JP6837580B2 - Powdered liquid crystal resin for hot press molded products and hot press molded products - Google Patents

Description

The present invention relates to a powdery liquid crystal resin for a hot press molded product and a hot press molded product.

Liquid crystal resins typified by liquid crystal polyester resins are widely used in various fields because they are excellent in high fluidity, low burr property, reflow resistance and the like. However, since the liquid crystal resin has a property (orientation) of being oriented in the flow direction of the resin during molding and cooling, the obtained molded product has anisotropy in which the physical properties differ depending on the flow direction of the resin and the direction perpendicular to the flow direction. May have.
Hot press molding is a molding method in which resin powder is heat press molded at a temperature at which the resin melts, and the orientation of the liquid crystal resin can be suppressed to be smaller than that of injection molding in which the resin powder is melted at a high temperature at which the resin flows. , It is not possible to eliminate the anisotropy of the obtained molded product. Patent Document 1 describes a method for producing a liquid crystal resin sheet, in which a plurality of types of liquid crystal resins having different thermal deformation temperatures are crushed, mixed to prepare a molding material, and the molding material is press-molded in a predetermined temperature range. Have been described.

Japanese Unexamined Patent Publication No. 2008-30397

An object of the present invention is to provide a powdery liquid crystal resin capable of producing a hot press molded product having a small anisotropy and a hot press molded product using the same.

The present invention relates to the following.
[1] A powdery liquid crystal resin for a thermosetting product, which contains 90 mol% or more of a structural unit derived from an aromatic hydroxycarboxylic acid in all the structural units and has an average particle size of 10 μm or more and 300 μm or less.
[2] The powdery liquid crystal resin according to [1], which has a crystallinity of 10% or more and 60% or less.
[3] In [1] or [2], the difference ΔTm (Tm2-Tm1 onset temperature) between the melting point Tm2 and the onset temperature of the melting point Tm1 measured by the differential scanning calorimeter is 30 ° C. or higher and 90 ° C. or lower. The powdery liquid crystal resin according to the above.
[4] The powdery liquid crystal resin according to any one of [1] to [3], wherein the melting point Tm2 measured by a differential scanning calorimeter is 250 ° C. or higher and 400 ° C. or lower.
[5] From [1], the melt viscosity measured at a cylinder temperature 10 to 30 ° C. higher than the melting point Tm2 measured by a differential scanning calorimeter and a shear rate of 100 sec ^-1 is 10 Pa · s or more and 1000 Pa · s or less. The powdery liquid crystal resin according to any one of [4].
[6] The powdery liquid crystal resin according to any one of [1] to [5], wherein the ratio of the maximum particle size to the average particle size (maximum particle size / average particle size) is 5 or less.
[7] A powder material for a hot press molded product containing the powdery liquid crystal resin according to any one of [1] to [6].
[8] A thermosetting product using the powdery liquid crystal resin according to any one of [1] to [6].
[9] The hot press molded product according to [8], which is in the form of a film having a thickness of less than 2 mm.

According to the present invention, it is possible to provide a powdery liquid crystal resin capable of producing a hot press molded product having a small anisotropy and a hot press molded product using the same.

It is an optical micrograph of the surface of the heat press molding film obtained in Example 1. FIG. It is an optical micrograph of the surface of the heat press molding film obtained in Comparative Example 1.

Hereinafter, one embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications as long as the effects of the present invention are not impaired.

[Powdered liquid crystal resin]
The powdery liquid crystal resin for a thermosetting product according to the present embodiment (hereinafter, also simply referred to as “powdered liquid crystal resin”) contains 90 mol% of the constituent units derived from aromatic hydroxycarboxylic acid in all the constituent units. Contains the above. In the present specification, the term "powder" means that the particles are composed of fine particles having an average particle size of about 0.1 μm to 1000 μm, and the “average particle size” is a laser diffraction / scattering type particle size. It means the arithmetic average particle size based on the volume by the distribution measurement method. The average particle size can be measured using, for example, a laser diffraction / scattering type particle size distribution measuring device LA-920 manufactured by HORIBA, Ltd.
"Liquid crystal" means having a property of being able to form an optically anisotropic molten phase. The properties of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizing element. More specifically, the anisotropic molten phase can be confirmed by observing the molten sample placed on the Leitz hot stage at a magnification of 40 times under a nitrogen atmosphere using a Leitz polarizing microscope. A liquid crystal resin normally transmits polarized light even in a molten and stationary state when inspected between orthogonal polarizers, and exhibits optical anisotropy.

