a preferred embodiment that 10 to 60 parts by mass of the maleimide copolymer (F) is contained.

The semiaromatic polyamide resin (A) used in the present invention is not particularly limited, and is a semiaromatic polyamide having an acid amide bond (-CONH-) in the molecule and having an aromatic ring (benzene ring). It is.
Examples of semi-aromatic polyamides include 6T polyamides (for example, polyamide 6T6I consisting of terephthalic acid / isophthalic acid / hexamethylene diamine, polyamide 6T66 consisting of terephthalic acid / adipic acid / hexamethylene diamine, terephthalic acid / isophthalic acid / adipine Acid / hexamethylenediamine polyamide 6T6I66, terephthalic acid / hexamethylenediamine / 2-methyl-1, 5-pentamethylenediamine polyamide 6T / M-5T, terephthalic acid / hexamethylenediamine / ε-caprolactam polyamide 6T6, polyamide 6T / 4T) consisting of terephthalic acid / hexamethylenediamine / tetramethylenediamine, 9T polyamide (terephthalic acid / 1,9-nonanediamine / 2-methyl-1) 8-Octane diamine), 10 T polyamide (terephthalic acid / 1, 10-decane diamine), 12 T polyamide (terephthalic acid / 1, 12-dodecane diamine), polyamide consisting of sebacic acid / paraxylene diamine, etc. .

The semi-aromatic polyamide resin (A) used in the present invention needs to have a peak area (ΔH _Tc2 ) associated with temperature-drop crystallization measured by the method described in the section of the following examples at 40 mJ / mg or less. Also, it is preferably 35 mJ / mg or less, more preferably 30 mJ / mg or less. When ΔH _Tc2 exceeds the above upper limit, the adhesion to the thermosetting resin (E) is lowered, and the strength necessary for the molded product may not be achieved, which is not preferable. The lower limit of ΔH _Tc2 is 5 mJ / mg, and 10 mJ / mg or more is more preferable. Below the above lower limit, the molding cycle time may be prolonged and the production efficiency may be reduced. Moreover, when the obtained molded object is subjected to secondary processing in a high temperature environment, dimensional change, deformation, etc. may occur, 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 measured by the method described in the section of 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 the 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 adhesion to the thermosetting resin (E) is reduced, and the molded article It is not preferable that the required strength may not be achieved. The lower limit of Tg is 50 ° C. or higher, preferably 60 ° C. or higher, and more preferably 70 ° C. or higher. Below the lower limit, depending on the use environment, the molded product may be softened, which may cause deformation or malfunction of the product, which is not preferable.

The semiaromatic polyamide resin (A) used in the present invention needs to have a sum (AEG + CEG) of terminal amino group concentration (AEG) and terminal carboxyl group concentration (CEG) of 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-mentioned lower limit, adhesion with the thermosetting resin (E) may be lowered, and the strength necessary for the molded product 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 still more preferably 160 eq / ton. When it exceeds the above-mentioned upper limit, reaction of end groups with the heat at the time of processing arises, and a problem may arise in retention stability, and it is not preferable.

The terminal amino group concentration (AEG) of the semi-aromatic polyamide resin (A) used in the present invention is preferably 2 eq / ton or more, more preferably 10 eq / ton or more, and 15 eq / ton or more Is more preferably 20 eq / ton or more. Even when the terminal amino group concentration is below the above lower limit, the semi-aromatic polyamide resin (A) used in the present invention is excellent in adhesion to the thermosetting resin (E), and the molded article of the present invention has sufficient adhesion Although it has intensity | strength, it is preferable from the further higher adhesive strength being obtained by making the terminal amino group density | concentration more than the said lower limit.

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 40 eq / ton or more Is more preferred. Since the adhesiveness with a thermosetting resin (E) can be improved by making terminal carboxyl group density | concentration into the said lower limit or more, it is preferable.
The semiaromatic polyamide resin (A) used in the present invention preferably has a larger CEG than AEG. The CEG / AEG is preferably 2 or more, more preferably 5 or more.

The semi-aromatic polyamide resin (A) used in the present invention preferably has a DSC melting peak temperature (Tm) located at the lowest temperature side measured by the method described in the section of the following examples and is 280 ° C. or higher. Moreover, it is more preferable that it is 290 degreeC or more, and it is further more preferable that it is 300 degreeC or more. When Tm is less than the above lower limit, when the molded body of the present invention is processed in a solder reflow process, melting or deformation of the molded body may occur, which is not preferable. As an upper limit of Tm, 340 degrees C or less is preferable, 330 degrees C or less is more preferable, 320 degrees C or less is more preferable. When Tm exceeds the above-mentioned upper limit, processing temperature at the time of molding processing becomes extremely high, and decomposition of resin by heat may occur, which is not preferable.

The semiaromatic polyamide resin (A) used in the present invention is preferably the following semiaromatic polyamide resin from the viewpoint of ΔH _Tc2 , Tg, and Tm.
The semi-aromatic polyamide resin (A) comprises 50 to 100 mol% of a repeating unit consisting of a diamine having 6 to 12 carbon atoms and terephthalic acid, and 0 to 50 mol of a repeating unit consisting of an aminocarboxylic acid or lactam having 10 or more carbon atoms. % Is preferably a semi-aromatic polyamide resin containing 50% to 98% by mole of a repeating unit consisting of a diamine having 6 to 12 carbon atoms and terephthalic acid, and 2 repeating units consisting of an aminocarboxylic acid or a lactam having 10 or more carbon atoms. It is more preferable that the semi-aromatic polyamide resin contains 50 to 50 mol%, and 55 to 98 mol% of repeating units consisting of diamine having 6 to 12 carbon atoms and terephthalic acid, and aminocarboxylic acid or lactam having 10 or more carbon atoms More preferably, it is a semiaromatic polyamide resin containing 2 to 45 mol% of repeating units. .
When the proportion of the repeating unit composed of a 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 becomes longer due to the decrease of ΔH _Tc2 and the Tm decreases. It is not preferable because there is a possibility that problems may occur due to the melting or deformation of the molded product in the solder reflow process due to the above, and the softening of the molded product in the use environment due to the decrease in Tg. On the other hand, since ΔH _Tc2 , Tg and Tm of the semiaromatic polyamide resin (A) can be appropriately improved, it is composed of a diamine having 6 to 12 carbon atoms and terephthalic acid in the semiaromatic polyamide resin (A) It is more preferable to set the proportion of repeating units to 55 mol% or more (45 mol% or less of repeating units consisting of an aminocarboxylic acid having 10 or more carbon atoms or lactams), and 60 mol% or more (aminocarboxylic acids having 10 or more carbon atoms) It is more preferable that the repeating unit consisting of lactam be 40 mol% or less).

