JP5759111B2 - Copolymer and molded body - Google Patents

Description

  The present invention relates to a molded body comprising a copolymer and a resin composition containing the copolymer.

  Liquid crystal polymers typified by wholly aromatic polyesters have high heat resistance and excellent electrical properties, and are mainly used for electrical and electronic parts. Such parts are produced by injection molding or extrusion molding of a wholly aromatic polyester resin composition, and are joined to other members with an epoxy, urethane, acrylic, or other adhesive.

  Generally, when producing a molded object from the resin composition containing a copolymer, changing a copolymerization component is performed so that the characteristic suitable for a use may be acquired. As for wholly aromatic polyesters, attempts have been made to improve the properties of wholly aromatic polyesters by incorporating specific structural units using various compounds as copolymerization components (see, for example, Patent Documents 1 and 2). .

JP 2009-227807 A Japanese Patent No. 4302638

  By the way, a molded product of wholly aromatic polyester has a low affinity with an adhesive, so that it may be difficult to join the same or different members. Although the adhesive has been improved, there is a limit to the improvement of the adhesive strength by the adhesive.

  It is conceivable to improve the adhesiveness by changing the copolymerization component of the wholly aromatic polyester as in the above patent document. However, if the proportion of structural units to be changed in order to obtain a sufficient improvement effect becomes too large, advantages such as heat resistance and moldability of the wholly aromatic polyester are impaired.

  The present invention has been made in view of the above circumstances, and a copolymer and a molded body capable of improving the adhesive strength of the molded body while sufficiently maintaining the excellent heat resistance and moldability of the wholly aromatic polyester. The purpose is to provide.

In order to solve the above problems, the present invention provides 40 to 99 mol% of a repeating structural unit represented by the following general formula (1) and 1 to 15 mol of a repeating structural unit represented by the following general formula (3). %, A repeating structural unit represented by the following general formula (4) more than 0 mol% and 30 mol% or less, and a repeating structural unit represented by the following general formula (5) more than 1 mol% and 30 mol% or less , Ri Na contain a total of 100 mole% of structural units of the following general formula (1) and (3) to (5), and, the structural units of the following general formula (3) and (4) Provided is a copolymer in which the total content is equal to the content of the structural unit of the following general formula (5) .

式（１）中、Ｘは、下記式（Ａ）又は（Ｂ）で表される２価の芳香族基を示す。

In formula (1), X represents a divalent aromatic group represented by the following formula (A) or (B) .

Two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.

式（３）中、Ｌ^１は、−ＣＨ_２−、−（ＣＨ_３）_２Ｃ−、−Ｏ−、又は−ＳＯ_２−を示す。

In Formula (3), L ¹ represents —CH ₂ —, — (CH ₃ ) ₂ C—, —O—, or —SO ₂ —.

式（４）中、Ｙは、下記式（４−１）で表される２価の基を示す。

式（４−１）中、Ａｒ ^１ は下記式（Ａ）又は（Ｂ）で表される２価の芳香族基を示し、Ｙ ^１ は下記式（４−２）で表される２価の基を示し、ｔは、０又は１の整数を示す。

なお、式（Ａ）で表されるベンゼン環の２つの結合手はメタ位又はパラ位の関係にある。

式（４−２）中、Ｌ ^２ は−Ｏ−、−Ｓ−又は−ＳＯ−を示し、ｓは０又は１の整数を示す。なお、式（４−２）で表されるベンゼン環の２つの結合手はメタ位又はパラ位の関係にある。

In formula (4), Y represents a divalent group represented by the following formula (4-1).

In formula (4-1), Ar ¹ represents a divalent aromatic group represented by the following formula (A) or (B), and Y ¹ represents a divalent group represented by the following formula (4-2). Represents a group, and t represents an integer of 0 or 1.

Note that the two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.

In formula (4-2), L ² represents —O—, —S— or —SO—, and s represents an integer of 0 or 1. In addition, the two bonds of the benzene ring represented by the formula (4-2) are in a meta position or a para position.