The liquid crystal resin preferably contains at least one selected from liquid crystal polyester and liquid crystal polyester amide, which contains a structural unit derived from an aromatic hydroxycarboxylic acid. The liquid crystal polyester and the liquid crystal polyester amide are not particularly limited, but are preferably aromatic polyester or aromatic polyester amide, and include at least one resin selected from total aromatic polyester and total aromatic polyester amide. Is more preferable. Further, an aromatic polyester or a polyester partially containing an aromatic polyester amide in the same molecular chain can also be used.

More specifically, as an aromatic polyester or an aromatic polyester amide containing a structural unit derived from an aromatic hydroxycarboxylic acid,
(1) Polyester containing one or more selected from structural units derived mainly from aromatic hydroxycarboxylic acids and derivatives thereof;
(2) Mainly derived from (a) one or more selected from the constituent units derived from aromatic hydroxycarboxylic acids and their derivatives, and (b) derived from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their derivatives. Polyester containing one or more selected from the constituent units of
(3) Mainly (a) one or more selected from the constituent units derived from aromatic hydroxycarboxylic acids and derivatives thereof, and (b) derived from aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof. One or more selected from the constituent units of (c) aromatic diols, alicyclic diols, aliphatic diols, and one or more selected from the constituent units derived from their derivatives. And including polyester;
(4) One or more selected mainly from (a) constituent units derived from aromatic hydroxycarboxylic acids and their derivatives, and (b) constituents derived from aromatic hydroxyamines, aromatic diamines, and their derivatives. Polyester containing one or more selected from units and (c) one or more selected from constituent units derived from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof. Amide;
(5) One or more selected mainly from (a) constituent units derived from aromatic hydroxycarboxylic acids and their derivatives, and (b) constituents derived from aromatic hydroxyamines, aromatic diamines, and their derivatives. One or more selected from the units, (c) one or more selected from the constituent units derived from aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and their derivatives, and (d). Examples thereof include polyesteramides containing one or more selected from aromatic diols, alicyclic diols, aliphatic diols, and structural units derived from their derivatives. Further, a molecular weight adjusting agent may be used in combination with the above-mentioned constituent components, if necessary.

Examples of the aromatic hydroxycarboxylic acid include 4-hydroxybenzoic acid (HBA), 3-hydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, and 6-hydroxy-2-naphthoe. Acids (HNA), 5-hydroxy-1-naphthoic acid, 4'-hydroxy [1,1'-biphenyl] -4-carboxylic acid, derivatives thereof and the like can be mentioned. Examples of the derivative include a compound in which the aromatic ring (aromatic ring) of the aromatic hydroxycarboxylic acid is substituted with a substituent having 0 to 20 carbon atoms (preferably 0 to 10 carbon atoms). Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, a halogen atom, a hydroxyl group, an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, a mercapto group, an alkylthio group and an alkenylthio group. Arylthio group, aralkylthio group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, amino group, mono or dialkylamino group, mono or diphenylamino group, acylamino group, epoxy group containing group, acyl group, Examples include an oxo group and an isocyanate. The liquid crystal resin may have one kind of the structural unit derived from these aromatic hydroxycarboxylic acids, or may have two or more kinds.

（Ｘ：アルキレン（Ｃ_１〜Ｃ_４）、アルキリデン、−Ｏ−、−ＳＯ−、−ＳＯ_２−、−Ｓ−、及び−ＣＯ−より選ばれる基である。）

（Ｙ：−（ＣＨ_２）_ｎ−（ｎ＝１〜４）及び−Ｏ（ＣＨ_２）_ｎＯ−（ｎ＝１〜４）より選ばれる基である。）Examples of other monomers constituting the liquid crystal resin include 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, hydroquinone, resorcin, and compounds represented by the following general formula (I). And aromatic diols such as compounds represented by the following general formula (II); terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and the following general formula (III). Aromatic dicarboxylic acids such as compounds to be used; aromatic amines such as p-aminophenol and p-phenylenediamine can be mentioned.

(X: _{A group selected from alkylene (C 1 to} C ₄ ), alkylidene, -O-, -SO-, -SO _2- , -S-, and -CO-.)