Examples of the diamine component having 6 to 12 carbon atoms constituting the semiaromatic polyamide resin (A) include 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9- Nonamethylenediamine, 2-methyl-1,8-octamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine can be mentioned. These may be used alone or in combination.

The aminocarboxylic acid having 10 or more carbon atoms or the lactam having 10 or more carbon atoms constituting the semiaromatic polyamide resin (A) is preferably an aminocarboxylic acid or lactam having 11 to 18 carbon atoms. Among these, 11-aminoundecanoic acid, undecanelactam, 12-aminododecanoic acid and 12-lauryl lactam are preferable.

In the semiaromatic polyamide resin (A) used in the present invention, other components can be copolymerized in 50% by mole or less of the constituent units. Other copolymerizable diamine components include 1,13-tridecamethylenediamine, 1,16-hexadecamethylenediamine, 1,18-octadecamethylenediamine, 2,2,4 (or 2,4,4 (or 2,4,4) Aliphatic diamines such as) -trimethylhexamethylene diamine, fats such as piperazine, cyclohexane diamine, bis (3-methyl-4-aminohexyl) methane, bis- (4,4'-aminocyclohexyl) methane, isophorone diamine Aromatic diamines such as cyclic diamines, metaxylylene diamines, para-xylylene diamines, para-phenylene diamines, meta-phenylene diamines, and hydrogenated products thereof can be mentioned.

Other copolymerizable acid components include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 2,2'-diphenyldicarboxylic acid Aromatic dicarboxylic acids such as 4,4'-diphenyletherdicarboxylic acid, sodium 5-sulfonate isophthalic acid, 5-hydroxyisophthalic acid, fumaric acid, maleic acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,18-octadecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 , 2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, Aliphatic and alicyclic dicarboxylic acids such as mer acid.
In addition, another component capable of copolymerizing includes ε-caprolactam and the like.

Among the above components, from the viewpoint of ΔH _{Tc 2} , Tg and Tm, as a copolymerization component, one or more of an aminocarboxylic acid having 11 to 18 carbon atoms or a lactam having 11 to 18 carbons are copolymerized Is preferred.

The semiaromatic polyamide resin (A) used in the present invention contains 50 to 100 mol% of repeating units consisting of hexamethylene diamine and terephthalic acid, and 0 to 50 mol% of repeating units consisting of aminoundecanoic acid or undecanelactam. A semi-aromatic polyamide resin, preferably a semi-aromatic polyamide resin, containing 50 to 98 mol% of repeating units consisting of hexamethylene diamine and terephthalic acid, and 2 to 50 mol% of repeating units consisting of amino undecanoic acid or undecane lactam It is more preferable that the resin is a semi-aromatic polyamide resin containing 55 to 80 mol% of repeating units consisting of hexamethylene diamine and terephthalic acid and 20 to 45 mol% of repeating units consisting of aminoundecanoic acid or undecanelactam What's more Preferred, a repeating unit composed of hexamethylenediamine and terephthalic acid 60-70 mol%, contains a repeating unit composed of aminoundecanoic acid or undecanoic lactam 30-40 mol%, and particularly preferably is a semi-aromatic polyamide resin.
When the proportion of repeating units consisting of hexamethylenediamine and terephthalic acid in the semi-aromatic polyamide resin (A) is less than 50 mol%, the molding cycle time becomes longer due to the decrease in ΔH _{Tc2 and} the solder reflow process due to the decrease in Tm. There is a possibility that a failure may occur due to the melting or deformation of the molded product in the above, and the softening of the molded product in the use environment due to the decrease of Tg. On the other hand, by setting the ratio of repeating units consisting of hexamethylenediamine and terephthalic acid in the semiaromatic polyamide resin (A) to 55 to 80 mol%, the crystallinity and molecular motion of the semiaromatic polyamide resin (A) It is more preferable because it is possible to control the property and to appropriately improve ΔH _Tc2 , Tg and Tm. Further, by setting the ratio of repeating units consisting of hexamethylenediamine and terephthalic acid in the semi-aromatic polyamide resin (A) to 60 to 70 mol%, the Tm can be in the range of 300 ° C. to 320 ° C. In addition to facilitating molding, ΔH _Tc2 can be made 10 to 35 mJ / mg, Tg can be made 70 to 100 ° C., and high adhesiveness with the thermosetting resin (E) can be obtained. And more preferred.

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

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

The semi-aromatic polyamide resin (A) is to adjust the amount of terminal groups and the molecular weight of polyamide by adjusting the molar ratio between the amount of amino groups and the carboxyl group and performing polycondensation or adding an end capping agent. Can.

The timing for adding the end-capping agent may be at the time of raw material charging, at the start of polymerization, at the end of polymerization, or at the end of polymerization. The end capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with an amino group or a carboxyl group at a polyamide end, and an acid anhydride such as monocarboxylic acid or monoamine, phthalic anhydride, Monoisocyanates, mono acid halides, monoesters, monoalcohols and the like can be used. Examples of end capping agents include aliphatic monobasics such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid and the like Alicyclic monocarboxylic acids such as carboxylic acids and cyclohexanecarboxylic acids, benzoic acids, toluic acids, α-naphthalenecarboxylic acids, β-naphthalenecarboxylic acids, aromatic monocarboxylic acids such as methylnaphthalenecarboxylic acids and phenylacetic acids, and maleic anhydride Acids, acid anhydrides such as phthalic anhydride and hexahydrophthalic anhydride, methylamine, ethylamine, propylamine, butylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine etc. Aliphatic monoamines, Alicyclic monoamines such as clohexylamine and dicyclohexylamine; and aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine.

The semi-aromatic polyamide resin (A) can be produced by a conventionally known method, and can be easily synthesized, for example, by co-condensation reaction of raw material monomers. The order of the cocondensation polymerization reaction is not particularly limited, and all the raw material monomers may be reacted at once, or some raw material monomers may be reacted first, and then the remaining raw material monomers may be reacted. Also, the polymerization method is not particularly limited, but it may be carried out in a continuous process from raw material charging to polymer production, or once an oligomer is produced, then polymerization is advanced by an extruder or the like in another process, or the oligomer is solidified You may use methods, such as high molecular weight formation by phase polymerization. By adjusting the feed ratio of the raw material monomers, it is possible to control the proportion of each structural unit in the copolymerized polyamide to be synthesized.