式（５）中、Ｚは、下記式（５−１）で表される２価の基を示す。

式（５−１）中、Ａｒ ^２ は下記式（Ａ）又は（Ｂ）で表される２価の芳香族基を示し、Ｚ ^１ は下記式（５−２）で表される２価の基を示し、ｖは、０又は１の整数を示す。

なお、式（Ａ）で表されるベンゼン環の２つの結合手はメタ位又はパラ位の関係にある。

式（５−２）中、Ｌ ^３ は、２価の炭化水素基、−Ｏ−、−ＳＯ−、−ＳＯ _２ −、又は−ＣＯ−を示し、ｕは、０又は１の整数を示す。なお、式（５−２）で表されるベンゼン環の２つの結合手はメタ位又はパラ位の関係にある。

In the formula (5), Z represents a divalent group represented by the following formula (5-1) .

In formula (5-1), Ar ² represents a divalent aromatic group represented by the following formula (A) or (B), and Z ¹ represents a divalent group represented by the following formula (5-2). Represents a group, and v represents an integer of 0 or 1.

Note that the two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.

In formula (5-2), L ³ represents a divalent hydrocarbon group, —O—, —SO—, —SO ₂ —, or —CO—, and u represents an integer of 0 or 1. Note that the two bonds of the benzene ring represented by the formula (5-2) are in a meta position or a para position.

  According to the copolymer of the present invention, by containing the specific structural unit in the specific ratio, while maintaining the excellent heat resistance and moldability of the wholly aromatic polyester, Adhesive strength can be improved.

  The present invention also provides a molded article obtained by molding a resin composition containing the copolymer of the present invention. A molded body made of such a resin composition can be excellent in heat resistance and improved in adhesiveness.

  ADVANTAGE OF THE INVENTION According to this invention, the copolymer and molded object which can improve the adhesive strength of a molded object can be provided, fully maintaining the outstanding heat resistance and moldability of wholly aromatic polyester.

  The copolymer of the present invention is represented by 40 to 99 mol% of a repeating structural unit represented by the following general formula (1), a repeating structural unit represented by the following formula (2), and the following general formula (3). 1 to 15 mol% in total of one or more kinds of repeating structural units among the repeating structural units to be expressed, and a repeating structure represented by the following general formula (4) other than the repeating structural unit represented by the formula (2) The unit contains 0 to 30 mol% and the repeating structural unit represented by the following general formula (5) contains 0 to 30 mol%.

式（１）中、Ｘは、芳香族基を含む２価の有機基を示す。

In formula (1), X represents a divalent organic group containing an aromatic group.

式（３）中、Ｌ^１は、−ＣＨ_２−、−（ＣＨ_３）_２Ｃ−、−Ｏ−、又は−ＳＯ_２−を示す。

In Formula (3), L ¹ represents —CH ₂ —, — (CH ₃ ) ₂ C—, —O—, or —SO ₂ —.

式（４）中、Ｙは、芳香族基を含む２価の有機基を示す。

In formula (4), Y represents a divalent organic group containing an aromatic group.

式（５）中、Ｚは、芳香族基を含む２価の有機基を示す。

In formula (5), Z represents a divalent organic group containing an aromatic group.

  X in the general formula (1) is preferably a divalent aromatic group represented by the following formula (A) or the following formula (B) from the viewpoint of heat resistance and molding processability. Note that the two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.

  Examples of Y in the general formula (4) include a divalent group represented by the following general formula (4-1).

式（４−１）中、Ａｒ^１は２価の芳香族基を示し、Ｙ^１は芳香環を有する２価の基を示し、ｔは、０又は１の整数を示す。

In formula (4-1), Ar ¹ represents a divalent aromatic group, Y ¹ represents a divalent group having an aromatic ring, and t represents an integer of 0 or 1.

Ar ¹ is preferably a divalent aromatic group represented by the following formula (A) or (B) in terms of heat resistance and molding processability. Note that the two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.

Examples of Y ¹ include a divalent group represented by the following formula (4-2).

式（４−２）中、Ｌ^２は、−Ｏ−、−Ｓ−、又は−ＳＯ−を示し、ｓは、０又は１の整数を示す。なお、式（４−２）中のベンゼン環の２つの結合手はメタ位又はパラ位の関係にある。

In formula (4-2), L ² represents —O—, —S—, or —SO—, and s represents an integer of 0 or 1. In addition, the two bonds of the benzene ring in formula (4-2) are in a meta-position or a para-position.

  In the copolymer of the present invention, Y in the general formula (4) is a divalent group represented by the following formula (4-3) particularly from the viewpoint of improving fluidity during injection molding. It is preferable.

