JP5066789B2 - Liquid crystalline resin, method for producing the same, liquid crystalline resin composition and molded article - Google Patents

Description

The present invention has an extremely small amount of gas generation, hardly causes blistering on the surface when formed into a molded product, and does not cause cloudiness in these transparent parts when used in combination with transparent parts made of glass or plastic. The present invention relates to a liquid crystalline resin that is optimal for electrical and electronic applications that do not corrode these metal parts when used in contact with the parts, a manufacturing method thereof, a liquid crystalline resin composition, and a molded product.

  Demand for liquid crystalline resins is growing, mainly for small precision molded products for electrical and electronic applications, taking advantage of their excellent heat resistance, fluidity, and electrical properties. In recent years, attention has been paid to its thermal stability and high thermal dimensional accuracy, and studies have been made on use as a support base for heat-generating components, such as a liquid crystal display support base for OA devices and mobile phones, and structural parts for lamps.

  In these applications, since it is often used in contact with metal parts such as terminals that generate heat, it is necessary not to attack these metal parts, but many liquid crystalline resins are used for deacetic acid polycondensation and phenol removal. Since it is produced by polycondensation, corrosive gases such as acetic acid and phenol are generated, and its use may be limited in these applications.

  In addition, in the liquid crystal display support base material, problems such as clouding of the display lens due to these gases occur. In particular, phenol gas with poor volatility causes fogging as if the glass surface was doubled. In addition, when these gases are generated in a large amount, oligomers are released along with the gas through the same decomposition route, which causes a problem of fogging the glass surface.

  In these applications, surface fitting with other parts may be required or sliding resistance with metal parts may be required, but liquid crystalline resins are processed at a high temperature close to the decomposition temperature during molding. For this reason, the surface of the molded product may be blistered due to gas, thereby reducing the yield.

Regarding such a gas problem, studies have been made to improve the terminal group of the liquid crystalline resin to reduce the gas amount. (For example, Patent Documents 1 to 3).
JP-A-2-16150 (pages 1 and 2) Japanese Patent No. 3309459 (pages 1 and 2) JP-A-11-263829 (pages 1 and 2)

  However, although the method described in Patent Document 1 increases the amount of carboxylic acid end groups of the liquid crystalline resin, it has been found that this method increases the amount of carbon dioxide and decreases the mechanical properties of the liquid crystalline resin. . Patent Document 2 describes a method of reducing the amount of acetic acid gas generated by reducing the ratio of the acetylated hydroxyl group terminal to the carboxylic acid terminal of the liquid crystalline resin. However, according to the method described in the document, the gas generation at about 200 ° C. is certainly improved. However, when improvement of the gas generation amount at a high temperature exceeding 330 ° C. is required, it is not sufficient. There wasn't.

  Further, Patent Document 3 describes that gas burning can be improved by compounding a liquid crystalline resin and water to increase the hydroxyl terminal by hydrolyzing the acetylated hydroxyl terminal, and this method. In this case, not only the hydrolysis of the terminal but also the decomposition of the ester bond in the polymer chain occurs, so the total amount of terminal groups increases, and the amount of carbon dioxide and phenol gas is not sufficiently reduced. As the amount increased, the cloudiness of the glass was not improved.

  The present invention relates to a reduced liquid crystalline resin, a method for producing the same, a liquid crystalline resin composition, and an acetic acid gas, a phenol gas, and a carbon dioxide gas that cause such metal corrosion, clouding of glass, blistering of molded products, and the like. It is an object to provide those molded products.

  As a result of intensive studies to solve the above problems, the present inventors have found a liquid crystalline polyester that exhibits a specific low gas property.

That is, the present invention
(1) Consists of structural units of the following (I), (II), (III), (IV) and (V), and the structural unit (I) is the sum of the structural units (I), (II) and (III) The structural unit (II) is 60 to 75 mol% based on the total of the structural units (II) and (III), and the structural unit (IV) is the structural unit (IV). And (V) is 60 to 92 mol%, and the total of structural units (II) and (III) and the sum of (IV) and (V) are substantially equimolar. The acetic acid gas generated from the liquid crystalline resin when held for 30 minutes at a melting point of + 10 ° C. (however, when the melting point is less than 325 ° C.) for 30 minutes in a helium gas atmosphere is less than 100 ppm, phenol gas is less than 20 ppm, and Carbon dioxide is not 100ppm Liquid crystalline resin is,

(2) The liquid crystalline resin according to the above (1), wherein ΔS (melting entropy) defined by Formula 1 is 0.9 × 10 ⁻³ J / g · K or less,
ΔS (J / g · K) (= ΔHm (J / g) / [Tm (° C.) + 273] − [1]
(Tm is a differential calorimetry. After observing the endothermic peak temperature (Tm1) observed when polymerized polymer is measured at room temperature to 20 ° C./min from the room temperature, it is held at a temperature of Tm1 + 20 ° C. for 5 minutes. After that, the temperature is once cooled to room temperature under a temperature decrease condition of 20 ° C./min, and again indicates an endothermic peak temperature (Tm2) observed when measured under a temperature increase condition of 20 ° C./min. ΔHm is the melting at the endothermic peak. (The amount of heat (ΔHm2).)
(3) structural unit (IV) is 7 2-92 mole percent is based on the combined total of the structural units (IV) and (V) above (1) or (2), wherein liquid resin,
(4) A liquid crystalline resin obtained by acetylating a phenolic hydroxyl group in a liquid crystalline resin raw material and then polycondensing the acetylation reaction from a monoacetylated product to a diacetylated product among the aromatic diols used. The above-mentioned obtained by carrying out until the remaining amount of the monoacetylated product calculated by the following formula of the aromatic diol (I) having the slowest reaction rate is 0.8 to 5 mol% of the charged aromatic diol (I) The liquid crystalline resin according to any one of (1) to (3),
Residual amount of monoacetylated product (%) = {[monoacetylated product] / ([monoacetylated product] + [diacetylated product])} × 100
[Monoacetylated product]: Molar amount of monoacetylated product of aromatic diol (I)
[Diacetylated product]: molar amount of diacetylated product of aromatic diol (I) ( 5 ) Filler of 30 to 200 weights per 100 weight parts of liquid crystalline resin described in any one of (1) to ( 4 ) above Liquid crystalline resin composition comprising a part,
( 6 ) A liquid crystalline resin raw material containing hydroquinone and 4,4′-dihydroxybiphenyl is used, and a phenolic hydroxyl group in the liquid crystalline resin raw material and 1.03 to 1.09 molar equivalents relative to the total of the phenolic hydroxyl groups A method for producing a liquid crystalline resin by performing an acetylation reaction of acetic anhydride at a temperature of 140 ° C. or more and 150 ° C. or less for 2.1 to 2.9 hours, followed by polycondensation using the acetylation reaction Among aromatic diols, the remaining reaction rate of the monoacetylated product calculated by the following formula of the aromatic diol (I) having the slowest reaction rate from the monoacetylated product to the diacetylated product is 0.8 to 0.8 of the aromatic diol (A) charged. The method for producing a liquid crystalline resin according to any one of the above (1) to ( 4 ), wherein the acetylation reaction is carried out until the concentration becomes 5 mol%,
Residual amount of monoacetylated product (%) = {[monoacetylated product] / ([monoacetylated product] + [diacetylated product])} × 100
[Monoacetylated product]: Molar amount of monoacetylated product of aromatic diol (I) [Diacetylated product]: Mole amount of diacetylated product of aromatic diol (I) ( 7 ) Any of (1) to ( 4 ) above A molded product comprising the liquid crystalline resin according to claim 5 or the liquid crystalline resin composition according to ( 5 ) above,
( 8 ) The present invention relates to a film comprising the liquid crystalline resin according to any one of (1) to ( 4 ) or the liquid crystalline resin composition according to ( 5 ).

  The liquid crystalline resin of the present invention generates very little gas, and when it is used to form a molded product, it is difficult to cause blistering on the surface. When used in combination with transparent parts made of glass or plastic, these transparent resins When the parts are not cloudy and are used in contact with metal parts, they are optimal for electrical and electronic applications that do not corrode these metal parts.

  The liquid crystalline resin of the present invention has at least two types of structural units derived from aromatic diol as essential structural units, and is maintained for 30 minutes at a melting point of + 10 ° C. (however, when the melting point is less than 325 ° C., 335 ° C.) in a helium gas atmosphere. In this case, the acetic acid gas generated from the resin or the resin composition is 100 ppm or less, the phenol gas is less than 20 ppm, and the carbon dioxide gas is less than 100 ppm. The amount of acetic acid gas generated is preferably 80 ppm or less, more preferably 50 ppm or less, and even more preferably 20 ppm or less. The phenol gas amount is preferably 10 ppm or less, more preferably 8 ppm or less, and the carbon dioxide gas amount is preferably 80 ppm or less, more preferably 60 ppm or less.

  Here, the melting point is the temperature of Tm1 + 20 ° C. after observing the endothermic peak temperature (Tm1) observed when the polymer having been polymerized is measured at room temperature to 20 ° C./min in the differential calorimetry. This is the endothermic peak temperature (Tm2) observed when the sample is held for 5 minutes, then cooled to room temperature under a temperature drop condition of 20 ° C./min, and measured again under a temperature rise condition of 20 ° C./min.

  Less generation of acetic acid gas and phenol gas is preferable because there is less corrosion on metal parts and no cloudiness of glass occurs. Further, it is preferable that the generation of carbon dioxide gas is small, so that no blistering or surface roughness of the molded product occurs.

  The amount of acetic acid gas, phenol gas, and carbon dioxide gas generated can be determined, for example, with a pyrolysis gas chromatograph-mass spectrometer (TG / GC-MS) under a helium stream.

  The liquid crystalline resin of the present invention contains at least two types of structural units derived from aromatic diols. Examples of aromatic diols include 4,4′-dihydroxybiphenyl, hydroquinone, resorcinol, t-butylhydroquinone, and phenylhydroquinone. Chlorohydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 3,4'-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, and 4,4'-dihydroxydiphenyl ether 4,4′-dihydroxybiphenyl, hydroquinone and 2,6-dihydroxynaphthalene are preferable, and 4,4′-dihydroxybiphenyl and hydroquinone are more preferable.