The reinforcing material (B) used in the present invention is for improving the moldability of the semiaromatic polyamide resin composition (C) and the strength of the molded article (D) comprising the semiaromatic polyamide resin composition (C). It is preferable to use at least one selected from fibrous reinforcing materials and needle-like reinforcing materials. Examples of fibrous reinforcing materials include glass fibers, carbon fibers, boron fibers, ceramic fibers, metal fibers and the like, and examples of needle-like reinforcing materials include potassium titanate whiskers, aluminum borate whiskers, zinc oxide whiskers, carbonates Calcium whiskers, magnesium sulfate whiskers, wollastonite and the like can be mentioned. As glass fibers it is possible to use chopped strands or continuous filament fibers having a length of 0.1 mm to 100 mm. As a cross-sectional shape of glass fiber, glass fiber of circular cross section and non-circular cross section can be used. The diameter of the round cross section glass fiber is 20 μm or less, preferably 15 μm or less, more preferably 10 μm or less. Further, glass fibers having a non-circular cross section are preferable in terms of physical properties and fluidity. The glass fibers having a non-circular cross section include those having a substantially oval shape, a substantially oval shape, or a substantially wedge shape in a cross section perpendicular to the length direction of the fiber length, and the flatness is 1.5 to 8 Is preferred. Here, the flatness is assumed to be a rectangle having a minimum area circumscribing the cross 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. Ratio of major axis / minor axis when The thickness of the glass fiber is not particularly limited, but the minor diameter is about 1 to 20 μm and the major diameter is about 2 to 100 μm. In addition, it is preferable to use a chopped strand-like glass fiber cut into fibers of about 1 to 20 mm as a fiber bundle. Moreover, in order to improve the affinity to the polyamide resin, it is preferable to use a fibrous reinforcing material that has been treated with an organic treatment or a coupling agent, or to use it together with the coupling agent at the time of melt compounding. Although any of a coupling agent, a titanate coupling agent, and an aluminum type coupling agent may be used, an aminosilane coupling agent and an epoxy silane coupling agent are especially preferable among these.

The reinforcing material (B) used in the present invention needs to be 0 to 200 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide resin (A). Also, 10 to 200 parts by mass is preferable, 10 to 180 parts by mass is more preferable, and 15 to 160 parts by mass is more preferable. When the proportion of the reinforcing material (B) exceeds the above-mentioned upper limit, the proportion of the semiaromatic polyamide resin (A) in direct contact with the thermosetting resin (E) decreases at the time of adhesion with the thermosetting resin (E) Adhesion, which is not preferable. On the other hand, depending on the product, there may be a case where sufficient molded body strength can be expressed without using the reinforcing material (B), so the lower limit of the ratio of the reinforcing material (B) is 0 parts by mass. From the viewpoint of product strength, the amount is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more.

The styrene-maleimide 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). In addition, 12 to 50 parts by mass is preferable, and 15 to 40 parts by mass is more preferable. If the proportion of the styrene-maleimide copolymer (F) is below the above lower limit, the adhesion may be lowered upon adhesion with the thermosetting resin (E), which is not preferable. When the proportion of the styrene-maleimide copolymer (F) exceeds the above upper limit, the flowability at the time of injection molding may be reduced, and the appearance of the molded article may be deteriorated, which is not preferable.

The styrene-maleimide copolymer (F) used in the present invention is a copolymer containing a styrene monomer and a maleimide monomer as a component. A maleic anhydride may be copolymerized with the styrene-maleimide copolymer (F) for the purpose of improving the compatibility with the semiaromatic polyamide resin (A). Although the ratio of the components of the styrene-maleimide copolymer (F) is not particularly limited, examples of specific components include 25 to 40 mol% of a styrene monomer, N-phenylmaleimide 50 to 70 mol% and 5 to 15 mol% of maleic anhydride can be mentioned. Commercially available products include Denka IP MS-NIP manufactured by Denka Co., Ltd.

The semi-aromatic polyamide resin composition (C) used in the present invention is a solder used not only for suppressing dimensional change of the molded product obtained according to the present invention under actual use environment but also for mounting of electric and electronic parts In order to suppress the occurrence of blisters in the reflow process, the 80 ° C. 95% RH equilibrium water absorption as measured by the method described in the item of the following example needs to be 3.0% (3.0 mass%) or less . Moreover, it is preferable that 80 degreeC 95% RH equilibrium water absorption is 2.5% or less. When the 80 ° C 95% RH equilibrium water absorption rate exceeds the above upper limit, the water absorption dimensional change of the obtained molded article becomes large, and problems occur during product assembly or product operation or blisters occur in the solder reflow process, resulting in product failure It is not possible because it may lead. Although the lower limit of 80 ° C. 95% RH equilibrium water absorption is 0%, about 1.0% is preferable in view of the characteristics of the semiaromatic polyamide resin (A) used in the present invention.

Various additives used in conventional polyamide resin compositions can be used in the semiaromatic polyamide resin composition (C) used in the present invention. Additives include stabilizers, impact modifiers, mold release agents, slide improvers, colorants, plasticizers, crystal nucleating agents, polyamides different from semi-aromatic polyamide resins (A), thermoplastics other than polyamides Resin etc. are mentioned. The possible blending amounts of these components in the semiaromatic polyamide resin composition (C) are as described below, but the total of these components is 30 mass% in the semiaromatic polyamide resin composition (C) % Or less is preferable, 20 mass% 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 semiaromatic polyamide resin composition (C) also includes the case where it is composed of only the semiaromatic polyamide resin (A), but also in that case, it is referred to as the semiaromatic polyamide resin composition (C) for convenience.