  Examples of Z in the general formula (5) include a divalent group represented by the following general formula (5-1).

式（５−１）中、Ａｒ^２は２価の芳香族基を示し、Ｚ^１は芳香環を有する２価の基を示し、ｖは、０又は１の整数を示す。

In Formula (5-1), Ar ² represents a divalent aromatic group, Z ¹ represents a divalent group having an aromatic ring, and v represents an integer of 0 or 1.

Ar ² is preferably a divalent aromatic group represented by the following formula (A) or (B) in terms of heat resistance and molding processability. Note that the two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.

Examples of Z ¹ include a divalent group represented by the following formula (5-2).

式（５−２）中、Ｌ^３は、２価の炭化水素基、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、又は−ＣＯ−を示し、ｕは、０又は１の整数を示す。２価の炭化水素基としては、炭素数１〜３のアルカンジイル基が挙げられ、そのうち、−Ｃ（ＣＨ_３）_２−又は−ＣＨ（ＣＨ_３）−が好ましい。なお、式（５−２）中のベンゼン環の２つの結合手はメタ位又はパラ位の関係にある。

In Formula (5-2), L ³ represents a divalent hydrocarbon group, —O—, —S—, —SO—, —SO ₂ —, or —CO—, and u is 0 or 1 Indicates an integer. Examples of the divalent hydrocarbon group include alkanediyl groups having 1 to 3 carbon atoms, and among them, —C (CH ₃ ) ₂ — or —CH (CH ₃ ) — is preferable. In addition, the two bonds of the benzene ring in formula (5-2) are in a meta-position or a para-position.

  In the copolymer of the present invention, Z in the general formula (5) is preferably a divalent group represented by the following formula (5-3) or the following formula (5-4). In particular, when a divalent group represented by the formula (5-3) is incorporated using terephthalic acid or the like, the heat resistance can be improved. When the divalent group represented by the formula (5-4) is incorporated using isophthalic acid or the like, the heat resistance tends to be lowered, but the above two types of compounds are used in combination to formula (5-3). ) And a divalent group represented by the formula (5-4) can be finely adjusted.

  The copolymer of the present invention can be produced according to a conventional polyester polycondensation method.

  The repeating structural unit represented by the general formula (1) includes, for example, parahydroxybenzoic acid, metahydroxybenzoic acid, salicylic acid, those obtained by modifying these phenol sites with propionate, acetate or formate, and these Carboxylic acid moiety modified with methyl ester, ethyl ester, isopropyl ester or phenyl ester, etc., as well as 2-hydroxy-6-naphthoic acid, its positional isomer, and these phenol moieties as propionic acid ester, acetate ester or formic acid Incorporation into the copolymer by using one or more compounds of those modified with esters and those modified with methyl ester, ethyl ester, isopropyl ester or phenyl ester as the copolymer component. It can be.

  These compounds are blended in such a proportion that the repeating structural unit represented by the general formula (1) is 40 to 99 mol% in the copolymer.

  In the case of producing a copolymer for injection molding, it is preferable to use parahydroxybenzoic acid and / or a derivative thereof that reduces entanglement of polymer molecules. When producing a copolymer for extrusion molding, it is preferable to try 2-hydroxy-6-naphthoic acid and / or a derivative thereof that increases the entanglement of polymer molecules.

  Parahydroxybenzoic acid and derivatives thereof, and 2-hydroxy-6-naphthoic acid and derivatives thereof can be used singly or in combination of two or more. In this embodiment, for example, (a) parahydroxybenzoic acid and / or a derivative thereof and (b) 2-hydroxy-6-naphthoic acid and / or a derivative thereof can be used in combination. As a use ratio in this case, the range in which the molar ratio (a) / (b) is 0.1 to 10 is preferable, the range in which 0.3 to 8 is more preferable, and the range in which 0.4 to 5 is set. Even more preferred. When the proportion of (a) increases, the entanglement of polymer molecules decreases, and properties unfavorable for extrusion molding, particularly film molding, such as longitudinal tearability tend to be exhibited.

  The repeating structural unit represented by the general formula (2) is, for example, a compound represented by the following formula (2-A), one of those obtained by modifying this phenol moiety with a propionic acid ester, acetate ester or formate ester. More than one type of compound can be incorporated into the copolymer by using it as a copolymerization component.