  As combinations of two kinds of aromatic diols, combinations of 4,4′-dihydroxybiphenyl and hydroquinone, combinations of 4,4′-dihydroxybiphenyl and 2,6-dihydroxynaphthalene, combinations of hydroquinone and 2,6-dihydroxynaphthalene Is preferable, and a combination of 4,4′-dihydroxybiphenyl and hydroquinone is particularly preferable.

  Two or more types of aromatic diols can be used in addition to the two types of aromatic diols.

  In the aromatic diol component, one of the phenolic hydroxyl groups of the aromatic diol component is usually acetylated by an acetylation reaction to become a monoacetylated product, and further acetylation proceeds to a diacetylated product. When chemical compounds are used, the reaction rate often differs.

  Here, the acetylation in this invention shows the concept of reaction which converts the hydroxyl group containing all monoacetylation, diacetylation, etc. into an acetyl group.

  The at least two kinds of diol components used in the present invention are generally similar in reactivity in the monoacetylation reaction, but a combination having a difference in reactivity from a monoacetylated product to a diacetylated product is preferable. For example, 4,4'-dihydroxybiphenyl and hydroquinone have almost the same monoacetylation reaction rate. However, when the reaction is performed under the same conditions, hydroquinone is converted from a monoacetylated product to a diacetylated product compared to 4,4'-dihydroxybiphenyl. The reaction rate to (the diacetylation reaction rate of the monoacetylated product) is small, and a long reaction time is required to reduce the residual amount of the monoacetylated product.

  The present invention has found that when the acetylation reaction is performed using two or more kinds of aromatic diols, a difference occurs in the residual amount of the monoacetylated product. Then, when the residual amount of the monoacetylated product of the aromatic diol having a low diacetylation reaction rate is controlled to be 0.8 to 5 mol% with respect to 100 mol% of the charged molar amount of the aromatic diol having a low diacetylation reaction rate. Since the phenolic hydroxyl group remaining without being acetylated is inferior in polycondensation reactivity, the phenolic hydroxyl group of the aromatic diol is preferentially produced at the terminal of the produced liquid crystalline resin. In the present invention, by forming the phenolic hydroxyl group end of the aromatic diol at the end of the liquid crystalline resin in this way, it becomes the cause of generation of acetylated hydroxyl group that causes acetic acid gas generation, carbon dioxide gas, and phenol gas. It is thought that the carboxylic acid terminal derived from p-hydroxybenzoic acid can be reduced.

  That is, when producing a liquid crystalline resin, an acetylation reaction is performed using a phenolic hydroxyl group in a monomer which is a raw material for the liquid crystalline resin to be used and an acetylating agent such as acetic anhydride, and the resultant is subjected to polycondensation. In order to obtain the liquid crystalline resin specified in the present invention, the acetylation reaction is carried out while refluxing at a temperature of 140 ° C. or higher and 150 ° C. or lower until the residual amount of monoacetylated aromatic diol reaches a specific range. (Hereinafter also referred to as “acetylation step”) is preferable. As an apparatus for the acetylation reaction, for example, a reaction vessel equipped with a return tube and a rectifying column can be used. The reaction time of acetylation is roughly 1 to 5 hours, but the time until the residual amount of monoacetylated aromatic diol reaches a specific range depends on the liquid crystalline resin raw material used and the reaction temperature. Different.

  Preferably, the time is 2.1 to 2.9 hours. The shorter the reaction temperature, the shorter the time, and the shorter the molar ratio of acetic anhydride to the phenolic hydroxyl terminal, the shorter the time.

  In the present invention, in the acetylation step, the remaining amount of the monoacetylated product of the aromatic diol (a) having the slowest diacetylation reaction rate of the monoacetylated product among the aromatic diols used is the amount of the aromatic diol (a). When the charged molar amount is 100 mol%, it is preferably carried out until it becomes 0.8 to 5 mol%, more preferably less than 1 to 3 mol%, until 1.2 to 2.4 mol%. More preferably it is performed.

The residual amount of monoacetylated product can be derived from the following equation.
Residual amount of monoacetylated product (%) = {[monoacetylated product] / ([monoacetylated product] + [diacetylated product])} × 100
[Monoacetylated product]: Mole amount of monoacetylated product of aromatic diol (I) [Diacetylated product]: Mole amount of diacetylated product of aromatic diol (I)

  Here, at the end of the acetylation reaction, the unreacted product in which neither of the two hydroxyl groups of the aromatic diol is acetylated, monoacetylation proceeds relatively easily, and usually affects the above formula. Therefore, ([monoacetylated product] + [diacetylated product]) can be regarded as a concentration corresponding to the total number of moles of the charged aromatic diol.

  Further, among the aromatic diols used, the residual amount of the monoacetylated product of the aromatic diol monomer having the fastest diacetylation reaction rate of the monoacetylated product is 0. When the molar amount of each aromatic diol is 100 mol%. It is preferably less than 5 mol%.

  The composition ratio of the aromatic diol having a large residual amount of monoacetylated compound to other aromatic diols is preferably 10 to 40 mol%, more preferably 20 to 30 mol%.

The residual amount of monoacetylated product can be obtained from the above-described calculation formula. Specifically, for example, a part of the reaction mixture after the acetylation step is sampled, and can be calculated from the following peak intensity by ¹ H-nuclear magnetic resonance spectrum measurement. Here, the peak intensity corresponds to the peak area.

Since two or more types of diols used can be attributed to a peak derived from each of the aromatic diol by peak separation for each of the aromatic diol component, it can be obtained the residual amount of the mono-acetylated product.
Ia: peak attributed to a bound aromatic nucleus hydrogen atom bonded to the α-position carbon of the carbon in the water group which are not acetylated mono acetylated aromatic diol intensity Ib: mono acetylated aromatic diol and Peak intensity attributed to the hydrogen atom bonded to the α-position carbon of the aromatic carbon to which the acetyl group of the diacetylated compound is bonded Remaining amount of monoacetylated compound (%) = [Ia / (Ia + Ib)] × 100

  In addition, as a model reaction, only one kind of aromatic diol for which the residual amount of monoacetylated compound is to be obtained is charged into a reaction vessel, and a molar ratio of acetic anhydride to be actually used for the reaction is added to actually adopt it. Even if the model reaction is performed under the reaction conditions and the residual amount of the monoacetylated product is analyzed, the same analysis result as in the case of using the mixture can be obtained.

  In general, acetylation is generally carried out at a sufficient molar ratio of acetic anhydride, reaction temperature, and reaction time, and the residual amount of monoacetylated product is generally close to 0. As for the terminal of the functional resin, the acetylated hydroxyl group terminal and the carboxyl group terminal are almost equal, and acetic acid gas, carbon dioxide gas and phenol gas are easily generated.

  Conversely, when acetylation is extremely incomplete, too much monoacetylated diol of aromatic diol is formed, and the degree of polymerization may not increase and a liquid crystalline resin may not be obtained. Since almost the same amount of carboxyl end groups are present in the hydroxyl group to be produced, the amount of generated phenol gas and carbon dioxide gas is large.

  By controlling as described above, the carboxyl group of the aromatic dicarboxylic acid and the hydroxyl group of the aromatic diol are preferentially generated at the terminal, and there is almost no carboxyl terminal group of p-hydroxybenzoic acid. It is considered that a liquid crystalline resin having an improved carbon dioxide generation amount can be obtained.

  The liquid crystalline resin of the present invention has at least two types of structural units derived from aromatic diol as essential structural units, but the other structural units can provide a liquid crystalline resin satisfying the gas amount defined by the present invention. If there is, it will not be specifically limited.

  The liquid crystalline resin is a resin that forms an anisotropic molten phase, and examples thereof include liquid crystalline resins having an ester bond such as liquid crystalline polyester and liquid crystalline polyester amide.

  The liquid crystalline polyester is a polyester that forms an anisotropic molten phase. For example, the liquid crystalline polyester includes a structural unit derived from at least two kinds of aromatic diols, that is, an aromatic dioxy unit, an aromatic oxycarbonyl unit, and an aromatic diester. Examples thereof include polyesters that form an anisotropic molten phase composed of structural units selected from carbonyl units and ethylenedioxy units to form liquid crystalline polyesters.

  Specific examples of the aromatic oxycarbonyl unit include, for example, structural units generated from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and the like, and specific examples of the aromatic dicarbonyl unit include, for example, Terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 1,2-bis (2-chloro) Examples thereof include structural units formed from phenoxy) ethane-4,4′-dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, and the like.

  Specific examples of the liquid crystalline polyester include a structural unit generated from p-hydroxybenzoic acid, a structural unit generated from 4,4′-dihydroxybiphenyl, a structural unit generated from hydroquinone, and generated from terephthalic acid and / or isophthalic acid. Liquid crystalline polyester composed of structural units, structural units generated from p-hydroxybenzoic acid, structural units generated from ethylene glycol, structural units generated from 4,4'-dihydroxybiphenyl, structural units generated from hydroquinone, terephthalic acid, and Liquid crystalline polyester composed of structural units generated from isophthalic acid, structural units generated from p-hydroxybenzoic acid, structural units generated from hydroquinone, structural units generated from 4,4′-dihydroxybiphenyl, 2,6- Naphthalene Structural units generated from carboxylic acid, liquid crystalline polyesters consisting of structural units generated from terephthalic acid, structural units generated from p-hydroxybenzoic acid, structural units generated from 2,6-dihydroxynaphthalene, 4,4′-dihydroxy Examples thereof include a liquid crystalline polyester composed of a structural unit formed from biphenyl and a structural unit formed from terephthalic acid and / or isophthalic acid.

  Preferable examples of the liquid crystalline polyester forming the anisotropic molten phase include liquid crystalline polyesters comprising the following structural units (I), (II), (III), (IV) and (V).