(Y: _{A group selected from − (CH 2} ) _n − (n = 1 to 4) and −O (CH ₂ ) _n O − (n = 1 to 4).)

The liquid crystal resin contains 90 mol% or more of the structural units derived from the aromatic hydroxycarboxylic acid in all the structural units. The constituent unit derived from the aromatic hydroxycarboxylic acid is preferably 93 mol% or more, more preferably 95 mol% or more. The upper limit is not particularly limited and can be, for example, 98 mol% or less. By using a powdery liquid crystal resin (liquid crystal resin fine particles) containing 90 mol% or more of a constituent unit derived from aromatic hydroxycarboxylic acid, the orientation of the resin during hot press molding is small, so the anisotropy is small. A thermosetting product can be manufactured.
The content of the structural unit derived from the aromatic hydroxycarboxylic acid in the liquid crystal resin can be measured by thermal decomposition gas chromatography or the like.

The method for producing the liquid crystal polyester and the liquid crystal polyester amide is not particularly limited, and it is produced by a known method using the above-mentioned monomer compound (or a mixture of monomers) by a direct polymerization method or a transesterification method. However, usually, a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, etc., or a combination of two or more of these is used, and a melt polymerization method, or a melt polymerization method and a solid phase polymerization method are used. The combination with is preferably used. When the compound has an ester-forming ability, it may be used as it is for the polymerization, or it is modified from the precursor to the derivative having the ester-forming ability by using an acylating agent or the like in the pre-polymerization step. You may use the thing. Examples of the acylating agent include acetic anhydride and other anhydrous carboxylic acids.

Various catalysts can be used for the polymerization. Typical usable catalysts are potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, tris (2,4-pentandionato) cobalt (III). ) And other metal salt-based catalysts, and organic compound-based catalysts such as N-methylimidazole and 4-dimethylaminopyridine. The amount of the catalyst used is generally about 0.001 to 1% by mass, particularly preferably about 0.01 to 0.2% by mass, based on the total weight of the monomer.

The deflection temperature under load measured according to ASTM D648 of the liquid crystal resin is preferably 150 ° C. or higher and 280 ° C. or lower, more preferably 160 ° C. or higher and 270 ° C. or lower, and further preferably 170 ° C. or higher and 260 ° C. or lower. It is as follows. By setting the deflection temperature under load to 150 ° C. or higher and 280 ° C. or lower, the orientation of the resin during hot press molding can be made smaller, and a hot press molded product having less anisotropy can be manufactured.

Various fibrous, powdery, plate-like inorganic and organic fillers can be added to the liquid crystal resin at the manufacturing stage. As the fibrous filler, glass fiber, milled glass fiber, carbon fiber, asbestos fiber, silica fiber, silica / alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, Examples thereof include silicate fibers such as wollastonite, magnesium sulfate fibers, aluminum borate fibers, and inorganic fibrous substances such as metal fibrous materials such as stainless steel, aluminum, titanium, copper and brass. A particularly typical fibrous filler is glass fiber. In addition, high melting point organic fibrous substances such as polyamide, fluororesin, polyester resin, and acrylic resin can also be used.
Examples of the powder / granular filler include carbonates such as carbon black, graphite, silica, quartz powder, glass beads, glass balloons, glass powder, calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, and wollastonite. , Iron oxide, titanium oxide, zinc oxide, antimony trioxide, metal oxides such as alumina, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, and other ferrites and carbides. Examples thereof include silicon, silicon nitride, boron nitride, and various metal powders.
Examples of the plate-shaped filler include mica, glass flakes, talc, and various metal foils.
These inorganic and organic fillers can be used alone or in combination of two or more.
The content of the filler can be 0 to 100 parts by mass with respect to 100 parts by mass of the liquid crystal resin.
Further, the liquid crystal resin may contain additives such as an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a pigment, and a crystal nucleating agent as other components.

The average particle size of the powdery liquid crystal resin is 10 μm or more and 300 μm or less, preferably 10 μm or more and 100 μm or less, and more preferably 10 μm or more and 50 μm or less. By setting the average particle size to 10 m or more and 300 μm or less, the orientation of the resin during hot press molding can be reduced, and a hot press molded product having low anisotropy can be manufactured. The "average particle size" is as described above.