As the stabilizer, organic antioxidants and heat stabilizers such as hindered phenol type antioxidants, sulfur type antioxidants and phosphorus type antioxidants, light stabilizers such as hindered amine type, benzophenone type and imidazole type and the like UV absorbers, metal deactivators, copper compounds and the like can be mentioned. As a copper compound, cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, cupric iodide, cupric phosphate, cupric pyrophosphate, Copper salts of organic carboxylic acids such as copper sulfide, copper nitrate and copper acetate can be used. Furthermore, as a component other than the copper compound, it is preferable to contain an alkali metal halide compound, and as the alkali metal halide compound, lithium chloride, lithium bromide, lithium iodide, sodium iodide, sodium fluoride, sodium chloride, bromide Sodium, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide and the like can be mentioned. These additives may be used not only singly but also in combination of several kinds. Although the addition amount of the stabilizer may be selected as an optimum amount, 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 the semiaromatic polyamide resin composition (C) used in the present invention, a polyamide having a composition different from that of the semiaromatic polyamide resin (A) may be polymer-blended. Although the addition amount of the polyamide having a composition different from that of the semiaromatic polyamide resin (A) may be selected optimally, adding up to 50 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide resin (A) Is possible.

A thermoplastic resin other than polyamide may be added to the semiaromatic polyamide resin composition (C) used in the present invention. As polymers other than polyamide, polyphenylene sulfide (PPS), liquid crystal polymer (LCP), aramid resin, polyetheretherketone (PEEK), polyetherketone (PEK), polyetherimide (PEI), thermoplastic polyimide, polyamideimide (PAI), polyether ketone ketone (PEKK), polyphenylene ether (PPE), polyether sulfone (PES), polysulfone (PSU), polyarylate (PAR), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene na Phthalate, polycarbonate (PC), polyoxymethylene (POM), polypropylene (PP), polyethylene (PE), polymethylpentene (TPX), polystyrene ( S), polymethyl methacrylate, acrylonitrile - styrene copolymer (AS), acrylonitrile - butadiene - styrene copolymer (ABS) and the like. Although these thermoplastic resins can be blended in a molten state by melt-kneading, they may be dispersed in the polyamide resin composition of the present invention into fibrous and particulate thermoplastic resins. Although the addition amount of the thermoplastic resin may be selected as an optimum amount, 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).

Impact modifiers include ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene- Methacrylic acid ester copolymer, polyolefin resin such as ethylene vinyl acetate copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene -A vinyl polymer resin such as styrene copolymer (SIS) or acrylic ester copolymer, polybutylene terephthalate or polybutylene naphthalate as a hard segment, polytetramethylene glycol or polycaprolactone or poly Polyester block copolymer in which the turbo sulfonate diol as a soft segment, a polyamide elastomer, urethane elastomer, acrylic elastomer, silicone rubber, fluorinated rubber, and the like polymer particles having a core-shell structure constituted from two different polymers. Although the addition amount of the impact modifier may be selected optimally, 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 a thermoplastic resin other than the aromatic polyamide resin (A) and an impact modifier are added to the semiaromatic polyamide resin composition (C) used in the present invention, the reactive group capable of reacting with the polyamide is co It is preferable to be polymerized, and the reactive group is a group capable of reacting with an amino group which is a terminal group of a polyamide resin, a carboxyl group and a main chain amide group. Specific examples thereof include a carboxylic acid group, an acid anhydride group, an epoxy group, an oxazoline group, an amino group, and an isocyanate group. Among these, the acid anhydride group is most excellent in reactivity.

As a mold release agent, a long chain fatty acid or ester or metal salt thereof, an amide based compound, polyethylene wax, silicone, polyethylene oxide and the like can be mentioned. The long chain fatty acid preferably has 12 or more carbon atoms in particular, and examples thereof include stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, etc. Partial or whole carboxylic acid is esterified with monoglycol or polyglycol Or a metal salt may be formed. As an amide system compound, ethylene bis terephthalamide, methylene bis stearyl amide, etc. are mentioned. These release agents may be used alone or as a mixture. The addition amount of the release agent may be selected as an optimum amount, but 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 the above-mentioned respective components by a conventionally known method. For example, each component is added during the polycondensation reaction of the semiaromatic polyamide resin (A), the semiaromatic polyamide resin (A) and the other components are dry blended, or a twin screw extruder is used. The method of melt-kneading each component using can be mentioned.

The semiaromatic polyamide resin composition (C) used in the present invention can be made 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 the chemical structure, and one or more kinds of components having a glycidyl group may be contained. The thermosetting resin containing a glycidyl group in the chemical structure means a resin in which the glycidyl group is bonded as a part of the chemical structure of the resin. As a thermosetting resin containing a glycidyl group in the chemical structure, bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, cyclic aliphatic epoxy resin, long chain aliphatic epoxy resin, glycidyl ester epoxy resin Epoxy resin, glycidyl amine type epoxy resin, flame retardant epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, etc. may be mentioned. Among these, bisphenol A epoxy resin and bisphenol F epoxy resin are preferable from the viewpoints of adhesiveness with a semiaromatic polyamide resin (A), processability and versatility.

The thermosetting resin (E) used in the present invention contains various curing agent components for the purpose of promoting the curing reaction. As curing agents, aliphatic polyamines, aromatic amines, modified amines, polyamidoamines, secondary amines, tertiary amines, imidazole compounds, polymercaptan compounds, acid anhydrides, boron trifluoride-amine complexes, dicyandiamides, organic acids Hydrazide is mentioned. Examples of aliphatic polyamines include diethylenetriamine, triethylenetriamine, tetraethylenepentamine, dipropenediamine, diethylaminopropylamine, N-aminoethylpiperazine, mensene diamine, isophorone diamine, 1,3-bisaminocyclohexane Be Examples of aromatic amines include m-xylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone. An example of a secondary amine includes piperidine. Examples of tertiary amines include N, N-dimethylpiperazine, triethylenediamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol. Examples of the imidazole compound include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-aminoethyl-2-undecylimidazolium trimellitate, and an epoxy-imidazole adduct. Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis trimellitate, glycerol tris trimellitate, maleic anhydride, tetrahydrophthalic anhydride, endo Methylenetetrahydrophthalic anhydride, Methyl endo methylenetetrahydrophthalic anhydride, Methylbutenyltetrahydrophthalic anhydride, Dodecenyl succinic anhydride, Hexahydrophthalic anhydride, Methylhexahydrophthalic anhydride, Succinic anhydride, Methylcyclohexene dicarboxylic anhydride, Alkylstyrene-maleic anhydride copolymer, chlorendic anhydride, polyazelaic anhydride can be mentioned. The curing agent may be contained singly or in combination. As the thermosetting resin (E) used in the present invention, one-component and two-component thermosetting epoxy resins commercially available for bonding and sealing can be used. Among them, one-pack thermosetting epoxy resin is preferable.