  The structural unit (I) is a structural unit generated from p-hydroxybenzoic acid, the structural unit (II) is a structural unit generated from 4,4′-dihydroxybiphenyl, and the structural unit (III) is generated from hydroquinone. The structural unit, the structural unit (IV) represents a structural unit produced from terephthalic acid, and the structural unit (V) represents a structural unit produced from isophthalic acid.

  Hereinafter, this liquid crystalline polyester will be described as an example.

  The copolymerization amount of the structural units (I), (II), (III), (IV) and (V) is arbitrary. However, in order to make it the range prescribed | regulated by this invention and to exhibit the characteristic, it is preferable that it is the following copolymerization amount.

  That is, the structural unit (I) is preferably 40 to 85 mol%, more preferably 65 to 80 mol%, still more preferably based on the total of the structural units (I), (II) and (III). Is 68-75 mol%. Further, the structural unit (II) is preferably 60 to 90 mol%, more preferably 60 to 75 mol%, and still more preferably 65 to 73 mol, based on the total of the structural units (II) and (III). Mol%. The structural unit (IV) is preferably 40 to 95 mol%, more preferably 60 to 92 mol%, still more preferably 72 to 92 mol% based on the total of the structural units (IV) and (V). It is.

  In such a composition range, a liquid crystalline polyester having a melting entropy (ΔS) in a preferable range as described later is obtained, which is preferable.

    The sum of structural units (II) and (III) and (IV) and (V) are substantially equimolar. Here, “substantially equimolar” means that the unit constituting the polymer main chain excluding the terminal is equimolar, but the unit constituting the terminal is not necessarily equimolar.

  In such a composition range, the low gas property and the effect of improving blistering which are the effects of the present invention are particularly exhibited and preferable.

    In the liquid crystalline resin composed of the structural units (I) to (V), a liquid crystalline resin using 2,6-dihydroxynaphthalene instead of hydroquinone which gives the structural unit (III) is also preferable. The ratio is the same as the ratio obtained by replacing (III) with a structural unit generated from 2,6-dihydroxynaphthalene.

    In addition, in the liquid crystalline resin composed of the structural units (I) to (V), a liquid crystalline resin using 2,6-naphthalenedicarboxylic acid instead of isophthalic acid giving the structural unit (V) is also preferable. A desirable ratio of the structural unit is the same as the ratio in which the above (V) is replaced with the structural unit generated from 2,6-naphthalenedicarboxylic acid.

  The liquid crystal polyester preferably used includes 3,3′-diphenyldicarboxylic acid, 2 in addition to the components constituting the structural units (I) to (V), 2,6-dihydroxynaphthalene and 2,6-naphthalenedicarboxylic acid. Aromatic dicarboxylic acids such as 2,2'-diphenyldicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, 3, Aromatic diols such as 4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxybenzophenone, 3,4′-dihydroxybiphenyl, propylene glycol, 1, 4-butanediol, 1,6-hexa Liquids such as diol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and other aliphatic, alicyclic diol, m-hydroxybenzoic acid, p-aminobenzoic acid, p-aminophenol, etc. The copolymer can be further copolymerized within a range that does not impair the properties and properties.

The liquid crystalline resin of the present invention preferably has a ΔS (melting entropy) defined by Formula 1 of 0.9 × 10 ⁻³ J / g · K or less, and such a liquid crystalline resin is non-oriented. Even in a close state, it exhibits a particularly high mechanical strength.
ΔS (J / g · K) = ΔHm (J / g) / [Tm (° C.) + 273] − [1]

  Here, Tm is an endothermic peak temperature (Tm1) observed when a polymer having been polymerized is measured at 20 ° C./min from room temperature in differential calorimetry, and then at a temperature of Tm1 + 20 ° C. After holding for 5 minutes, the temperature is once cooled to room temperature under a temperature drop condition of 20 ° C./min, and again indicates the endothermic peak temperature (Tm 2) observed when measured under a temperature rise condition of 20 ° C./min. ΔHm is the endotherm It is the heat of fusion (ΔHm2) calculated from the peak area.

ΔS is preferably 0.9 × 10 ⁻³ J / g · K or less, more preferably 0.7 × 10 ⁻³ J / g · K or less, and even more preferably 0.5 × 10 10. ^-3 J / g · K or less.

  However, since ΔS is not 0 and does not become a negative value, it takes a real number range larger than 0.

  In the measurement of ΔHm and Tm, when no peak is obtained, ΔS cannot be calculated, and it is interpreted that a liquid crystalline resin in which such a peak is not observed does not satisfy the above preferable range.

  When ΔS is in such a range, the molecular chain of the liquid crystalline resin exists in a very ordered state in the molten state and the solid state, and the molecular chain can be obtained without being highly oriented during molding. It is considered that a molded product having particularly excellent mechanical strength and heat resistance can be obtained because the disturbance is small and neatly arranged.

  Note that neat arrangement of molecular chains is different from high crystallinity. High crystallinity means a state in which the proportion of crystal parts increases as a result of less restraint of amorphous parts. In such a state, there is a large gap in the existence state of the molecular chain between the high-density crystal part and the low-density non-constant amorphous part, and in the molded product solidified without giving the orientation, the whole part is hard and soft. The part is turbulent with great turbulence, and both the mechanical strength and heat resistance are reduced.

  On the contrary, when ΔS of the liquid crystalline resin is in the above preferable range, the crystalline part and the amorphous part are not turbulent, the molecules are arranged neatly, and the state of all the molecular chains is almost the same as a whole. Since it is very ordered, it exhibits high mechanical strength and heat resistance without giving orientation.

  At the crystal part, the molecular chains are packed (the molecular chains are arranged at high density), and the distance between the molecular chains is reduced. At the amorphous part, the distance between the molecular chains is disturbed, and the difference between the small part and the large part is different. Becomes larger. When ΔS of the liquid crystalline resin is in the preferred range, the intermolecular chain distance is in the middle. Such a liquid crystalline resin contains a moderate looseness and is preferable.

    Crystallinity can be evaluated by evaluating the heat of fusion (ΔH). The intermolecular chain distance can be evaluated by, for example, X-ray diffraction using α-alumina as an internal standard, from the peak diffraction angle (2θ).

  The melt viscosity of the liquid crystalline resin in the present invention is preferably 10 to 500 Pa · s, more preferably 12 to 200 Pa · s. This melt viscosity is a value measured by a Koka flow tester under the condition of melting point (Tm) + 10 ° C. and shear rate of 1000 (1 / second).

  The melting point of the liquid crystalline resin in the present invention is not particularly limited, but it is preferable to combine the copolymer components so as to be 280 ° C. or higher for use in high heat resistance applications, and more preferably to be 300 ° C. or higher. Preferably, the combination is more preferably 310 ° C or higher, and most preferably the combination is 325 ° C or higher. As the upper limit, the decomposition temperature of the liquid crystalline resin is preferably −10 ° C. or lower, and since the decomposition temperature of the liquid crystalline polyester as described above is around 370 ° C., it is preferable to combine them so as to be 360 ° C. or lower.

  The basic production method of the liquid crystalline resin of the present invention is not particularly limited as long as the liquid crystalline resin specified in the present invention can be obtained. However, in order to exhibit the effects of the present invention, at least two kinds of aromatic diols are used. A liquid crystalline resin raw material containing, preferably an aromatic hydroxycarboxylic acid, and acetylating a phenolic hydroxyl group in the liquid crystalline resin raw material, for example, a phenolic hydroxyl group of an aromatic hydroxycarboxylic acid or aromatic diol, and acetic anhydride. A process comprising a step of reacting and then a step of polycondensation (preferably polycondensation by reacting under reduced pressure at a temperature at which the liquid crystalline resin melts) with the remaining liquid crystal resin raw materials (aromatic dicarboxylic acid and other monomers) The method is preferred.

  The amount of acetic anhydride used is preferably 1.00 to 1.10 mole equivalent, more preferably 1.03 to 1.09 mole equivalent of the total of phenolic hydroxyl groups in the liquid crystal resin raw material to be used. More preferred is 05 to 1.08 molar equivalent.

  In the case where the amount of acetic anhydride is within the above range, the residual amount of the monoacetylated aromatic diol in the acetylation step is particularly easy to control, which is preferable.

  For example, in the production of the liquid crystalline polyester, the following production method is preferred. The following is an example of the synthesis of a liquid crystalline polyester composed of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid, but the copolymer composition is limited to these. However, each can be replaced with other hydroxycarboxylic acid, aromatic diol or aromatic dicarboxylic acid, and can be produced according to the following method.

  For example, a predetermined amount of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, isophthalic acid, acetic anhydride (1.03 to 1.09 molar equivalent to the hydroxyl group in the liquid crystalline resin raw material) Was charged in a reaction vessel equipped with a stirring blade, a rectifying column, and a distillation pipe, and provided with a discharge port at the bottom, heated while stirring in a nitrogen gas atmosphere, and 2.1 to 140-150 ° C. while refluxing. After reacting for 2.9 hours to acetylate the hydroxyl group, the acetylation process is completed by switching to a distillation tube, and the melting point of the liquid crystalline polyester is 2.5 to 2.5 ° C. while distilling acetic acid. After heating up for 6.5 hours and stirring with heating for about 0.2 to 1.5 hours, the pressure is then reduced to 665 Pa or less for 0.5 to 2 hours, and polycondensation is carried out for about 0.1 to 3 hours. The method of completing is mentioned.

  In addition, although acetylation and polycondensation may be performed continuously in the same reaction vessel, acetylation and polycondensation may be performed in different reaction vessels.

    As conditions for the polycondensation, the degree of vacuum is more preferably 133 Pa or less, and the final polymerization temperature is preferably about melting point + 20 ° C., and preferably 360 ° C. or less. The stirring speed is preferably 50 rpm or less.

  The polymerization time from when the degree of vacuum becomes 665 Pa or less until the predetermined torque is detected and the polymerization is completed is more preferably 0.5 to 1 hour.