The ratio of the maximum particle size to the average particle size (maximum particle size / average particle size) of the powdery liquid crystal resin is preferably 5 or less, and more preferably 2.5 or less. The lower limit is not particularly limited and may be 1 or more. The "maximum particle size" means the maximum value among the values measured by the laser diffraction / scattering type particle size distribution measurement method. By setting the ratio of the maximum particle size to the average particle size (maximum particle size / average particle size) to 5 or less, the powder fluidity during hot press molding can be improved.

In the production of the powdery liquid crystal resin having the average particle size, the liquid crystal resin obtained by the method for producing the liquid crystal resin can be used as it is as the powder liquid liquid resin, or the method for producing the liquid crystal resin. The liquid crystal resin obtained by the above method is molded into pellets, fibers, films, etc., and then dried, wet, and frozen using a jet mill, bead mill, hammer mill, ball mill, cutter mill, stone mill type grinder, etc. It is also possible to use the one crushed by. In addition, a method of dissolving the liquid crystal resin in a solvent and then spray-drying, a poor solvent precipitation method of forming an emulsion in the solvent and then contacting the poor solvent, and a method of forming the emulsion in the solvent and then drying the organic solvent. An in-liquid drying method or the like for removing can also be used. A method of mixing the liquid crystal resin and the non-liquid crystal resin and then dissolving and removing the non-liquid crystal resin with a solvent to obtain a powdery liquid crystal resin having the above average particle size can also be used. Alternatively, a method can be used in which the oligomer of the liquid crystal resin is pulverized and then solid-phase polymerized to obtain a powdery liquid crystal resin having the above average particle size.

Above all, it is preferable that the powder is finely divided to the above average particle size in an environment lower than the glass transition temperature Tg of the liquid crystal resin constituting the powdery liquid crystal resin by 30 ° C. to 50 ° C. For example, it is possible to use a powder finely divided in an environment of −40 ° C. (40 ° C. lower than Tg) of the liquid crystal resin having a glass transition temperature of Tg. A powder finely divided in an environment lower than the glass transition temperature Tg of a liquid crystal resin at 30 ° C. to 50 ° C. usually has a narrow particle size distribution, excellent powder fluidity, and a low crystallinity.

The crystallinity of the powdery liquid crystal resin is 10% or more and 60% or less, preferably 12% or more and 58% or less, and more preferably 15% or more and 55% or less. By setting the crystallinity of the powdery liquid crystal resin to 10% or more and 60% or less, the orientation of the resin during hot press molding can be made smaller, and a hot press molded product with less anisotropy can be manufactured. can do. In addition, the strength of the hot press molded product can be increased and the heat resistance can be further increased. The crystallinity can be measured by an X-ray diffractometer. When the crystallinity is less than the above range, it can be adjusted to the above range by heat-treating the liquid crystal resin. For example, the crystallinity can be adjusted to the above range by heat-treating the liquid crystal resin in the temperature range of the glass transition temperature Tg or more and the melting point Tm2 or less. The glass transition temperature Tg can be measured by dynamic viscoelasticity measurement.

The melting point Tm2 measured by a differential scanning calorimeter of a powdery liquid crystal resin is 250 ° C. or higher and 400 ° C. or lower, preferably 260 ° C. or higher and 380 ° C. or lower, and more preferably 280 ° C. or higher and 350 ° C. or lower. By setting the melting point Tm2 to 250 ° C. or higher and 400 ° C. or lower, the orientation of the resin during hot press molding can be made smaller, and a hot press molded product having less anisotropy can be manufactured. In addition, the strength of the hot press molded product can be increased and the heat resistance can be further increased.
The melting point Tm2 is the peak top temperature (melting point Tm1) at the heat absorption peak observed when heating (1st RUN) from room temperature at a heating rate of 20 ° C./min by a method based on JIS K-7121 (1999). ), Held at (melting point Tm1 + 40) ° C. for 2 minutes, then cooled to room temperature at a temperature lowering rate of 20 ° C./min, and then heated again from room temperature at a heating rate of 20 ° C./min (2ndRUN). Let it be the temperature of the peak top at the heat absorption peak of the 2nd RUN to be performed. The onset temperature (peak rising start temperature) at the melting point Tm1, which will be described later, is the onset temperature at the endothermic peak of the 1st RUN.