  The repeating structural unit represented by the general formula (3) includes, for example, 4,4′-diaminodiphenylmethane, 4,4′-diamino-2,2-diphenylpropane, 4,4′-diaminodiphenyl ether, 4 , 4'-diaminodiphenylsulfone and one or more of these amine moieties modified with propionic acid amide, acetic acid amide or formic acid amide can be incorporated into the copolymer as a copolymerization component. it can.

  Said compound is mix | blended in the ratio from which the repeating structural unit represented by said Formula (2) and the repeating structural unit represented by the said General formula (3) become 1-15 mol% in a copolymer in total. , Preferably 1 to 14 mol%, more preferably 1 to 13 mol%. When the above compound is used in an amount exceeding 15 mol%, the viscosity excessively increases during polymerization or, in the extreme case, carbonization occurs. Further, when the amount of the structural unit is less than 1%, the effect of improving adhesiveness cannot be obtained sufficiently.

  The repeating structural unit represented by the general formula (4) includes, for example, 4,4′-biphenol, hydroquinone, 2,6-naphthalenediol, and these phenol moieties as propionate, acetate, formate, phenyl. One or more of the compounds modified with an ester can be incorporated into the copolymer by using it as a copolymerization component. Among these, 4,4'-biphenol is preferably used from the viewpoint of mechanical strength.

  These compounds are blended in such a proportion that the repeating structural unit represented by the above general formula (4) is 0 to 30 mol% in the copolymer, and preferably 27 mol% or less from the viewpoint of cost reduction. Preferably, it is blended at a ratio of 25 mol% or less.

  The repeating structural unit represented by the general formula (5) is, for example, one or more of terephthalic acid, isophthalic acid, and those obtained by modifying these carboxylic acid sites with methyl ester, ethyl ester, isopropyl ester or phenyl ester The compound can be incorporated into the copolymer by using it as a copolymerization component.

  These compounds are blended in such a proportion that the repeating structural unit represented by the general formula (5) is 0 to 30 mol% in the copolymer, preferably 27 mol% or less, more preferably 25 mol%. It mix | blends in the ratio used as follows. If the above compound is used in such an amount that the repeating structural unit represented by the general formula (5) exceeds 30 mol%, it is not preferable because the viscosity becomes high during the polymerization.

  About each copolymer component mentioned above, a composition is selected so that the total mole number of a carboxylic acid residue in said formula (1)-(5) and the total mole number of a hydroxy residue and an amino residue may become equal. It is important. In the copolymer of the present invention, the structural unit represented by the general formula (4) and the structural unit represented by the general formula (5) may not be included. When the structural units of (5) and (5) are included, the sum of the structural units of the formulas (1) to (5) is 100 mol%, and the total content of the structural units of the formulas (2) to (4) It can be set so that the content ratio of the structural unit in 5) is equal. When the structural unit of formula (4) is not included and the structural unit of (5) is included, the total of the structural units of formulas (1) to (3) and (5) is 100 mol%, and the formula (2 ) To (3) can be set so that the total content of the structural units is equal to the content of the structural units (5).

The copolymer of the present invention preferably has a surface energy of 35 mJ / m ² or more when the copolymer is molded into a plate, sheet or film. In this case, the affinity with an adhesive or metal having a polar group is increased, and it is possible to firmly adhere to another member. For example, the surface energy of the copolymer can be increased by increasing the content of the repeating structural unit represented by the above formula (2) and / or the repeating structural unit represented by the formula (3). .

  The copolymer of the present invention preferably has a melting point measured by a differential scanning calorimeter (DSC) in the range of 300 to 400 ° C. If the melting point is less than 300 ° C, the heat resistance tends to be insufficient. On the other hand, if the melting point exceeds 400 ° C, a large amount of energy is required at the time of molding, and the moldability is remarkably lowered.