  In order to take out the obtained polymer from the reaction vessel after completion of the polymerization, the inside of the reaction vessel is pressurized to, for example, about 0.02 to 0.5 MPa at a temperature at which the polymer melts, and is discharged from a discharge port provided at the lower portion of the reaction vessel. It is discharged in the form of a strand, and the strand is cooled in cooling water and cut into a pellet to obtain a resin pellet. The melt polymerization method is an advantageous method for producing a uniform polymer, and is preferable because an excellent polymer with less gas generation can be obtained.

  When the liquid crystalline resin of the present invention is produced, the polycondensation reaction can be completed by a solid phase polymerization method. For example, the polymer or oligomer of the liquid crystalline resin of the present invention is pulverized with a pulverizer and heated in a nitrogen stream or under reduced pressure for 1 to 50 hours in the range of the melting point of the liquid crystalline resin from -5 ° C to the melting point -50 ° C. And a method of polycondensation to a desired degree of polymerization to complete the reaction. Solid phase polymerization is an advantageous method for producing polymers with a high degree of polymerization.

  The polycondensation reaction of the liquid crystalline resin proceeds even without a catalyst, but metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and magnesium metal can also be used.

  The liquid crystalline resin of the present invention preferably has a number average molecular weight of 3,000 to 25,000, more preferably 5,000 to 20,000, and more preferably 8,000 to 18,000. .

  The number average molecular weight can be measured by GPC-LS (gel permeation chromatography-light scattering) method using a solvent in which the liquid crystalline resin is soluble.

  The liquid crystalline resin produced by deacetic acid polycondensation can be hydrolyzed by a method such as adding water to change the terminal acetyl group to a hydroxyl group. Becomes a hydroxyl group derived from oxycarboxylic acid, and the molecular weight is lowered to generate an oligomer, which is not preferable. When the terminal is a hydroxyl group derived from an aromatic oxycarboxylic acid, heat resistance stability and oxidation resistance are low, and carbon dioxide gas and phenol gas are generated due to elimination and thermal decomposition of the aromatic oxycarboxylic acid, which is not preferable.

  In the present invention, a filler can be further blended in order to impart mechanical strength and other characteristics of the liquid crystalline resin. The filler is not particularly limited, but fillers such as a fiber, a plate, a powder, and a granule can be used. Specifically, for example, glass fibers, PAN and pitch carbon fibers, stainless fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers and liquid crystalline polyester fibers, gypsum fibers, ceramic fibers , Asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, etc. Powder, granular or plate-like filling of wood, mica, talc, kaolin, silica, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, titanium oxide, zinc oxide, calcium polyphosphate and graphite Material And the like. The above-mentioned filler used in the present invention can be used by treating the surface thereof with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.) or other surface treatment agents. .

  Among these fillers, glass fiber is particularly preferably used from the viewpoint of balance between availability and mechanical strength. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing resin, and can be selected from, for example, long fiber type or short fiber type chopped strands and milled fibers. Two or more of these can be used in combination. As the glass fiber used in the present invention, a weakly alkaline glass fiber is excellent in terms of mechanical strength and can be preferably used. The glass fiber is preferably treated with an epoxy-based, urethane-based, acrylic-based coating or sizing agent, and epoxy-based is particularly preferable. Further, it is preferably treated with a silane-based or titanate-based coupling agent or other surface treatment agent, and an epoxysilane or aminosilane-based coupling agent is particularly preferable.

  The glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

  The blending amount of the filler is usually 30 to 200 parts by weight, preferably 40 to 150 parts by weight with respect to 100 parts by weight of the liquid crystalline polyester.

  Further, the liquid crystalline resin of the present invention includes antioxidants and heat stabilizers (for example, hindered phenols, hydroquinones, phosphites and their substitutes), ultraviolet absorbers (for example, resorcinol, salicylate), phosphorous acid. Colorants including salts, anti-coloring agents such as hypophosphite, lubricants and mold release agents (such as montanic acid and its metal salts, its esters, their half esters, stearyl alcohol, stearamide and polyethylene wax), dyes and pigments Carbon black, crystal nucleating agent, plasticizer, flame retardant (bromine flame retardant, phosphorus flame retardant, red phosphorus, silicone flame retardant, etc.), flame retardant aid, antistatic agent, etc. The conventional additive and a polymer other than the thermoplastic resin can be blended to further impart predetermined characteristics.

  The method of blending these additives is preferably by melt kneading, and known methods can be used for melt kneading. For example, using a Banbury mixer, rubber roll machine, kneader, single-screw or twin-screw extruder, etc., it can be melt kneaded at a temperature of 180 to 350 ° C., more preferably 250 to 320 ° C. to obtain a liquid crystalline resin composition. . In that case, 1) a batch kneading method with a liquid crystalline resin, optional fillers and other additives, 2) a liquid crystalline resin composition containing a high concentration of other additives in a liquid crystalline polyester ( Master pellet), and then adding other thermoplastic resins, fillers and other additives to the specified concentration (master pellet method), 3) one of liquid crystalline resin and other additives Any method may be used, such as a split addition method in which the part is kneaded once and then the remaining filler and other additives are added.

  The liquid crystalline resin of the present invention and the liquid crystalline resin composition containing the same are excellent in low gas properties, and have an excellent surface appearance (color tone) and machine by a molding method such as normal injection molding, extrusion molding, or press molding. It can be processed into three-dimensional molded products, sheets, containers, pipes, films, and the like having natural properties, heat resistance, and flame retardancy. In particular, it is suitable for electrical and electronic parts obtained by injection molding because of its excellent fluidity and low gasity.

  In particular, since blistering is very unlikely, the productivity of precision molded products can be significantly improved.

  Moreover, since the liquid crystalline resin of the present invention has a low solidification rate and high homogeneity, it has excellent processability as a film, and a film with little thickness unevenness can be obtained.

  As a processing method for the film, the T-die method is preferable in order to make use of the characteristic that the thickness unevenness is small. For example, in the T-die, the flow paths are gradually inclined from the discharge direction of the film from a plurality of manifolds. While the length of the flow path is narrowed, the end of the flow path overlaps with the flow of liquid crystalline resin with another orientation angle that has escaped from the other manifolds, and rips into a single flow. By discharging more, the obtained film can obtain the film which has the orientation state from which a multilayer differs in the inside. The film thus obtained is excellent in mechanical properties and dimensional stability in all directions.

  There is no particular limitation on the formation of the liquid crystalline resin with a T-die, but the lip opening is preferably about 0.5 to 4 mm for a thick film, and the lip opening is 0.3 mm or less for a thin film. Is preferably 0.2 mm or less, and is preferably 0.1 mm or less from the viewpoint of thickness unevenness.

  As a method for controlling the anisotropy of the film, it is possible to stretch the melt-formed film. As the stretching method, uniaxial stretching using a tenter or sequential biaxial stretching, simultaneous biaxial stretching, between rollers Various methods such as rolling can be used.

  In uniaxial stretching using a tenter or sequential biaxial stretching and simultaneous biaxial stretching, the liquid crystalline resin film itself can be at a temperature lower than the flow start temperature of the liquid crystalline resin, but heat resistance other than the liquid crystalline resin It is preferable to carry out by laminating the resin at a temperature higher than the flow start temperature of the liquid crystalline resin.

  As the heat-resistant resin, for example, fluororesins represented by thermoplastic polyimide, polyethersulfone, polyphenylene sulfide, polyethylene terephthalate, polytetrafluoroethylene, and the like can be used. May be. The thickness of the heat-resistant resin film to be used is not particularly limited, but is preferably about 1 to 5 times the thickness of the liquid crystalline resin film to be obtained from the viewpoint of co-stretchability.

  Lamination methods include coextrusion, a method of laminating a heat-resistant resin film to a liquid crystalline resin immediately after extrusion, a method of once laminating a liquid crystalline resin film, and then heat laminating at a temperature above the melting point of the liquid crystalline resin. Used.

  Lamination is preferably performed on both surfaces of the liquid crystalline resin from the viewpoint of suppressing unevenness in stretching and surface properties.

  As the stretching method, a biaxial stretching method is preferable from the viewpoint of anisotropy control, and simultaneous biaxial stretching, sequential biaxial stretching, and the like can be appropriately selected. The draw ratio is 1.001 to 5 times, preferably 1.002 to 3 times. The stretching speed can be 0.01 to 300% / min, and preferably 0.03 to 100% / min.

  In the method of rolling between rollers, it is preferable to perform rolling to a thickness of 85% or less of the lip opening by a roll controlled at exactly the same temperature as the T-die for orientation control.

  Although it is possible for the liquid crystalline resin film to be at a temperature lower than the flow start temperature of the liquid crystalline resin, it should be performed at a temperature higher than the flow start temperature of the liquid crystalline resin by laminating a heat-resistant resin or metal film other than the liquid crystalline resin. Is preferred.

  As the heat-resistant resin, for example, fluororesins represented by thermoplastic polyimide, polyethersulfone, polyphenylene sulfide, polyethylene terephthalate, polytetrafluoroethylene, and the like can be used. May be.

  As the metal film, for example, a film such as gold, silver, copper, aluminum, nickel, and a partial oxide thereof can be used, and the thickness is not particularly limited, but from the viewpoint of co-rollability, It is preferably at least about 0.01 to 5 times the thickness of the liquid crystalline resin film to be obtained.

  As a lamination method, when using a heat-resistant resin, co-extrusion, a method of laminating a heat-resistant resin film on a liquid crystalline resin immediately after extrusion, or after once forming a liquid crystalline resin film, the melting point of the liquid crystalline resin or higher A method of heat laminating at a temperature is used.

  When using a metal film, a method of laminating a heat-resistant resin film on a liquid crystalline resin immediately after extrusion, a method of once laminating a liquid crystalline resin film, and then thermally laminating at a temperature equal to or higher than the melting point of the liquid crystalline resin is used. When copper is used, the production of the copper-clad laminate and the anisotropy control can be performed in one step, which is preferable.