The thermosetting resin (E) used in the present invention may be heat-cured at a temperature suitable for each of the thermosetting resins, but preferably is heat-curable at 23 to 140 ° C., It is more preferable that the heat curing process can be performed at a temperature of 120 ° C., and further preferably, the heat curing process can be performed at 60 to 100 ° C. If the temperature at which the thermosetting treatment of the thermosetting resin (E) can be carried out is lower than the above lower limit, there is a possibility that a problem may occur that the thermosetting reaction does not proceed sufficiently. When the temperature at which the thermosetting process of the thermosetting resin (E) can be carried out exceeds the above upper limit, crystallization and softening of the semiaromatic polyamide resin composition (C) occur by the heat applied during the curing reaction, and the obtained molded article is obtained There is a possibility that a defect may occur in the dimensions.

The adhesive strength between the thermosetting resin (E) and the molded article (D) comprising the semiaromatic polyamide resin composition (C) obtained in the present invention is measured by the method described in the section of the following examples. The adhesive strength is an item related to the durability of the molded article obtained by the present invention. In the present invention, the adhesive strength can achieve 1.5 MPa or more. Moreover, 2.0 MPa or more is preferable, 2.5 MPa or more is more preferable, and 3.0 MPa or more is more preferable. When the adhesive strength is less than the above lower limit, peeling of the adhesive surface between the molded article (D) comprising the semiaromatic polyamide resin (C) and the thermosetting resin (E) easily occurs, and the strength and sealing of the molded article There is a possibility that sex can not be satisfied. It is more preferable that the failure state at the time of the adhesive strength measurement is a state of base material failure in which the test piece itself is broken. When the semi-aromatic polyamide resin composition (C) contains a predetermined amount of the styrene-maleimide copolymer (F), adhesive strength to such an extent that base material destruction occurs can be achieved.

The molded product obtained in the present invention is a molded product obtained by assembling a molded product (D) comprising the semi-aromatic polyamide resin composition (C) and a thermosetting resin (E) containing a glycidyl group in the chemical structure. As a method of assembling, a method of assembling by injecting or applying a thermosetting resin (E) to a molded article (D) comprising the semi-aromatic polyamide resin composition (C) is preferable.

The molded article (D) obtained in the present invention can be made into a composite molded article by bonding to the same material and different materials via the thermosetting resin (E). The different material is not particularly limited, but examples thereof include resins other than the semi-aromatic polyamide resin (A) and metal materials.

The molded article of the present invention uses a semi-aromatic polyamide resin composition containing a semi-aromatic polyamide resin having specific physical properties such as the amount of end groups in addition to the composition, and a thermosetting resin having a glycidyl group Thus, it has high water absorption dimensional stability, heat resistance, and adhesiveness, and it is possible to provide a molded article (composite molded article) that highly satisfies user needs. By including a predetermined amount of the styrene-maleimide copolymer (F) in the semi-aromatic polyamide resin composition, a more preferable embodiment is obtained.

The molded article of the present invention can be widely used for automobile parts and electric and electronic parts, and is not particularly limited, but is particularly preferably used for various connectors, switches, and camera parts. Connectors, switches, camera parts, etc. often have a small molded product size, and if dimensional change occurs due to water absorption, this may lead to contact failure with the terminals. When the molded body is mounted in a solder reflow process, blisters may occur on the surface of the molded body due to the influence of water absorption. When the molded body is used for a camera part, displacement of the optical axis may occur due to dimensional change due to water absorption, which may cause a failure in the operation as a camera.
Further, in the case of connectors, switches, and camera parts, a thermosetting resin is often used to seal a molded body for the purpose of preventing entry of moisture and foreign matter from the outside. If the adhesion to the thermosetting resin is low, the sealing property may be insufficient, and the product may be damaged due to the influence of moisture and foreign matter entering from the outside.

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

(1) Terminal amino group concentration, terminal carboxyl group concentration After dissolving semiaromatic polyamide resin (A) in a solvent of deuterated chloroform (CDCl ₃ ) / hexafluoroisopropanol (HFIP) = 1/1, and dropping formic acid Each end group concentration was measured by ¹ H-NMR.

(2) Peak area (ΔH _Tc2 ) associated with thermal crystallization
Measure 10 mg of semi-aromatic polyamide resin dried under reduced pressure at 105 ° C for 15 hours in a pan made of aluminum (manufactured by SII Nano Technology Inc., part number 170421S), and use an aluminum lid (manufactured by SAI nano technology Inc, part number 170420) After preparing a measurement sample in a sealed state, the temperature was raised from room temperature at 20 ° C./min using a high sensitivity type differential scanning calorimeter DSC 7020 (manufactured by SII Nano Technology Inc.) and held at 350 ° C. for 3 minutes Later, the measurement sample pan was taken out, dipped in liquid nitrogen, and quenched. Thereafter, the sample is taken out of liquid nitrogen and left at room temperature for 30 minutes, and then heated again from room temperature at a rate of 20 ° C./minute using a high sensitivity type differential scanning calorimeter DSC7020 (manufactured by SII Nano Technology Inc.) After holding at 350 ° C. for 3 minutes, the temperature was lowered to 30 ° C. at 10 ° C./min. The peak area of heat _release derived from cold crystallization at the time of temperature lowering was taken as (ΔH _Tc2 ).

(3) Melting point (Tm)
Measure 10 mg of semi-aromatic polyamide resin dried under reduced pressure at 105 ° C for 15 hours in a pan made of aluminum (manufactured by SII Nano Technology Inc., part number 170421S), and use an aluminum lid (manufactured by SAI nano technology Inc, part number 170420) After preparing a measurement sample in a sealed state, the temperature was raised from room temperature at 20 ° C./min using a high sensitivity type differential scanning calorimeter DSC 7020 (manufactured by SII Nano Technology Inc.) and held at 350 ° C. for 3 minutes Later, the measurement sample pan was taken out, dipped in liquid nitrogen, and quenched. Thereafter, the sample is taken out of liquid nitrogen and left at room temperature for 30 minutes, and then heated again from room temperature at a rate of 20 ° C./minute using a high sensitivity type differential scanning calorimeter DSC7020 (manufactured by SII Nano Technology Inc.) And held at 350 ° C. for 3 minutes. The peak temperature of endotherm due to melting at the time of temperature rise was taken as the melting point (Tm).