The powdery liquid crystal resin preferably has a difference ΔTm (Tm2-Tm1 onset temperature) between the melting point Tm2 and the onset temperature of the melting point Tm1 measured by a differential scanning calorimeter of 30 ° C. or higher and 90 ° C. or lower. More preferably, it is ℃ or more and 80 ℃ or less. By setting the difference ΔTm between the melting point Tm2 and the onset temperature of the melting point Tm1 in this range, the workability at the time of hot press molding can be improved and the heat resistance of the hot press molded product can be improved.

The powdery liquid crystal resin has a cylinder temperature 10 to 30 ° C. higher than the melting point Tm2 measured by a differential scanning calorimeter ^{and a melt viscosity measured at a shear rate of 100 sec -1} of 10 Pa · s or more and 1000 Pa · s or less. Is preferable, and more preferably 50 Pa · s or more and 800 Pa · s or less. The melt viscosity measured at "a cylinder temperature 10 to 30 ° C. higher than the melting point Tm2" is any one of the temperatures in which the cylinder temperature is 10 to 30 ° C. higher than the melting point Tm2, which is appropriately selected depending on the type of liquid crystal resin. It means the melt viscosity measured at the above temperature, and the melt viscosity measured in all the temperature ranges 10 to 30 ° C. higher than the melting point Tm2 does not have to be within the above range. By setting the melt viscosity of the powdery liquid crystal resin in the above range, the appearance of the hot press molded product can be improved. The melt viscosity can be adjusted by adjusting the final polymerization temperature at the time of melt polymerization of the liquid crystal resin. For example, the melt viscosity can be set to 10 Pa · s by setting the final polymerization temperature at the time of melt polymerization of the liquid crystal resin to more than 300 ° C.

The shape of the fine particles in the powdery liquid crystal resin is not particularly limited, and may be in any form such as spherical (including substantially spherical), spindle-shaped, amorphous particulate, fibril-like, and fibrous. In terms of powder fluidity, it is preferably spherical (including substantially spherical) or irregularly shaped particles.

[Hot press molded product]
The hot press molded product is a molded product formed by using the above-mentioned powdery liquid crystal resin. Since it is formed by using the powdery liquid crystal resin described above, it can be a hot press molded product having a small anisotropy. Since the anisotropy is small, physical properties such as strength and heat resistance can be made uniform in the flow direction of the resin and the direction perpendicular to the flow direction thereof, and a highly reliable molded product can be obtained. Therefore, it can be preferably used as an automobile part used at a high temperature, an electric / electronic part mounted in a solder reflow process, a flexible copper-clad laminate, and the like. The hot press molded product can be configured to be, for example, a film-shaped molded product having a thickness of less than 2 mm.

In the production of the hot press molded product, the powder material containing the powdery liquid crystal resin is pressed by a heat press molding machine at a temperature (for example, 250 ° C. to 400 ° C.) of the powdery liquid crystal resin having a melting point of Tm2 or more. It can be obtained by molding. The pressure at the time of molding is not particularly limited, and can be a pressure capable of molding to a desired thickness.

The powder material contains one or more of the above-mentioned powdery liquid crystal resins. The total content of the powdery liquid crystal resin is preferably 50% by mass or more, and more preferably 70% by mass or more in the powder material for hot press molding. The upper limit value is not particularly limited and may be, for example, 95% by mass or less.

The powder material may contain additives such as an inorganic filler in addition to the powdery liquid crystal resin, depending on the physical characteristics and applications required for the obtained molded product. Examples of the inorganic filler include a powder-granular filler having an average particle size of 500 nm or less or 400 nm or less, a plate-shaped filler, and a fibrous filler having an average fiber length of 100 μm or less. The material of the inorganic filler is not particularly limited, and for example, the same material as the inorganic filler that can be blended with the liquid crystal resin described above can be used. By using the powder granular filler and the plate-shaped filler having the average particle size, the powder fluidity and dispersibility of the liquid crystal resin fine particles can be improved. By using the fibrous filler having the above average particle size, the strength of the obtained hot press molded product can be further increased. The average particle size can be measured by the same method as the above-mentioned resin fine particles. The average fiber length can be measured using, for example, the image measuring device LUZEXFS manufactured by Nicolet Co., Ltd. The content of the inorganic filler is preferably 50% by mass or less, more preferably 30% by mass or less in the powder material.