  Lamination may be carried out on either one or both sides of the liquid crystalline resin, but it is preferable to carry out lamination on both sides from the viewpoint of suppressing stretching unevenness and surface properties.

  The liquid crystalline resin thus obtained and the liquid crystalline resin composition containing the same are, for example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, Variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal display component, FDD carriage , FDD chassis, HDD parts, motor brush holder, parabolic antenna, electric and electronic parts represented by computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustics Products, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, home appliances, office computer parts, telephone parts , Facsimile-related parts, copier-related parts, cleaning jigs, oilless bearings, stern bearings, underwater bearings and other bearings, motor-related parts such as motor parts, lighters, typewriters, microscopes, binoculars, cameras , Optical equipment such as watches, precision machinery related parts; alternator terminal, alternator connector, IC regulator, light meter potentiometer base, various valves such as exhaust gas valve, fuel-related / exhaust / intake system pipes, air Intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear Sensor, air conditioner thermostat base, air conditioner motor insulator, separator, heating hot air flow control valve, radiator motor brush holder, water pump impeller, turbine vane, wiper motor related parts, dust distributor, starter switch, starter relay, Wire harness for transmission, window washer nozzle, air conditioner Panel switch board, coil for fuel related electromagnetic valve, connector for fuse, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, etc. It can be used for automobile and vehicle related parts. When used as a film, magnetic recording media film, photographic film, capacitor film, electrical insulation film, packaging film, drafting film, ribbon film, and sheet use as automotive interior ceiling, door trim, instrument panel It is useful for pad materials, bumper and side frame cushioning materials, sound absorbing pads such as the back of bonnets, seat materials, pillars, fuel tanks, brake hoses, nozzles for window washer fluid, air conditioner refrigerant tubes and their peripheral components.

  Hereinafter, although an example explains the present invention still in detail, the gist of the present invention is not limited only to the following example.

Example 1
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 932 parts by weight of p-hydroxybenzoic acid, 293 parts by weight of 4,4'-dihydroxybiphenyl, 74 parts by weight of hydroquinone, 344 parts by weight of terephthalic acid, 30 parts by weight of isophthalic acid And 1240 parts by weight of acetic anhydride (1.08 equivalents of total phenolic hydroxyl groups) were added and reacted at 145 ° C. for 2.5 hours with stirring under a nitrogen gas atmosphere to complete acetylation, and then to 360 ° C. in 4 hours. The temperature rose. Thereafter, the polymerization temperature was maintained at 360 ° C., and the mixture was heated and stirred for 1 hour. Thereafter, the pressure was reduced to 133 Pa in 1.0 hour, the reaction was continued for another 50 minutes, and the polycondensation was completed when the torque reached 20 kgcm. Next, the inside of the reaction vessel was pressurized to 0.1 MPa, the polymer was discharged to a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  This liquid crystalline resin (A-1) has a structural unit derived from p-hydroxybenzoic acid (structural unit (I)) of 60 mol% and a structural unit derived from 4,4′-dihydroxybiphenyl (structural unit (II)). 14 mol%, structural unit derived from hydroquinone (structural unit (III)) 6 mol%, structural unit derived from terephthalic acid (structural unit (IV)) 18.4 mol%, structural unit derived from isophthalic acid (structure (Unit (V)) is composed of 1.6 mol%, and a structural unit derived from two kinds of aromatic diols of 4,4′-dihydroxybiphenyl and hydroquinone is 70:30 (structural unit (II): structural unit (III)) ) Ratio. The structural unit (I) is 75 mol% with respect to the total of the structural units (I), (II) and (III), and the structural unit (IV) is the total of the structural units (IV) and (V). The total of structural units (II) and (III) and (IV) and (V) was equimolar.

The melting point of this liquid crystalline resin is 348 ° C., ΔS is 0.6 × 10 ⁻³ J / g · K, and melt viscosity measured at a temperature of 360 ° C. and a shear rate of 1000 / s using a Koka flow tester. Was 20 Pa · s.

  The melting point (Tm) is determined by differential calorimetry. After observing the endothermic peak temperature (Tm1) observed when the polymer is measured at room temperature to 20 ° C./minute, the temperature is maintained at Tm1 + 20 ° C. for 5 minutes. Then, after cooling to room temperature under a temperature drop condition of 20 ° C./minute, the endothermic peak temperature (Tm 2) observed when measured again under a temperature rise condition of 20 ° C./minute was used. The same applies to the following reference examples.

  The following (1) to (5) were evaluated.

(1) Residual amount of monoacetylated product of aromatic diol A small amount of sample was sampled when acetylation was completed, and fractionated by GPC, then measured by ¹ H-NMR at 400 MHz with heavy acetone solvent, and charged with aromatic diol. The residual amount of monoacetylated product relative to the amount was determined.

  Peak separation was performed for each of the two aromatic diols.

For each of the two aromatic diols, the residual amount of the monoacetylated product of the aromatic diol was calculated from the following formula.
Residual amount (%) of monoacetylated aromatic diol = [Ia / (Ia + Ib)] × 100
Ia: peak intensity attributed to the hydrogen atom bonded to the α-position carbon of the aromatic nucleus carbon bonded with the non-acetylated hydroxyl group of the monoacetylated product of the aromatic diol Ib: monoacetylated product and diacetylated product of the aromatic diol Peak intensity attributed to hydrogen atoms bonded to the α-position carbon of the aromatic carbon bonded with acetyl groups

(2) Gas generation amount Using a simultaneous measurement device that combines Shimadzu TG40M and Shimadzu GC / MS QP5050A, traps the generated gas with the adsorbent simultaneously with the TG-MS measurement, and the adsorbent is the thermal desorption device (280 ° C, adsorbent C300), reheat and perform GC-MS measurement (column PTEM-5) to identify the gas type from the mass number, and generate acetic acid gas, phenol gas, carbon dioxide gas from the total weight loss and peak intensity The amount was calculated (sample weight 150 mg, pre-dried 150 ° C. for 5 hours, kept in a helium atmosphere at a melting point + 10 ° C. for 30 minutes) (however, a liquid crystalline resin having a melting point of less than 325 ° C. is held at 335 ° C., It was measured).

(3) In a TEX30 type twin screw extruder manufactured by Nippon Steel Works equipped with a blister side feeder, 100 parts by weight of liquid crystalline resin is introduced from a hopper, and 40 parts by weight of glass fiber (03T-790G, manufactured by Nippon Electric Glass) is introduced from the side. The cylinder heater set temperature is adjusted so that the resin temperature becomes the melting point + 10 ° C., and the screw rotation speed is 100 r. p. It was melt-kneaded under the conditions of m to obtain pellets. The following evaluation was performed after hot air drying.

  The liquid crystalline resin composition pellets were supplied to a FANUC 30α-C injection molding machine and extruded at a cylinder temperature melting point + 10 ° C. to form a rod-shaped molded product having a length of 150 mm × width of 12.7 mm × thickness of 1 mm. After heat-moisture treatment at 120 RH% and 95 ° C. for 8 hours, heat treatment was performed in a reflow bath at 275 ° C. for 10 minutes, and the number of blisters generated was evaluated for 1000 molded articles.

(4) Metal corrosion test The above molded product and a 2 cm square 2 mm thick iron plate were placed in a glass petri dish, capped and treated in an oven at 150 ° C for 200 hours. The discoloration and corrosion of the iron plate were judged visually.
○: Discoloration, no corrosion, Δ: Discoloration, no corrosion, ×: Discoloration, corrosion

(5) Cloudiness test of glass In the same manner as in (4), a molded product was put in a glass petri dish, covered, and allowed to stand on a hot plate at 270 ° C. The time until cloudiness of the upper lid of the glass petri dish was determined (maximum 50 hours).

  The same evaluation was performed for the following examples.

Example 2
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 870 parts by weight of p-hydroxybenzoic acid, 352 parts by weight of 4,4′-dihydroxybiphenyl, 89 parts by weight of hydroquinone, 374 parts by weight of terephthalic acid, 2,6-naphthalene After 97 parts by weight of dicarboxylic acid and 1191 parts by weight of acetic anhydride (1.08 equivalents of the total phenolic hydroxyl groups) were added, the reaction was allowed to proceed at 145 ° C. for 2.5 hours with stirring in a nitrogen gas atmosphere, and acetylation was completed. The temperature was raised to 4 ° C. in 4 hours. Thereafter, the polymerization temperature was maintained at 350 ° C., and the mixture was heated and stirred for 1 hour. Thereafter, the pressure was reduced to 133 Pa in 1.0 hour, and the reaction was continued for another 42 minutes. When the torque reached 20 kgcm, the polycondensation was completed. Next, the inside of the reaction vessel was pressurized to 0.1 MPa, the polymer was discharged to a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  This liquid crystalline resin (A-2) has a structural unit derived from p-hydroxybenzoic acid (structural unit (I)) of 54 mol% and a structural unit derived from 4,4′-dihydroxybiphenyl (structural unit (II)). 16.1 mol%, structural unit derived from hydroquinone (structural unit (III)) 6.9 mol%, structural unit derived from terephthalic acid (structural unit (IV)) 19.2 mol%, 2,6-naphthalene The structural unit (structural unit (V) ′) derived from dicarboxylic acid is composed of 3.8 mol%, and the structural unit derived from two kinds of aromatic diols of 4,4′-dihydroxybiphenyl and hydroquinone is 70:30 (structure Unit (II): structural unit (III)). The structural unit (I) is 70 mol% with respect to the total of the structural units (I), (II) and (III), and the structural unit (IV) is composed of the structural units (IV) and (V) ′. The total amount was preferably 83 mol%, and the total of structural units (II) and (III) and (IV) and (V) were equimolar.

This liquid crystalline resin has a melting point of 335 ° C. and ΔS of 0.5 × 10 ⁻³ J / g · K, and has a melt viscosity measured at a temperature of 345 ° C. and a shear rate of 1000 / s using a Koka flow tester. 22 Pa · s.