(4) Glass transition temperature (Tg)
Measure 10 mg of semi-aromatic polyamide resin dried under reduced pressure at 105 ° C for 15 hours in a pan made of aluminum (manufactured by SII Nano Technology Inc., part number 170421S), and use an aluminum lid (manufactured by SAI nano technology Inc, part number 170420) After preparing a measurement sample in a sealed state, the temperature was raised from room temperature at 20 ° C./min using a high sensitivity type differential scanning calorimeter DSC 7020 (manufactured by SII Nano Technology Inc.) and held at 350 ° C. for 3 minutes Later, the measurement sample pan was taken out, dipped in liquid nitrogen, and quenched. Thereafter, the sample is taken out of liquid nitrogen and left at room temperature for 30 minutes, and then heated again from room temperature at a rate of 20 ° C./minute using a high sensitivity type differential scanning calorimeter DSC7020 (manufactured by SII Nano Technology Inc.) And held at 350 ° C. for 3 minutes. The inflection point of the baseline at the time of temperature rise was taken as the glass transition temperature (Tg).

(5) 80 ° C 95% RH equilibrium water absorption rate Using the injection molding machine EC-100 made by Toshiba Machine, the cylinder temperature is set to the melting point + 20 ° C of the resin, the mold temperature is set to 140 ° C, 100mm long, 100mm wide, 1mm thick The flat plate was injection-molded to prepare a test piece for evaluation. After annealing the test piece in an atmosphere at 150 ° C. for 2 hours, the mass was measured, and the mass at this time was taken as the mass at the time of drying. Further, the annealed test piece was allowed to stand in an atmosphere at 85 ° C. and 95% RH (relative humidity) for 1000 hours, and then its mass was measured, and the mass at this time was taken as the mass at the time of saturated water absorption. From the mass at the time of saturated water absorption and drying measured by the above-mentioned method, 80 ° C. 95% RH equilibrium water absorption was determined from the following equation.
80 ° C 95% RH equilibrium water absorption (%) = {(mass at saturated water absorption-mass at drying) / mass at drying} × 100

(6) 80 ° C 95% RH equilibrium water absorption dimensional change rate The cylinder temperature is set to + 20 ° C of the melting point of the resin and the mold temperature is set to 140 ° C using an injection molding machine EC-100 made by Toshiba Machine, 100 mm long, 100 mm wide, A flat plate with a thickness of 1 mm was injection molded to prepare a test piece for evaluation. After annealing the test piece in an atmosphere at 150 ° C. for 2 hours, the dimensions in the parallel direction and the perpendicular direction to the film gate are measured with a caliper at a position of 50 mm from the end, respectively, I asked for. Moreover, 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 perpendicular direction) / 2
Furthermore, after leaving the annealed test specimen to stand in an atmosphere of 85 ° C. and 95% RH (relative humidity) for 1000 hours, the average size is determined by the same method as described above, and the average size at this time is the average at the time of equilibrium water absorption. It was a size. From the average dimensions at the time of equilibrium water absorption and drying measured by the above-mentioned method, the 80 ° C. 95% RH equilibrium water absorption dimensional change rate was determined from the following equation.
80 ° C. 95% RH equilibrium water absorption dimensional change rate (%) = {(average size at equilibrium water absorption−average size at drying) / average size at drying} × 100

(7) Bonding strength Using an injection molding machine EC-100 made by Toshiba Machine, the cylinder temperature is set to the melting point of the resin + 20 ° C, the mold temperature is set to 140 ° C, and the evaluation test piece described in FIG. , Made. The upper view of FIG. 1 is a top view seen from the top, and the lower view is a side view seen from the side. After uniformly applying 0.04 g of a thermosetting resin to the adhesive surface (area 310 mm ² : total area of the arrow end in the upper view of FIG. 2) of the prepared test specimen for evaluation, the test specimen of the same shape is used. Heat treatment was performed for 60 minutes in an atmosphere of 100 ° C. in a state of bonding and fixing so that the bonding surfaces were paired (lower in FIG. 2), to prepare a test piece for adhesive strength evaluation. The prepared test piece was allowed to stand at room temperature for 24 hours, and then evaluated at a tensile speed of 5 mm / min with a precision universal testing machine AG-IS manufactured by Shimadzu Corporation, and adhesion strength was determined from the following equation.
Bonding strength (MPa) = test force at the time of specimen failure / bonding area (310 mm ² )

(8) Adhesion failure mode The state of failure when the adhesion strength was evaluated by the method described above was classified using the following index.
Base material: No breakage occurs at the adhesive (thermosetting resin) portion or at the interface between the resin composition test piece and the adhesive, and the test piece itself is broken Interface: Adhesive (thermosetting resin) portion or resin composition Fracture at the interface of the specimen and adhesive

(9) Solder Reflow Resistance Using an injection molding machine EC-100 manufactured by Toshiba Machine, the cylinder temperature is set to the melting point of the resin + 20 ° C., the mold temperature is set to 140 ° C., length 127 mm, width 12.6 mm, thickness 0. Test pieces of 8 mm for UL combustion test were injection molded to prepare test pieces. The test piece was left for 72 hours in an atmosphere at 85 ° C. and 85% RH (relative humidity). The test piece is preheated by raising the temperature from room temperature to 150 ° C over 60 seconds in an air reflow furnace (AIS AIS-20-82C), then at a heating rate of 0.5 ° C / min to 190 ° C. Preheating was performed. Thereafter, the temperature was raised to a predetermined set temperature at a rate of 100 ° C./min, and held at the predetermined temperature for 10 seconds, followed by cooling. The set temperature was increased every 240 ° C. to 5 ° C., and the highest set temperature at which surface swelling or deformation did not occur was used as a reflow heat resistance temperature and was used as an index of solder heat resistance.
○: Reflowable temperature limit is 260 ° C or higher ×: Reflowable temperature limit is less than 260 ° C