As a mixing method in the case of using a powdery liquid crystal resin as a mixing material, a conventionally known method can be used, for example, a mixing method by shaking, a mixing method involving pulverization of a ball mill or the like, a stirring blade of a Henschel mixer or the like. The mixing method according to the above can be used. As other additives, antioxidants, heat stabilizers, ultraviolet absorbers, lubricants and the like can also be used.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the interpretation of the present invention is not limited by these Examples.

The liquid crystal resin LCPs 1 to 4 used in Examples and Comparative Examples were produced as follows.
[Production Example 1] LCP1: After charging the following raw materials into an all-aromatic polyester polymerization vessel, the temperature of the reaction system was raised to 140 ° C., and the reaction was carried out at 140 ° C. for 1 hour. Then, the temperature is further raised to 325 ° C. over 3.5 hours, and then the pressure is reduced to 5 Torr (that is, 667 Pa) over 20 minutes while distilling acetic acid, excess acetic anhydride, and other low boiling points. Polycondensation was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to bring the mixture from a reduced pressure state to a pressurized state through normal pressure, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized to obtain LCP1 pellets.
(material)
4-Hydroxybenzoic acid (HBA); 1660 g (73 mol%)
6-Hydroxy-2-naphthoic acid (HNA); 837 g (27 mol%)
Metal catalyst (potassium acetate catalyst); 165 mg
Acylating agent (acetic anhydride); 1714 g

[Production Example 2] LCP2: After charging the following raw materials into an all-aromatic polyester polymerization vessel, the temperature of the reaction system was raised to 140 ° C., and the reaction was carried out at 140 ° C. for 1 hour. Then, the temperature is further raised to 330 ° C. over 3.5 hours, and then the pressure is reduced to 10 Torr (that is, 1330 Pa) over 15 minutes while distilling acetic acid, excess acetic anhydride, and other low boiling points. Polycondensation was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to bring the mixture from a reduced pressure state to a pressurized state through normal pressure, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized to obtain LCP2 pellets.
(material)
4-Hydroxybenzoic acid (HBA); 2524 g (79.3 mol%)
6-Hydroxy-2-naphthoic acid (HNA); 867 g (20 mol%)
Terephthalic acid (TA); 27 g (0.3 mol%)
Metal catalyst (potassium acetate catalyst); 150 mg
Acylating agent (acetic anhydride); 2336 g

[Production Example 3] LCP3: Total Aromatic Polyester Amid After charging the following raw materials into a polymerization vessel, the temperature of the reaction system was raised to 140 ° C., and the reaction was carried out at 140 ° C. for 1 hour. Then, the temperature is further raised to 340 ° C. over 4.5 hours, and then the pressure is reduced to 10 Torr (that is, 1330 Pa) over 15 minutes while distilling acetic acid, excess acetic anhydride, and other low boiling points. Polycondensation was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to bring the mixture from a reduced pressure state to a pressurized state through normal pressure, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized to obtain LCP3 pellets.
(material)
4-Hydroxybenzoic acid (HBA); 1380 g (60 mol%)
6-Hydroxy-2-naphthoic acid (HNA); 157 g (5 mol%)
Terephthalic acid (TA); 484 g (17.5 mol%)
4,4'-Dihydroxybiphenyl (BP); 388 g (12.5 mol%)
4-acetoxyaminophenol (APAP); 160 g (5 mol%)
Metal catalyst (potassium acetate catalyst); 110 mg
Acylating agent (acetic anhydride); 1659 g

[Production Example 4] LCP4: After charging the following raw materials into an all-aromatic polyester polymerization vessel, the temperature of the reaction system was raised to 140 ° C., and the reaction was carried out at 140 ° C. for 1 hour. Then, the temperature is further raised to 360 ° C. over 5.5 hours, and then the pressure is reduced to 5 Torr (that is, 667 Pa) over 30 minutes while distilling acetic acid, excess acetic anhydride, and other low boiling points. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to bring the mixture from a reduced pressure state to a pressurized state through normal pressure, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized to obtain pellets. The obtained pellets were heated in a nitrogen atmosphere from room temperature to 290 ° C. over 20 minutes, held for 3 hours, and then allowed to cool to obtain LCP4 pellets.
(material)
4-Hydroxybenzoic acid (HBA); 37 g (2 mol%)
6-Hydroxy-2-naphthoic acid (HNA); 1218 g (48 mol%)
Terephthalic acid (TA); 560 g (25 mol%)
4,4'-Dihydroxybiphenyl (BP); 628 g (25 mol%)
Metal catalyst (potassium acetate catalyst); 165 mg
Acylating agent (acetic anhydride); 1432 g