Reference example 3
In a 5 L reaction vessel equipped with a stirring blade and a distillation pipe, 994 parts by weight of p-hydroxybenzoic acid, 298 parts by weight of 4,4′-dihydroxybiphenyl, 32 parts by weight of 2,6-dihydroxynaphthalene, 194 parts by weight of terephthalic acid, After charging 105 parts by weight of isophthalic acid and 1158 parts by weight of acetic anhydride (1.09 equivalents of the total phenolic hydroxyl groups) and reacting at 145 ° C. for 2.5 hours with stirring under a nitrogen gas atmosphere, acetylation was completed. The temperature was raised to 4 ° C. in 4 hours. Thereafter, the polymerization temperature was maintained at 370 ° C., and the mixture was heated and stirred for 1 hour. Thereafter, the pressure was reduced to 133 Pa in 1.0 hour, the reaction was continued for another 22 minutes, and the polycondensation was completed when the torque reached 20 kgcm. Next, the inside of the reaction vessel was pressurized to 0.1 MPa, the polymer was discharged to a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

This liquid crystalline resin (A-3) has a structural unit derived from p-hydroxybenzoic acid (structural unit (I)) of 66.8 mol% and a structural unit derived from 4,4′-dihydroxybiphenyl (structural unit (II )) 14.8 mol%, structural unit derived from 2,6-dihydroxynaphthalene (structural unit (III) ') 1.8 mol%, structural unit derived from terephthalic acid (structural unit (IV)) 10.8 It consists of 5.8 mol% of structural units derived from isophthalic acid (structural unit (V)), and is derived from two types of aromatic diols of 4,4'-dihydroxybiphenyl and 2,6-dihydroxynaphthalene. The unit was 89:11 (structural unit (II): structural unit (III) ′). The structural unit (I) is 80 mol% with respect to the total of the structural units (I), (II) and (III), and the structural unit (IV) is the total of the structural units (IV) and (V). The total of structural units (II) and (III) and (IV) and (V) was equimolar. This liquid crystalline resin has a melting point of 355 ° C. and ΔS of 0.4 × 10 ⁻³ J / g · K, and has a melt viscosity measured at a temperature of 365 ° C. and a shear rate of 1000 / s using a Koka flow tester. It was 24 Pa · s.

Example 4
870 parts by weight of p-hydroxybenzoic acid, 327 parts by weight of 4,4′-dihydroxybiphenyl, 104 parts by weight of hydroquinone, 292 parts by weight of terephthalic acid, 156 parts by weight of isophthalic acid in a 5 L reaction vessel equipped with a stirring blade and a distillation tube And 1254 parts by weight of acetic anhydride (1.05 equivalent of the total phenolic hydroxyl groups) were added and reacted at 148 ° C. for 2.5 hours with stirring under a nitrogen gas atmosphere to complete acetylation, and then to 330 ° C. in 4 hours. The temperature rose. Thereafter, the polymerization temperature was maintained at 330 ° C., and the mixture was heated and stirred for 1 hour. Thereafter, the pressure was reduced to 133 Pa in 1.0 hour, the reaction was continued for another 60 minutes, and the polycondensation was completed when the torque reached 20 kgcm. Next, the inside of the reaction vessel was pressurized to 0.1 MPa, the polymer was discharged to a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  This liquid crystalline resin (A-4) has a structural unit derived from p-hydroxybenzoic acid (structural unit (I)) of 53.8 mol% and a structural unit derived from 4,4′-dihydroxybiphenyl (structural unit (II )) 15 mol%, structural unit derived from hydroquinone (structural unit (III)) 8.1 mol%, structural unit derived from terephthalic acid (structural unit (IV)) 15 mol%, structural unit derived from isophthalic acid (Structural unit (V)) Consisting of 8.1 mol%, a structural unit derived from two kinds of aromatic diols of 4,4′-dihydroxybiphenyl and hydroquinone is 65:35 (structural unit (II): structural unit ( III)). The structural unit (I) is 70 mol% with respect to the total of the structural units (I), (II) and (III), and the structural unit (IV) is the total of the structural units (IV) and (V). The total of structural units (II) and (III) and (IV) and (V) was equimolar.

The melting point of this liquid crystalline resin is 310 ° C. and ΔS is 0.3 × 10 ⁻³ J / g · K, and the melt viscosity measured at a temperature of 320 ° C. and a shear rate of 1000 / s using a Koka flow tester. It was 20 Pa · s.

Example 5
50 parts by weight of glass fiber (ECS03T-747H manufactured by Asahi Electric Glass Co., Ltd.) was blended with 100 parts by weight of the liquid crystalline resin (A-1) of Example 1, and kneaded with a twin-screw extruder at 350 ° C. and pelletized (gas amount) Since the measurement was performed using the resin composition as a sample, the gas generation amount measured was calculated by multiplying the measured gas generation amount by 3/2 in order to evaluate the gas generation amount only from the liquid crystalline resin component).

Comparative Example 1
Polymerization was carried out under the same conditions as in Example 1, except that 1377 g of acetic anhydride alone (1.199 equivalents of the total phenolic hydroxyl groups) was charged and the acetylation conditions were carried out at 170 ° C. for 45 minutes.

  The reaction was continued for 2 minutes at a final polymerization temperature of 360 ° C. and a reduced pressure of 133 Pa, and the polycondensation was completed when the torque reached 20 kgcm. Next, the inside of the reaction vessel was pressurized to 0.1 MPa, the polymer was discharged to a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  This liquid crystalline resin (A-5) has a structural unit derived from p-hydroxybenzoic acid (structural unit (I)) of 60 mol% and a structural unit derived from 4,4′-dihydroxybiphenyl (structural unit (II)). 14 mol%, structural unit derived from hydroquinone (structural unit (III)) 6 mol%, structural unit derived from terephthalic acid (structural unit (IV)) 18.4 mol%, structural unit derived from isophthalic acid (structure (Unit (V)) is composed of 1.6 mol%, and a structural unit derived from two kinds of aromatic diols of 4,4′-dihydroxybiphenyl and hydroquinone is 70:30 (structural unit (II): structural unit (III)) ) Ratio. The structural unit (I) is 75 mol% with respect to the total of the structural units (I), (II) and (III), and the structural unit (IV) is the total of the structural units (IV) and (V). The total of structural units (II) and (III) and (IV) and (V) was equimolar.

The melting point of this liquid crystalline resin is 350 ° C. and ΔS is 1.4 × 10 ⁻³ J / g · K, and the melt viscosity measured at a temperature of 360 ° C. and a shear rate of 1000 / s using a Koka flow tester. It was 21 Pa · s.

Comparative Example 2
Polymerization was carried out under the same conditions as in Example 1 except that 1286 g of acetic anhydride alone (1.12 equivalents of the total phenolic hydroxyl groups) was charged and the acetylation conditions were carried out at 155 ° C. for 2 hours.

  The reaction was continued for 2 minutes at a final polymerization temperature of 360 ° C. and a reduced pressure of 133 Pa, and the polycondensation was completed when the torque reached 20 kgcm. Next, the inside of the reaction vessel was pressurized to 0.1 MPa, the polymer was discharged to a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  This liquid crystalline resin (A-6) has a structural unit derived from p-hydroxybenzoic acid (structural unit (I)) of 60 mol% and a structural unit derived from 4,4′-dihydroxybiphenyl (structural unit (II)). 14 mol%, structural unit derived from hydroquinone (structural unit (III)) 6 mol%, structural unit derived from terephthalic acid (structural unit (IV)) 18.4 mol%, structural unit derived from isophthalic acid (structure (Unit (V)) is composed of 1.6 mol%, and a structural unit derived from two kinds of aromatic diols of 4,4′-dihydroxybiphenyl and hydroquinone is 70:30 (structural unit (II): structural unit (III)) ) Ratio. The structural unit (I) is 75 mol% with respect to the total of the structural units (I), (II) and (III), and the structural unit (IV) is the total of the structural units (IV) and (V). The total of structural units (II) and (III) and (IV) and (V) was equimolar.

This liquid crystalline resin has a melting point of 349 ° C. and ΔS of 1.4 × 10 ⁻³ J / g · K, and has a melt viscosity measured at a temperature of 359 ° C. and a shear rate of 1000 / s using a Koka flow tester. It was 21 Pa · s.

Comparative Example 3
Polymerization was carried out under the same conditions as in Example 1, except that 1205 g of acetic anhydride alone (1.05 equivalents of the total phenolic hydroxyl groups) was charged and the acetylation conditions were carried out at 155 ° C. for 3 hours.

  The reaction was continued for 2 minutes at a final polymerization temperature of 360 ° C. and a reduced pressure of 133 Pa, and the polycondensation was completed when the torque reached 20 kgcm. Next, the inside of the reaction vessel was pressurized to 0.1 MPa, the polymer was discharged to a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  This liquid crystalline resin (A-7) has a structural unit derived from p-hydroxybenzoic acid (structural unit (I)) of 60 mol% and a structural unit derived from 4,4′-dihydroxybiphenyl (structural unit (II)). 14 mol%, structural unit derived from hydroquinone (structural unit (III)) 6 mol%, structural unit derived from terephthalic acid (structural unit (IV)) 18.4 mol%, structural unit derived from isophthalic acid (structure (Unit (V)) is composed of 1.6 mol%, and a structural unit derived from two kinds of aromatic diols of 4,4′-dihydroxybiphenyl and hydroquinone is 70:30 (structural unit (II): structural unit (III)) ) Ratio. The structural unit (I) is 75 mol% with respect to the total of the structural units (I), (II) and (III), and the structural unit (IV) is the total of the structural units (IV) and (V). The total of structural units (II) and (III) and (IV) and (V) was equimolar.

This liquid crystalline resin has a melting point of 349 ° C. and ΔS of 1.4 × 10 ⁻³ J / g · K, and has a melt viscosity measured at a temperature of 359 ° C. and a shear rate of 1000 / s using a Koka flow tester. It was 21 Pa · s.