This example was conducted using a semi-aromatic polyamide resin (A) synthesized as exemplified 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 hypophosphite as a catalyst, 40 g of acetic acid as a terminal regulator and 17.52 kg of ion exchanged water The autoclave was charged with N ₂ from atmospheric pressure to 0.05 MPa, released from pressure, and returned to atmospheric pressure. This operation was performed three times, and after performing N ₂ substitution, it was uniformly dissolved at 135 ° C. and 0.3 MPa with stirring. Thereafter, the solution was continuously supplied by a liquid feed pump, and the temperature was raised to 240 ° C. by a heating pipe, and heat was applied for 1 hour. Thereafter, the reaction mixture was supplied to the pressure reaction vessel, heated to 290 ° C., and a portion of water was distilled off to maintain the internal pressure of the vessel at 3 MPa, to obtain a low-order condensate. Then, this low-order condensate is directly supplied to a twin-screw extruder (screw diameter 37 mm, L / D = 60) while maintaining the molten state, and the resin temperature is 335 ° C. while removing water from three vents. The polycondensation was advanced under melting to obtain a semi-aromatic polyamide resin (A-1). The obtained semi-aromatic polyamide resin (A-1) has 65.1 mol% of a structural unit consisting of 1,6-hexamethylenediamine and terephthalic acid and 34.9 mol of a structural unit consisting of 11-aminoundecanoic acid %, Relative viscosity 2.1, melting point 314 ° C., AEG = 20 eq / ton, CEG = 140 eq / ton, analyzed by ¹ H-NMR.

Synthesis Example 2
8.57 kg of 1,6-hexamethylenediamine, 12.24 kg of terephthalic acid, 7.99 kg of 11-aminoundecanoic acid, 9 g of sodium hypophosphite as a catalyst, 150 g of acetic acid as an end blocking agent and 16.20 kg of ion exchanged water The autoclave was charged with N ₂ from atmospheric pressure to 0.05 MPa, released from pressure, and returned to atmospheric pressure. This operation was performed three times, and after performing N ₂ substitution, it was uniformly dissolved at 135 ° C. and 0.3 MPa with stirring. Thereafter, the solution was continuously supplied by a liquid feed pump, and the temperature was raised to 240 ° C. by a heating pipe, and heat was applied for 1 hour. Thereafter, the reaction mixture was supplied to the pressure reaction vessel, heated to 290 ° C., and a portion of water was distilled off to maintain the internal pressure of the vessel at 3 MPa, to obtain a low-order condensate. Thereafter, the low-order condensate was taken out into a container under normal temperature and pressure in the air, and then dried under an environment of 70 ° C. and a vacuum degree of 50 Torr using a vacuum dryer. After drying, the lower condensate was reacted with a blender (volume 0.1 m ³ ) for 6 hours at 210 ° C. under a vacuum of 50 Torr for 6 hours to obtain a semi-aromatic polyamide resin (A-2). The obtained semi-aromatic polyamide resin (A-2) has 65.3 mol% of a constituent unit consisting of 1,6-hexamethylenediamine and terephthalic acid and 34.7 mol of a constituent unit consisting of 11-aminoundecanoic acid % consists of a relative viscosity 2.03, melting point 313 ° ^C., was 1 AEG was analyzed by H-NMR = 2eq / ton, CEG = 111eq / ton.

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 diphosphite as a catalyst, 395 g of acetic acid as an end blocking agent and 12.68 kg of ion exchanged water The autoclave was charged with N ₂ from atmospheric pressure to 0.05 MPa, released from pressure, and returned to atmospheric pressure. This operation was performed three times, and after performing N ₂ substitution, it was uniformly dissolved at 135 ° C. and 0.3 MPa with stirring. Thereafter, the solution was continuously supplied by a liquid feed pump, and the temperature was raised to 240 ° C. by a heating pipe, and heat was applied for 1 hour. Thereafter, the reaction mixture was supplied to the pressure reaction vessel, heated to 290 ° C., and a portion of water was distilled off to maintain the internal pressure of the vessel at 3 MPa, to obtain a low-order condensate. Thereafter, the low-order condensate was taken out into a container under normal temperature and pressure in the air, and then dried under an environment of 70 ° C. and a vacuum degree of 50 Torr using a vacuum dryer. After drying, the low-order condensate was reacted with a blender (volume 0.1 m ³ ) for 6 hours at 210 ° C. under a vacuum of 50 Torr for 6 hours to obtain a semiaromatic polyamide resin (A-3). The obtained semi-aromatic polyamide resin (A-3) has 64.8 mol% of a structural unit consisting of 1,6-hexamethylenediamine and terephthalic acid and 35.2 mol of a structural unit consisting of 11-aminoundecanoic acid %, Relative viscosity 1.84, melting point 314 ° C., AEG = 29 eq / ton, CEG = 30 eq / ton, analyzed by ¹ H-NMR.

Synthesis Example 4
According to the method described in Example 1 of JP-A-7-228689, terephthalic acid units, 1,9-nonanediamine units and 2-methyl-1,8-octanediamine units (1,9-nonanediamine units: 2 The synthesis of a semi-aromatic polyamide resin consisting of 85:15 in the molar ratio of methyl-1,8-octanediamine units was carried out (end blocking agent is benzoic acid). The obtained semi-aromatic polyamide resin (A-4) had a relative viscosity of 2.1, a melting point of 286 ° C., AEG = 13 eq / ton and CEG = 50 eq / ton as analyzed by ¹ H-NMR.

Synthesis Example 5
According to the method described in Comparative Example 3 of WO 2006/098434, terephthalic acid units, 1,9-nonanediamine units and 2-methyl-1,8-octanediamine units (1,9-nonanediamine units: 2-methyl) The synthesis of a semi-aromatic polyamide resin consisting of a molar ratio of 80:20) 1,8-octanediamine units was carried out (end blocking agent is benzoic acid). The obtained semi-aromatic polyamide resin (A-5) had a relative viscosity of 2.1, a melting point of 282 ° C., AEG = 80 eq / ton, CEG = 46 eq / ton as analyzed by ¹ H-NMR.

This example was performed using the semi-aromatic polyamide resin composition (C) produced as illustrated below.