(Deflection temperature under load)
The pellets of the production example were molded using a molding machine (“SE100DU” manufactured by Sumitomo Heavy Industries, Ltd.) under the following molding conditions to prepare a test piece of 80 mm × 10 mm × 3.2 mm. Using this test piece, the deflection temperature under load was measured according to ASTM D648. As the bending stress, 1.8 MPa was used. The results are shown in Table 1.
〔Molding condition〕
Cylinder temperature:
300 ° C (LCP1)
340 ° C (LCP2)
350 ° C (LCP3)
370 ° C (LCP4)
Mold temperature: 80 ° C
Injection speed: 33 mm / sec

[Example 1]
LCP1 was wet-pulverized using a mass colloider (MKZA10-15JP, manufactured by Masuyuki Sangyo Co., Ltd.) in an environment of a water temperature of 35 ° C., and then spray-dried to obtain a powdery liquid crystal resin. The melt viscosity, average particle size and maximum particle size, crystallinity, and melting point (Tm2, Tm1 onset temperature) of this powdery liquid crystal resin were measured by the methods shown below.
Using the obtained powdery liquid crystal resin, using a thermosetting machine (“Mini Test Press-10” manufactured by Toyo Seiki Seisakusho Co., Ltd.), under the conditions of a press temperature of 290 ° C. and a pressure of 3 MPa, a radius of 50 mm × A film having a thickness of 0.1 mm was produced. The orientation of the resin of the obtained film was evaluated by the method shown below.

[Example 2]
A press-molded film was obtained in the same manner as in Example 1 except that the liquid crystal resin was as shown in Table 1 and the press temperature was 330 ° C. With respect to the obtained powdery liquid crystal resin and film, various physical properties were measured in the same manner as in Example 1, and the orientation of the resin was evaluated.

[Comparative Example 1]
A press-molded film was obtained in the same manner as in Example 1 except that the liquid crystal resin was as shown in Table 1 and the press temperature was 340 ° C. With respect to the obtained powdery liquid crystal resin and film, various physical properties were measured in the same manner as in Example 1, and the orientation of the resin was evaluated.

[Comparative Example 2]
A heat press-molded film was obtained in the same manner as in Example 2 except that the pellets of LCP2 were used as they were. With respect to the obtained powdery liquid crystal resin and film, various physical properties were measured in the same manner as in Example 1, and the orientation of the resin was evaluated.

[Comparative Example 3]
A thermosetting film was obtained in the same manner as in Example 1 except that the liquid crystal resin was as shown in Table 1 and the press temperature was 360 ° C. With respect to the obtained powdery liquid crystal resin and film, various physical properties were measured in the same manner as in Example 1, and the orientation of the resin was evaluated.

[Measurement and evaluation]
The method for measuring the melt viscosity, average particle size and maximum particle size, crystallinity, and melting point (Tm2, Tm1 onset temperature) of the powdery liquid crystal resin, and the method for evaluating the orientation state of the resin are as follows. .. The results are shown in Table 1.

(Melting viscosity)
Using a capillary rheometer (Capillary Graph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd .: piston diameter 10 mm), the apparent melt viscosity was measured in accordance with ISO 11443 under the following conditions. An orifice having an inner diameter of 1 mm and a length of 20 mm was used for the measurement.
Cylinder temperature:
300 ° C (LCP1)
340 ° C (LCP2)
350 ° C (LCP3)
370 ° C (LCP4)
Shear velocity: 100 sec ^-1

(Average particle size and maximum particle size)
The average particle size and the maximum particle size were measured using a laser diffraction / scattering particle size distribution measuring device (LA-920, manufactured by HORIBA, Ltd.) and methanol as a dispersion solvent. The average particle size is an arithmetic average particle size based on the volume.