Comparative Example 4
Polymerization was carried out under the same conditions as in Example 1 except that 1263 g of acetic anhydride alone (1.10 equivalents of the total phenolic hydroxyl groups) was charged and the acetylation conditions were carried out at 140 ° C. for 3 hours.

  The reaction was continued for 3 minutes at a final polymerization temperature of 360 ° C. and a reduced pressure of 133 Pa, and the polycondensation was completed when the torque reached 20 kgcm. Next, the inside of the reaction vessel was pressurized to 0.1 MPa, the polymer was discharged to a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  This liquid crystalline resin (A-8) has a structural unit derived from p-hydroxybenzoic acid (structural unit (I)) of 60 mol% and a structural unit derived from 4,4′-dihydroxybiphenyl (structural unit (II)). 14 mol%, structural unit derived from hydroquinone (structural unit (III)) 6 mol%, structural unit derived from terephthalic acid (structural unit (IV)) 18.4 mol%, structural unit derived from isophthalic acid (structure (Unit (V)) is composed of 1.6 mol%, and a structural unit derived from two kinds of aromatic diols of 4,4′-dihydroxybiphenyl and hydroquinone is 70:30 (structural unit (II): structural unit (III)) ) Ratio. The structural unit (I) is 75 mol% with respect to the total of the structural units (I), (II) and (III), and the structural unit (IV) is the total of the structural units (IV) and (V). The total of structural units (II) and (III) and (IV) and (V) was equimolar.

The melting point of this liquid crystalline resin is 348 ° C. and ΔS is 1.5 × 10 ⁻³ J / g · K, and the melt viscosity measured at a temperature of 349 ° C. and a shear rate of 1000 / s using a Koka flow tester. 22 Pa · s.

Comparative Example 5
Polymerization was carried out under the same conditions as in Example 1 except that 1183 g of acetic anhydride alone (1.03 equivalent of the total phenolic hydroxyl groups) was charged and the acetylation conditions were carried out at 145 ° C. for 2 hours.

  The reaction was continued for 121 minutes at a final polymerization temperature of 360 ° C. and a reduced pressure of 133 Pa, and the polycondensation was completed when the torque reached 20 kgcm. Next, the inside of the reaction vessel was pressurized to 0.1 MPa, the polymer was discharged to a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  This liquid crystalline resin (A-9) has a structural unit derived from p-hydroxybenzoic acid (structural unit (I)) of 60 mol% and a structural unit derived from 4,4′-dihydroxybiphenyl (structural unit (II)). 14 mol%, structural unit derived from hydroquinone (structural unit (III)) 6 mol%, structural unit derived from terephthalic acid (structural unit (IV)) 18.4 mol%, structural unit derived from isophthalic acid (structure (Unit (V)) is composed of 1.6 mol%, and a structural unit derived from two kinds of aromatic diols of 4,4′-dihydroxybiphenyl and hydroquinone is 70:30 (structural unit (II): structural unit (III)) ) Ratio. The structural unit (I) is 75 mol% with respect to the total of the structural units (I), (II) and (III), and the structural unit (IV) is the total of the structural units (IV) and (V). The total of structural units (II) and (III) and (IV) and (V) was equimolar.

The melting point of this liquid crystalline resin is 345 ° C. and ΔS is 1.4 × 10 ⁻³ J / g · K. The melt viscosity measured at a temperature of 355 ° C. and a shear rate of 1000 / s using a Koka flow tester. It was 23 Pa · s.

Comparative Example 6
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 932 parts by weight of p-hydroxybenzoic acid, 419 parts by weight of 4,4′-dihydroxybiphenyl, 344 parts by weight of terephthalic acid, 30 parts by weight of isophthalic acid and 1240 parts by weight of acetic anhydride Parts (1.08 equivalent of total phenolic hydroxyl groups) were added and reacted at 145 ° C. for 2.5 hours with stirring under a nitrogen gas atmosphere to complete acetylation, and then heated to 360 ° C. over 4 hours. Thereafter, the polymerization temperature was maintained at 360 ° C., and the mixture was heated and stirred for 1 hour. Thereafter, the pressure was reduced to 133 Pa in 1.0 hour, and the reaction was continued for another 12 minutes. When the torque reached 20 kgcm, the polycondensation was completed. Next, the inside of the reaction vessel was pressurized to 0.1 MPa, the polymer was discharged to a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.
This liquid crystalline resin (A-10) has a structural unit derived from p-hydroxybenzoic acid (structural unit (I)) of 60 mol% and a structural unit derived from 4,4′-dihydroxybiphenyl (structural unit (II)). 20 mol%, structural unit derived from terephthalic acid (structural unit (IV)) 15 mol%, structural unit derived from isophthalic acid (structural unit (V)) 5 mol%, melting point 342 ° C. and ΔS 2 0.1 × 10 ⁻³ J / g · K, and a melt viscosity measured using a Koka flow tester at a temperature of 352 ° C. and a shear rate of 1000 / s was 25 Pa · s. The structural unit (I) is 75 mol% with respect to the total of the structural units (I), (II) and (III), and the structural unit (IV) is the total of the structural units (IV) and (V). The total of structural units (II) and (III) and (IV) and (V) was equimolar.

Comparative Example 7
Polymerization was carried out under the same conditions as in Comparative Example 6 except that 1183 g of acetic anhydride alone (1.03 equivalent of the total phenolic hydroxyl groups) was charged and the acetylation conditions were carried out at 145 ° C. for 2 hours.

The reaction was continued for 145 minutes at a final polymerization temperature of 360 ° C. and a reduced pressure of 133 Pa. However, since the torque did not reach 20 kgcm, the polycondensation was terminated. Comparative Example 8
Polymerization was performed under the same conditions except that the same composition as in Example 2 was used and the acetylation conditions were performed at 155 ° C. for 2 hours.

  The reaction was continued for 8 minutes at a final polymerization temperature of 350 ° C. and a reduced pressure of 133 Pa, and the polycondensation was completed when the torque reached 20 kgcm. Next, the inside of the reaction vessel was pressurized to 0.1 MPa, the polymer was discharged to a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  This liquid crystalline resin (A-12) has a structural unit derived from p-hydroxybenzoic acid (structural unit (I)) of 54 mol% and a structural unit derived from 4,4′-dihydroxybiphenyl (structural unit (II)). 16.1 mol%, structural unit derived from hydroquinone (structural unit (III)) 6.9 mol%, structural unit derived from terephthalic acid (structural unit (IV)) 19.2 mol%, 2,6-naphthalene The structural unit (structural unit (V) ′) derived from dicarboxylic acid is composed of 3.8 mol%, and the structural unit derived from two kinds of aromatic diols of 4,4′-dihydroxybiphenyl and hydroquinone is 70:30 (structure Unit (V) ′). The structural unit (I) is 70 mol% with respect to the total of the structural units (I), (II) and (III), and the structural unit (IV) is composed of the structural units (IV) and (V) ′. The total amount was preferably 83 mol%, and the total of structural units (II) and (III) and (IV) and (V) were equimolar.

This liquid crystalline resin has a melting point of 335 ° C. and ΔS of 1.2 × 10 ⁻³ J / g · K, and has a melt viscosity measured using a Koka flow tester at a temperature of 345 ° C. and a shear rate of 1000 / s. 22 Pa · s.

Comparative Example 9
Polymerization was carried out under the same conditions as in Example 4, except that the same composition was used and the acetylation conditions were carried out at 170 ° C. for 1.5 hours.

  The reaction was continued for 4 minutes at a final polymerization temperature of 330 ° C. and a reduced pressure of 133 Pa, and the polycondensation was completed when the torque reached 20 kgcm. Next, the inside of the reaction vessel was pressurized to 0.1 MPa, the polymer was discharged to a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  This liquid crystalline resin (A-13) contains 53.8 mol% of a structural unit derived from p-hydroxybenzoic acid (structural unit (I)) and a structural unit derived from 4,4′-dihydroxybiphenyl (structural unit (II )) 15 mol%, structural unit derived from hydroquinone (structural unit (III)) 8.1 mol%, structural unit derived from terephthalic acid (structural unit (IV)) 15 mol%, structural unit derived from isophthalic acid (Structural unit (V)) Consisting of 8.1 mol%, a structural unit derived from two kinds of aromatic diols of 4,4′-dihydroxybiphenyl and hydroquinone is 65:35 (structural unit (II): structural unit ( III)). The structural unit (I) is 70 mol% with respect to the total of the structural units (I), (II) and (III), and the structural unit (IV) is the total of the structural units (IV) and (V). The total of structural units (II) and (III) and (IV) and (V) was equimolar.

This liquid crystalline resin has a melting point of 310 ° C. and ΔS of 0.8 × 10 ⁻³ J / g · K, and has a melt viscosity measured at a temperature of 320 ° C. and a shear rate of 1000 / s using a Koka flow tester. It was 20 Pa · s.

Comparative Example 10
Polymerization was carried out under the same conditions as in Example 4, except that the same composition was used and the acetylation conditions were carried out at 145 ° C. for 2 hours.

  The reaction was continued for 141 minutes at a final polymerization temperature of 330 ° C. and a reduced pressure of 133 Pa, and the polycondensation was completed when the torque reached 20 kgcm. Next, the inside of the reaction vessel was pressurized to 0.1 MPa, the polymer was discharged to a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  This liquid crystalline resin (A-14) contains 53.8 mol% of a structural unit derived from p-hydroxybenzoic acid (structural unit (I)) and a structural unit derived from 4,4′-dihydroxybiphenyl (structural unit (II )) 15 mol%, structural unit derived from hydroquinone (structural unit (III)) 8.1 mol%, structural unit derived from terephthalic acid (structural unit (IV)) 15 mol%, structural unit derived from isophthalic acid (Structural unit (V)) Consisting of 8.1 mol%, a structural unit derived from two kinds of aromatic diols of 4,4′-dihydroxybiphenyl and hydroquinone is 65:35 (structural unit (II): structural unit ( III)). The structural unit (I) is 70 mol% with respect to the total of the structural units (I), (II) and (III), and the structural unit (IV) is the total of the structural units (IV) and (V). The total of structural units (II) and (III) and (IV) and (V) was equimolar.