The copolymer of the present invention can be produced according to a conventional polyester polycondensation method. Although there is no limitation about a manufacturing method, the following method is mentioned, for example.
A: A method in which acetic anhydride is added to a mixture of an aromatic dihydroxy compound, aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, and optionally an aromatic diamine, followed by a deacetic acid polycondensation reaction.
B: A method of producing by deacetic acid polycondensation from a diacylated product of an aromatic dihydroxy compound, an acylated product of an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and optionally a diamide compound of an aromatic diamine.
C: A method of producing by dephenol polycondensation from an aromatic dihydroxy compound, a phenyl ester of an aromatic hydroxycarboxylic acid, a diphenyl ester of an aromatic dicarboxylic acid, and optionally an aromatic diamine.
D: produced by dephenol polycondensation after reacting aromatic hydroxycarboxylic acid and aromatic dicarboxylic acid with a predetermined amount of diphenyl carbonate to convert the carboxyl group to phenyl ester, adding aromatic dihydroxy compound, and optionally aromatic diamine how to.

  As a typical example, parahydroxybenzoic acid, terephthalic acid, isophthalic acid, 4,4′-biphenol, and 4,4′-diaminodiphenylmethane are put into a reactor, acetic anhydride is added and acetic anhydride is refluxed. Acetoxylation is performed. Thereafter, the polyester or polyester amide can be produced by performing deacetic acid polycondensation while raising the temperature and distilling acetic acid in the temperature range of 250 to 350 ° C. The polymerization time can be selected in the range of 1 to 100 hours.

  Moreover, a catalyst can be used when performing the above polycondensation reaction. Specifically, magnesium acetate, stannous acetate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, N-methyl Examples include imidazole.

  The copolymer of the present invention can be produced by using both melt polymerization and solid phase polymerization for each of the above polymerization reactions. Solid-phase polymerization is a method for further polymerizing a prepolymer that has been subjected to polycondensation by melt polymerization. Solid-phase polymerization can be performed, for example, by heat-treating a prepolymer obtained by melt polymerization in an atmosphere of an inert gas such as nitrogen or under reduced pressure at a temperature range of 200 to 350 ° C. for 1 to 30 hours. . At the laboratory level, a Kugelrohr device can be used. Industrially, a cylindrical rotary reactor is preferably used.

  The polymerization vessel in the melt polymerization is not particularly limited, but a stirring tank type polymerization having a stirrer having a shape such as a vertical type, a multistage type, a spiral band, and a helical axis, which is used for a general high viscosity reaction. More specifically, a Warner mixer, a Banbury mixer, a pony mixer, a Mueller mixer, a roll mill, a continuous scan capable kneader, a pug mill, a gear compounder, or the like can be used.

  The copolymer of the present invention can be used alone or mixed with other resins and used as a resin composition in which additives are blended as necessary.

  In the resin composition according to the present invention, for the purpose of mainly improving the mechanical strength, inorganic or organic fillers such as a fibrous shape, a granular shape, and a plate shape can be blended.

  Examples of the fibrous filler include glass fiber, silica fiber, silica alumina fiber, potassium titanate fiber, carbon fiber, metal fiber such as aluminum, titanium and copper.

  Examples of granular fillers include carbon black, graphite, silica, quartz powder, glass beads, milled glass fiber, glass balloon, glass powder, calcium silicate, aluminum silicate, talc, clay, diatomaceous earth, and wollastonite. Silicate, iron oxide, titanium oxide, zinc oxide, antimony trioxide, alumina, calcium sulfate, and other various metal powders.

  Examples of the plate-like filler include mica, glass flakes and various metal foils.

  Examples of the organic filler include fibers made of polyester, polyimide, and polyamide.

  When mix | blending an inorganic filler, it is preferable that the compounding quantity is 10-90 mass% with respect to the whole composition, and it is more preferable that it is 10-80 mass%. If the blending amount exceeds 90% by mass, the mechanical strength tends to decrease. On the other hand, if the blending amount is less than 10% by mass, the blending effect hardly appears.

  In addition to the above, additives such as conventionally known antioxidants, heat stabilizers, reinforcing agents, pigments, flame retardants and the like can be appropriately added to the resin composition according to the present invention. These additives can be used individually or in combination of 2 or more types as appropriate.

  The resin composition containing the copolymer of the present invention can be subjected to a melt molding process such as a conventionally known molding method, injection molding, film molding, sheet molding, blow molding, and compression molding. Through such a processing method, a molded product can be obtained by processing into a fiber, a film, a sheet, a container, a hose, a three-dimensional molded product, or the like. The molded product thus obtained can be increased in strength and elastic modulus by a heat treatment under appropriate conditions. This heat treatment can be performed, for example, by heating the molded article in an inert atmosphere, an oxygen-containing atmosphere, or under reduced pressure at a temperature below the melting point of the composition.