(Crystallinity)
From the diffraction information (wide-angle X-ray diffraction pattern or wide-angle X-ray diffraction profile) obtained by using an X-ray diffractometer (D2 PHASER, manufactured by Bruker), a scattering region derived from amorphous and a scattering region derived from crystal Divided into W. Ruland, Acta Cryst. , 14, 1180 (1961), and the crystallinity was measured by the following formula (I).
Crystallinity (%) = [Crystal-derived scattering intensity / (Crystal-derived scattering intensity + non-crystal-derived scattering intensity)] × 100 ... (I)

(Melting point Tm2 and melting point Tm1 onset temperature)
The peak top temperature (melting point Tm1) at the heat absorption peak observed when heating (1stRUN) from room temperature at a heating rate of 20 ° C./min using a differential scanning calorimeter (DSC7000X, manufactured by Hitachi High-Tech Science Co., Ltd.). After the measurement, the temperature is kept at (melting point Tm1 + 40) ° C. for 2 minutes, then cooled to room temperature at a temperature lowering rate of 20 ° C./min, and then heated again from room temperature at a heating rate of 20 ° C./min. The temperature of the peak top at the heat absorption peak of 2ndRUN was measured as the melting point Tm2. Further, the onset temperature (the temperature at which the peak starts to rise) at the endothermic peak of 1stRUN was measured as the melting point Tm1 onset temperature.

(Evaluation of resin orientation)
A surface photograph of the film was taken using an optical microscope (ultra-depth multi-angle microscope, "VHX-D510" manufactured by KEYENCE). The obtained photographs are shown in FIGS. 1 and 2. The surface was observed and evaluated according to the following criteria.
Good: There is no streak pattern.
Defective: There is a streak pattern.

Claims (6)

It contains 90 mol% or more of the structural units derived from aromatic hydroxycarboxylic acids, the average particle size is 10 μm or more and 50 μm or less, and the crystallinity is 10% or more and 60% or less.
(1) Polyester consisting of one or more selected from the structural units derived from aromatic hydroxycarboxylic acids and their derivatives;
(2) One or more selected from the constituent units derived from (a) aromatic hydroxycarboxylic acids and derivatives thereof, and (b) derived from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof. Polyester consisting of one or more selected from the structural units;
(3) (a) One or more selected from the constituent units derived from aromatic hydroxycarboxylic acids and derivatives thereof, and (b) derived from aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof. One or more selected from the constituent units, and (c) one or more selected from the constituent units derived from aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof. Polyol consisting of;
(4) One or more selected from (a) constituent units derived from aromatic hydroxycarboxylic acids and derivatives thereof, and (b) constituent units derived from aromatic hydroxyamines, aromatic diamines, and derivatives thereof. Polyesteramide consisting of one or more selected from, and (c) one or two or more selected from the constituent units derived from (c) aromatic dicarboxylic acid, alicyclic dicarboxylic acid, and derivatives thereof. ;, And (5) (a) one or more selected from the constituent units derived from aromatic hydroxycarboxylic acids and derivatives thereof, and (b) derived from aromatic hydroxyamines, aromatic diamines, and derivatives thereof. One or more selected from the constituent units of (c) aromatic dicarboxylic acid, alicyclic dicarboxylic acid, and one or more selected from the constituent units derived from their derivatives. d) A polyesteramide consisting of one or more selected from the constituent units derived from aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof;
A powdery liquid crystal resin for a thermosetting product, which comprises at least one selected from the group consisting of. The powdery liquid crystal resin according to claim 1, wherein the difference ΔTm (Tm2-Tm1 onset temperature) between the melting point Tm2 and the onset temperature of the melting point Tm1 measured by a differential scanning calorimeter is 30 ° C. or higher and 90 ° C. or lower. .. The powdery liquid crystal resin according to claim 1 or 2, wherein the melting point Tm2 measured by a differential scanning calorimeter is 250 ° C. or higher and 400 ° C. or lower. Any of claims 1 to 3, wherein the melt viscosity measured at a cylinder temperature 10 to 30 ° C. higher than the melting point Tm2 measured by a differential scanning calorimeter and a shear rate of 100 sec ^-1 is 10 Pa · s or more and 1000 Pa · s or less. The powdery liquid crystal resin according to item 1. The powdery liquid crystal resin according to any one of claims 1 to 4, wherein the ratio of the maximum particle size to the average particle size (maximum particle size / average particle size) is 5 or less. A powder material for a hot press molded product, which contains the powdery liquid crystal resin according to any one of claims 1 to 5.

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