The melting point of this liquid crystalline resin is 308 ° C. and ΔS is 0.9 × 10 ⁻³ J / g · K, and the melt viscosity measured at a temperature of 318 ° C. and a shear rate of 1000 / s using a Koka flow tester. 19 Pa · s.

Comparative Example 11
50 parts by weight of glass fiber (ECS03T-747H manufactured by Asahi Electric Glass Co., Ltd.) was blended with 100 parts by weight of the liquid crystalline resin (A-5) of Comparative Example 1, and kneaded and pelletized at 350 ° C. with a twin screw extruder (gas amount). Was evaluated in the same manner as in Example 5).

  As is clear from Table 1, the liquid crystalline resins of the examples are superior to the liquid crystalline resins that are not subjected to terminal control as shown in the comparative examples, and are excellent in low gas properties, and have little blistering of the molded product. Further, it can be seen that even when used as a sliding part, the metal shaft does not corrode, and when used as a glass supporting part such as a liquid crystal lens frame, the glass surface is not clouded.

Example 6
The liquid crystalline resin (A-1) obtained in Example 1 was divided into two flow paths, a gear pump connected to a twin-screw extruder having a vent mechanism via a die plate and the upper right and lower left of the die. It has a structure that gradually narrows the vertical width from the manifold to the position of 2 mm immediately before the lip, while increasing the horizontal width. From the upper right manifold, the vertical width at the right end is always narrower than the vertical width at the left end. The two resin flows led from the two manifolds narrowed to a thickness of 0.1 mm at the 2 mm position overlap each other and are led to a lip having a width of 0.2 mm and discharged. Using a film forming apparatus having a die, film formation was performed at a melting point of the liquid crystalline resin + 20 ° C.

  The obtained film had little anisotropy, and abnormalities such as foaming and fish eyes were not observed.

  A 0.1 mm thick copper foil was thermocompression bonded to the obtained film at a melting point of the liquid crystalline resin of −5 ° C. and heat-treated in an oven at 250 ° C. for 200 hours. Although the discoloration and corrosion of copper foil were judged visually, neither discoloration nor corrosion was seen.

Comparative Example 12
The liquid crystalline resin (A-12) obtained in Comparative Example 8 was formed in the same manner in the same apparatus as in Example 6.

  The obtained film remained anisotropy and easily cracked vertically in the discharge direction. Further, fine foaming was observed at the end in the width direction of the film.

  When the corrosion test was conducted in the same manner as in Example 6, the copper foil turned red and corrosion was observed at the edges.

Example 7
The liquid crystalline resin (A-1) obtained in Example 1 was formed into a film by the same apparatus as in Example 6, and a fluororesin film was laminated on both sides of the film discharged from the T die using a laminator. At 315 ° C., which is a temperature higher than the flow temperature of the liquid crystalline resin, stretching was performed 1.02 times in the direction parallel to the discharge flow direction and 2.41 times in the perpendicular direction using a simultaneous biaxial stretching machine.

  The fluororesin film was peeled off, and the resulting film had no anisotropy, and abnormalities such as foaming and fish eyes were not observed. Furthermore, the surface gloss was superior to the film obtained in Example 6.

  A 0.1 mm thick copper foil was thermocompression bonded to the obtained film at a melting point of the liquid crystalline resin of −5 ° C. and heat-treated in an oven at 250 ° C. for 200 hours. Although the discoloration and corrosion of copper foil were judged visually, neither discoloration nor corrosion was seen.

  According to ASTM D150, the dielectric constant at 10 arbitrary points of the copper-clad film was measured, and when the fluctuation rate was calculated, the dielectric constant fluctuation rate of the copper-clad film of Example 6 was 2% at maximum with respect to the average value. On the other hand, the dielectric constant fluctuation rate of the copper-clad film of Example 7 was 0.09%, and it had good circuit board characteristics.

Example 8
Polyphenylene sulfide resin obtained by forming the liquid crystalline resin (A-1) obtained in Example 1 with the same apparatus as in Example 6 and using a laminator on both sides of the film discharged from the T-die and performing a crosslinking heat treatment. At 315 ° C, which is a temperature higher than the flow temperature of the liquid crystalline resin, the films are laminated and stretched 1.02 times in the direction parallel to the discharge flow direction and 2.41 times in the perpendicular direction using a simultaneous biaxial stretching machine. went.

  The polyphenylene sulfide resin film was peeled off, and the resulting film had no anisotropy, and abnormalities such as foaming and fish eyes were not observed. Furthermore, the surface gloss was superior to the film obtained in Example 6.

  A 0.1 mm thick copper foil was thermocompression bonded to the obtained film at a melting point of the liquid crystalline resin of −5 ° C. and heat-treated in an oven at 250 ° C. for 200 hours. Although the discoloration and corrosion of copper foil were judged visually, neither discoloration nor corrosion was seen.

  According to ASTM D150, the measured dielectric constant variation rate was 0.10%, and the circuit board had good circuit board characteristics.

Example 9
The liquid crystalline resin (A-1) obtained in Example 1 was formed into a film by the same apparatus as in Example 6, and after the film discharged from the T-die was cooled once, the melting point of the liquid crystalline resin was −5 ° C. Then, using a high-temperature laminator, while rolling a 0.1 mm thick copper foil on both sides of the film, rolling equivalent to 1.02 times in the direction parallel to the discharge flow direction and 2.41 times in the perpendicular direction was performed. It heat-processed for 200 hours in 250 degreeC oven. Although the discoloration and corrosion of copper foil were judged visually, neither discoloration nor corrosion was seen.

  According to ASTM D150, the measured dielectric constant variation rate was 0.05%, and the circuit board had good circuit board characteristics.

  Thus, when the liquid crystalline resin of the present invention is used as a film, a film with small anisotropy is obtained, and a film with good quality is obtained in high yield because there is no abnormality such as foaming.

  Moreover, since the copper corrosivity is very low, a film suitable for a copper-clad circuit board material can be obtained.

Claims (8)

The following structural units (I), (II), (III), (IV) and (V) are included, and the structural unit (I) is based on the sum of the structural units (I), (II) and (III). 65 to 80 mol%, the structural unit (II) is 60 to 75 mol% based on the total of the structural units (II) and (III), and the structural unit (IV) is the structural units (IV) and (V). And a total of the structural units (II) and (III) and the total of (IV) and (V) are substantially equimolar , Acetic acid gas generated from the above liquid crystalline resin when held for 30 minutes at a melting point of + 10 ° C. (if the melting point is less than 325 ° C.) for 30 minutes in a helium gas atmosphere is less than 100 ppm, phenol gas is less than 20 ppm, and carbon dioxide gas is Less than 100ppm The liquid-crystalline resin.

The liquid crystalline resin according to claim 1, wherein ΔS (melting entropy) defined by Formula 1 is 0.9 × 10 ⁻³ J / g · K or less.
ΔS (J / g · K) (= ΔHm (J / g) / [Tm (° C.) + 273] − [1]
(Tm is a differential calorimetry. After observing the endothermic peak temperature (Tm1) observed when polymerized polymer is measured at room temperature to 20 ° C./min from the room temperature, it is held at a temperature of Tm1 + 20 ° C. for 5 minutes. After that, the temperature is once cooled to room temperature under a temperature decrease condition of 20 ° C./min, and again indicates an endothermic peak temperature (Tm2) observed when measured under a temperature increase condition of 20 ° C./min. ΔHm is the melting at the endothermic peak. (The amount of heat (ΔHm2).) The liquid crystalline resin according to claim 1 or 2, wherein the structural unit (IV) is 72 to 92 mol% based on the total of the structural units (IV) and (V). A liquid crystalline resin obtained by acetylating a phenolic hydroxyl group in a liquid crystalline resin raw material and then polycondensing it. The most recent aromatic diol (I) is obtained until the residual amount of monoacetylated product calculated by the following formula is 0.8 to 5 mol% of the charged aromatic diol (I). 4. The liquid crystalline resin according to any one of 3.
  Residual amount of monoacetylated product (%) = {[monoacetylated product] / ([monoacetylated product] + [diacetylated product])} × 100
  [Monoacetylated product]: Molar amount of monoacetylated product of aromatic diol (I)
  [Diacetylated product]: Molar amount of diacetylated product of aromatic diol (a)  The liquid crystalline resin composition formed by mix | blending 30-200 weight part of fillers with respect to 100 weight part of liquid crystalline resin in any one of Claims 1-4. Using a liquid crystalline resin raw material containing hydroquinone and 4,4′-dihydroxybiphenyl, 1.03 to 1.09 molar equivalent of acetic anhydride with respect to the total of the phenolic hydroxyl group in the liquid crystalline resin raw material and this phenolic hydroxyl group Is a method of producing a liquid crystalline resin by polycondensation after an acetylation reaction at a temperature of 140 ° C. or more and 150 ° C. or less for 2.1 to 2.9 hours, wherein the aromatic diol used is an acetylation reaction Of the aromatic diol (I) charged with the remaining amount of the monoacetylated product calculated by the following formula of the aromatic diol (I) having the slowest reaction rate from the monoacetylated product to the diacetylated product: The method for producing a liquid crystalline resin according to claim 1, wherein an acetylation reaction is performed until
  Residual amount of monoacetylated product (%) = {[monoacetylated product] / ([monoacetylated product] + [diacetylated product])} × 100
  [Monoacetylated product]: Molar amount of monoacetylated product of aromatic diol (I)
  [Diacetylated product]: Molar amount of diacetylated product of aromatic diol (a) A molded article comprising the liquid crystalline resin according to claim 1 or the liquid crystalline resin composition according to claim 5. The film which consists of a liquid crystalline resin in any one of Claims 1-4, or the liquid crystalline resin composition of Claim 5.