  Specific uses of the molded product formed by molding the resin composition containing the copolymer of the present invention include camera module parts such as mobile phones and digital cameras, LED parts, substrates such as copper-clad laminates, and other electrical devices. -It can be used suitably for electronic components.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

Example 1
In a 200 mL three-necked flask equipped with a mechanical stirrer, 33 g (0.24 mol) of parahydroxybenzoic acid (PHBA), 11 g (0.06 mol) of 4,4′-biphenol (BP), and 10 g of terephthalic acid (TPA) (0.06 mol), 3 g (0.02 mol) of isophthalic acid (IPA), and 5 g (0.02 mol) of 4,4′-diaminodiphenylsulfone were introduced. Furthermore, 40 mL of acetic anhydride, 10 mg of magnesium acetate and 10 mg of potassium acetate were added thereto. This acetic anhydride slurry was heated to reflux for 2 hours under control of 140 ° C. using a mantle heater.

  Next, the reflux device was changed to a distillation device, and the mantle heater was changed to a molten salt bath. While acetic acid was distilled off, the temperature was increased from 180 ° C. to 300 ° C. at a rate of 5 ° C./10 minutes. After maintaining at 300 ° C. for 10 minutes, the content was poured into a stainless steel vat, and the resulting polymer was allowed to cool. Next, the cooled polymer was pulverized with a pulverizer to obtain a powdery prepolymer.

  Next, the prepolymer obtained above was put into a Kugelrohr apparatus and heated to 290 ° C. under reduced pressure, whereby solid phase polymerization was performed while distilling off low molecular weight components. A copolymer was thus obtained.

  The copolymer obtained above was measured for surface energy, melting point, peel strength, and apparent viscosity according to the following method. The results are shown in Table 2. In addition, the destruction mode of the sample after the measurement of peel strength was resin destruction.

[Measurement of surface energy]
The copolymer was press-molded at 350 ° C. to prepare a plate-like sample (3 cm × 6 cm × 1.5 mm). Using an automatic contact angle meter (manufactured by Kyowa Interface Chemical Co., Ltd., DM-501), a drop of pure water and diiodomethane (1.0 μL) was dropped from the tip of a syringe onto a plate sample, and the contact angle The surface energy was determined using the Owens equation.

[Measurement of melting point]
Using a differential scanning calorimeter (manufactured by Seiko Denshi Kogyo Co., Ltd.), α-alumina was used as a reference. The measurement conditions were that the temperature was raised from room temperature to 420 ° C. at 20 ° C./min, the copolymer was melted, then the temperature was lowered to 150 ° C. at 10 ° C./min, and further raised to 430 ° C. at 20 ° C./min. The peak of the endothermic peak that was sometimes obtained was taken as the melting point.

[Measurement of peel strength]
A test piece of 3 cm × 6 cm × 1.5 mm was produced from the copolymer using a press molding machine. The production conditions were 330 ° C. and 5 MPa, and the time was 2 minutes. At that time, a copper foil (3 cm × 10 cm × 0.02 mm) previously degreased with acetone was adhered to one side. The peel strength of this sample was measured using a tensile tester under the conditions of a tensile angle of 90 degrees and a tensile speed of 5 cm / min.

[Apparent viscosity]
Using a capillary rheometer (2010 type) manufactured by Intesco with a capillary diameter of 1.0 mm, a length of 40 mm, and an inflow angle of 90 °, a melting rate of −30 ° C. to a melting point of + 20 ° C. at a shear rate of 100 sec ⁻¹ The viscosity at 320 ° C. was read in a constant temperature heating method in which heating was carried out at a constant rate of + 4 ° C./min.

(Example 2)
A copolymer was obtained in the same manner as in Example 1 except that 4 g (0.02 mol) of 4,4′-diaminodiphenyl ether was used in place of 4,4′-diaminodiphenyl sulfone. Evaluation similar to Example 1 was performed about the obtained copolymer. The results are shown in Table 2. In addition, the destruction mode of the sample after the measurement of peel strength was resin destruction.