The components and mass proportions (parts by mass) described in Tables 1 and 2 were melt-kneaded at a melting point of + 20 ° C. of each polyamide raw material using a twin screw extruder STS-35 manufactured by Coperion Co., Ltd. Examples 1-9 Semi-aromatic polyamide resin compositions (C) of Comparative Examples 1 to 5 were obtained. The raw materials used for preparation of a polyamide resin composition by the above-mentioned method using semi-aromatic polyamide resin composition (C) are as follows. The release agent and the stabilizer used as other additives were used at a mass ratio of 1: 5.
Semi-Aromatic Polyamide Resin (A-1): Semi-Aromatic Polyamide Resin Produced According to Synthesis Example 1 Semi-Aromatic Polyamide Resin (A-2): Semi-Production Produced According to Synthesis Example 2 Above Aromatic polyamide resin Semi-aromatic polyamide resin (A-3): Semi-aromatic polyamide resin produced based on the above-mentioned Synthesis Example 3 Semi-aromatic polyamide resin (A-4): Based on the above-mentioned Synthesis Example 4 Semi-aromatic polyamide resin produced Semi-aromatic polyamide resin (A-5): Semi-aromatic polyamide resin produced according to the above Synthesis Example 5 Semi-aromatic polyamide resin (A-6): PA10T (KINGFA SCI . & TECH.CO., LTD. Made Vicnyl (R) 700)
Reinforcing material (B): Glass fiber (manufactured by Nippon Electric Glass Co., Ltd., T-275H)
Styrene-maleimide copolymer (F): styrene-N-phenylmaleimide-maleic anhydride copolymer (Denka Co., Ltd., Denka IP MS-NIP)
Releasing agent: Magnesium stearate Stabilizer: pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, manufactured by Chiba Specialty Chemicals)

In this example, a molded article (D) comprising the semiaromatic polyamide resin composition (C) produced as described above and a thermosetting resin (E) were used. .

Examples 1 to 9 and Comparative Examples 1 to 5
Examples 1 to 9 and Comparative Examples 1 to 5 were carried out according to the method described above using the semiaromatic polyamide resin composition (C) and the thermosetting resin (E) described in Tables 1 and 2.
Thermosetting resin (E-1): one-component thermosetting epoxy resin (manufactured by ThreeBond 2222P)
Thermosetting resin (E-2): One-component thermosetting epoxy resin (Taoka Chemical Co., Ltd. AH-3031T)

As apparent from Tables 1 and 2, in Examples 1 to 3 not only high adhesiveness with the thermosetting resin (E) can be expressed, but also the 80% 95% RH equilibrium water absorption dimensional change rate is small, and the solder reflow resistance It can be seen that it has excellent characteristics, such as satisfying the property. Further, in Example 4, although the AEG value is as low as 2 eq / ton and the adhesion to the thermosetting resin (E) is slightly reduced as compared with Examples 1 to 3, the adhesive strength is 2.9 MPa, Sufficient characteristics have been obtained for practical use. In Example 5, the thermosetting resin (E) is changed, but sufficient adhesive strength is obtained, and it can be seen that the resin has excellent properties. On the other hand, Comparative Example 1 uses a semi-aromatic polyamide resin produced from the same monomers as in Examples 1 to 3, but the value of (AEG + CEG) is as low as 59 eq / ton, and a thermosetting resin (E) Adhesiveness with is insufficient. Comparative Examples 2 and 3 use a semi-aromatic polyamide resin (PA9T / M8T) manufactured from monomers different from those of Examples 1 to 5, and in Comparative Example 2, the value of (AEG + CEG) is as low as 63 eq / ton. In addition, since ΔH _Tc2 is large and Tg is high, adhesion to the thermosetting resin (E) is insufficient. In Comparative Example 3, although the value of (AEG + CEG) is appropriate at 126 eq / ton, the adhesiveness with the thermosetting resin (E) is insufficient because ΔH _Tc2 is large and Tg is high. Comparative Example 4 uses a semi-aromatic polyamide resin (PA10T) produced from monomers different from those of Examples 1 to 5, and in addition to the low value of (AEG + CEG) of 44 eq / ton, ΔH _Tc2 is large. Because of high Tg, adhesion to the thermosetting resin (E) is insufficient. In Comparative Example 5, although the thermosetting resin (E) is changed, although the value of (AEG + CEG) is appropriate to 126 eq / ton as in Comparative Example 3, the ΔH _Tc2 is large and the Tg is high. Adhesiveness with curable resin (E) is inadequate.
Further, in Examples 6 to 9, since the adhesion strength is high and the adhesion failure mode is also the base material, it is understood that the adhesive property with the thermosetting resin (D) is excellent. Furthermore, the 80 ° C. 95% RH equilibrium water absorption rate, the 80 ° C. 95% RH equilibrium water absorption dimensional change rate is also low, and the dimensional stability at the time of water absorption is also excellent.

The molded article of the present invention uses a semi-aromatic polyamide resin composition containing a semi-aromatic polyamide resin having specific physical properties such as the amount of end groups in addition to the composition, and a thermosetting resin having a glycidyl group Therefore, it has high water absorption dimensional stability, heat resistance and adhesiveness, and a molded article (composite molded article) highly satisfying user needs can be industrially advantageously manufactured.

Claims

The reinforcing material (B) contains 0 to 200 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide resin (A) satisfying the following requirements (a) to (c), and has an equilibrium water absorption of 80.degree. The molded object which has a structure which the molded article (D) which consists of a semi-aromatic polyamide resin composition (C) which is 3.0% or less, and the thermosetting resin (E) containing glycidyl group directly intervenes.
(A) Peak area (ΔH Tc2 ) associated with temperature-decreasing crystallization measured by differential scanning calorimetry (DSC) is 40 mJ / mg or less (b) Glass transition temperature (Tg) is 120 ° C. or less (c) Terminal amino group concentration (c) Sum of (AEG) and terminal carboxyl group concentration (CEG) (AEG + CEG) is at least 70 eq / ton
The semiaromatic polyamide resin composition (C) further comprises 10 to 60 parts by mass of a styrene-maleimide copolymer (F) with respect to 100 parts by mass of the semiaromatic polyamide resin (A). The molded body described.
The semi-aromatic polyamide resin (A) contains 50 to 100 mol% of a repeating unit consisting of a diamine having 6 to 12 carbon atoms and terephthalic acid, and 0 to 50 mol of a repeating unit consisting of an aminocarboxylic acid or lactam having 10 or more carbon atoms The molded article according to claim 1 or 2, which is a semi-aromatic polyamide resin containing%.
A semiaromatic polyamide resin comprising 50 to 100 mol% of repeating units consisting of hexamethylenediamine and terephthalic acid and 0 to 50 mol% of repeating units consisting of aminoundecanoic acid or undecanelactam as the semiaromatic polyamide resin (A) The molded object according to claim 1 or 2.
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 part comprising the molded body according to any one of claims 1 to 5.