(Example 3)
Except for using 4 g (0.04 mol) of 4,4′-diaminodiphenylmethane instead of 4,4′-diaminodiphenylsulfone and using 7.4 g (0.04 mol) of 4,4′-biphenol, A copolymer was obtained in the same manner as in Example 1. Evaluation similar to Example 1 was performed about the obtained copolymer. The results are shown in Table 2. In addition, the destruction mode of the sample after the measurement of peel strength was resin destruction.

Example 4
A copolymer was obtained in the same manner as in Example 1 except that 4 g (0.02 mol) of 4,4′-diamino-2,2-diphenylpropane was used in place of 4,4′-diaminodiphenylsulfone. It was. Evaluation similar to Example 1 was performed about the obtained copolymer. The results are shown in Table 2. In addition, the destruction mode of the sample after the measurement of peel strength was resin destruction.

( Reference Example 5)
In the same manner as in Example 1, except that 6.5 g (0.02 mol) of phosphorus compound A represented by the following formula (2-A) was used instead of 4,4′-diaminodiphenylsulfone. A polymer was obtained. Evaluation similar to Example 1 was performed about the obtained copolymer. The results are shown in Table 2. In addition, the destruction mode of the sample after the measurement of peel strength was resin destruction.

( Reference Example 6)
In a 200 mL three-necked flask equipped with a mechanical stirrer, 32 g (0.23 mol) of parahydroxybenzoic acid (PHBA), 11 g (0.06 mol) of 2-hydroxy-6-naphthoic acid (HNA), the above formula (2 Phosphorus compound A11 g (0.03 mol) represented by -A) and 6 g (0.04 mol) of isophthalic acid (IPA) were introduced. Furthermore, 40 mL of acetic anhydride, 10 mg of magnesium acetate and 10 mg of potassium acetate were added thereto. This acetic anhydride slurry was heated to reflux for 2 hours under control of 140 ° C. using a mantle heater.

  Next, the reflux device was changed to a distillation device, and the mantle heater was changed to a molten salt bath. While acetic acid was distilled off, the temperature was raised from 180 ° C. to 270 ° C. at a rate of 5 ° C./10 minutes. Thereafter, the content was poured into a stainless steel vat, and the resulting polymer was allowed to cool. Next, the cooled polymer was pulverized with a pulverizer to obtain a powdery prepolymer.

  Next, the prepolymer obtained above was put into a Kugelrohr apparatus and heated to 290 ° C. under reduced pressure, whereby solid phase polymerization was performed while distilling off low molecular weight components. A copolymer was thus obtained. Evaluation similar to Example 1 was performed about the obtained copolymer. The results are shown in Table 2. In addition, the destruction mode of the sample after the measurement of peel strength was resin destruction.

(Comparative Example 1)
A copolymer was obtained in the same manner as in Example 1 except that 4,4′-diaminodiphenylsulfone was not blended and 15 g (0.08 mol) of 4,4′-biphenol was used. Evaluation similar to Example 1 was performed about the obtained copolymer. The results are shown in Table 2. Note that the fracture mode of the sample after the peel strength measurement was peeling of the interface between copper and resin (interfacial fracture).

(Comparative Example 2)
In a 200 mL three-necked flask equipped with a mechanical stirrer, 11 g (0.08 mol) of parahydroxybenzoic acid (PHBA), 8 g (0.04 mol) of 2-hydroxy-6-naphthoic acid (HNA), 4,4 ′ -22 g (0.12 mol) of biphenol (BP), 20 g (TPA) (0.12 mol) of terephthalic acid, 3 g (0.02 mol) of isophthalic acid (IPA), 5 g of 4,4′-diaminodiphenylsulfone (0 .04 mol) was introduced. Furthermore, 40 mL of acetic anhydride, 10 mg of magnesium acetate and 10 mg of potassium acetate were added thereto. This acetic anhydride slurry was heated to reflux for 2 hours under control of 140 ° C. using a mantle heater.

  Next, the reflux device was changed to a distillation device, and the mantle heater was changed to a molten salt bath. While acetic acid was distilled off, the temperature was increased from 180 ° C. at a rate of 5 ° C./10 minutes. The fluidity of the polymer was lost at around 250 ° C., and marked scorching was observed from around 270 ° C.

(Comparative Example 3)
A copolymer was obtained in the same manner as in Reference Example 6 except that the phosphorus compound A was not blended and 6.5 g (0.03 mol) of 4,4′-biphenol was used. Evaluation similar to Example 1 was performed about the obtained copolymer. The results are shown in Table 2. Note that the fracture mode of the sample after the peel strength measurement was peeling of the interface between copper and resin (interfacial fracture).

(Comparative Example 4)
In a 200 mL three-necked flask equipped with a mechanical stirrer, 9.5 g (0.07 mol) of parahydroxybenzoic acid (PHBA), 10 g of terephthalic acid (TPA) (0.06 mol), 3 g of isophthalic acid (IPA) (0 0.02 mol), 16 g (0.08 mol) of 4,4′-diaminodiphenyl ether were introduced. Furthermore, 40 mL of acetic anhydride, 10 mg of magnesium acetate and 10 mg of potassium acetate were added thereto. This acetic anhydride slurry was heated to reflux for 2 hours under control of 140 ° C. using a mantle heater.

  Next, the reflux device was changed to a distillation device, and the mantle heater was changed to a molten salt bath. While acetic acid was distilled off, the temperature was increased from 180 ° C. at a rate of 5 ° C./10 minutes. The fluidity of the polymer was lost around 230 ° C., and significant scorching was seen from around 260 ° C.

ADVANTAGE OF THE INVENTION According to this invention, the copolymer which can improve the adhesive strength of a molded object can be provided, fully maintaining the outstanding heat resistance and moldability of wholly aromatic polyester. Moreover, the molded object which consists of a resin composition containing the copolymer of this invention is excellent in affinity with adhesives, such as an epoxy type, a urethane type, and an acryl type, and can express the outstanding adhesiveness. Further, according to the molded body according to the present invention, since the affinity with the metal is high, a composite with the metal, for example, a copper-clad laminate, is simply thermocompression bonded between the metal and the molded body according to the present invention. It becomes possible to mold with.

Claims (6)

40-99 mol% of repeating structural units represented by the following general formula (1),
1 to 15 mol% of repeating structural units represented by the following general formula (3),
The repeating structural unit represented by the following general formula (4) is more than 0 mol% and 30 mol% or less,
And 1 mol percent to 30 mol percent of the repeating structural unit represented by the following general formula (5), Ri greens contain,
The sum of the structural units of the general formulas (1) and (3) to (5) is 100 mol%, and the total content of the structural units of the general formulas (3) and (4) A copolymer having the same content ratio of the structural unit of the formula (5) .

[In Formula (1), X shows the bivalent aromatic group represented by a following formula (A) or (B).

(Two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.)]

[In the formula (3), L ¹ represents —CH ₂ —, — (CH ₃ ) ₂ C—, —O—, or —SO ₂ —. ]

[In formula (4), Y represents a divalent group represented by the following formula (4-1).

{In Formula (4-1), Ar ¹ represents a divalent aromatic group represented by the following Formula (A) or (B), and Y ¹ represents a divalent group represented by the following Formula (4-2). T represents an integer of 0 or 1.

(Two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.)

(In the formula (4-2), L ² represents —O—, —S— or —SO—, and s represents an integer of 0 or 1. The benzene ring represented by the formula (4-2) The two bonds in are in the meta or para position.)}]

[In the formula (5), Z represents a divalent group represented by the following formula (5-1).

{In Formula (5-1), Ar ² represents a divalent aromatic group represented by the following Formula (A) or (B), and Z ¹ is a divalent represented by the following Formula (5-2). V represents an integer of 0 or 1.

(Two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.)

(In Formula (5-2), L ³ represents a divalent hydrocarbon group, —O—, —SO—, —SO ₂ —, or —CO—, and u represents an integer of 0 or 1. Note that the two bonds of the benzene ring represented by the formula (5-2) are in a meta-position or a para-position)}] The repeating structural unit represented by the general formula (4) is a divalent group represented by the following formula (4-3),
The copolymer according to claim 1, wherein the repeating structural unit represented by the general formula (5) is a divalent group represented by the following formula (5-3) or the following formula (5-4). .

  The molded object formed by shape | molding the resin composition containing the copolymer of Claim 1 or 2.   The shaped body according to claim 3, which is used for forming a composite with a metal. The shaped body according to claim 3 , which is used for thermocompression bonding with a metal to form a composite.   The composite_body | complex obtained by thermocompression-bonding a metal and the molded object of Claim 3.