TWI636126B - Liquid crystal polyester guanamine resin composition and composition includes the same as an injection molded body Camera module parts - Google Patents

Abstract

The present invention provides a liquid crystal polyester guanamine resin composition capable of molding a camera module component, which is produced by the camera module component when impacted or dropped by a portable terminal device such as a smart phone equipped with a camera The number of particles is very small. The present invention can be achieved by a liquid crystal polyester guanamine resin composition characterized in that the liquid crystal polyester guanamine is 50 to 80% by mass and the whiskers are 10 to 30% by mass. 1 to 5 mass% of carbon black, 0 to 20 mass% of talc, and 0 to 20 mass% of precipitated barium sulfate (100% by mass or more in total) are obtained by melt-mixing and stirring, and the deflection temperature of the load is 220 ° C or more. The shearing speed is 100 sec ^-1 , and the melting viscosity at a measuring temperature of 370 ° C is 10 to 100 Pa ‧ S.

Description

Liquid crystal polyester guanamine resin composition and composition comprising the same as an injection molded body Camera module parts

Embedded small-sized digital cameras such as smart phones and tablet terminals are gradually being positioned as one of the main functional sections from the additional function section due to the accelerated performance improvement of the number of pixels and the image quality. The present invention relates to a liquid crystal polyester guanamine resin composition suitable for use in such a camera module component, and further relates to a molded body comprising the liquid crystal polyester guanamine resin composition which is injection-molded as a constituent component Camera module components.

Along with the above situation, the problem of preventing particles which are detached from the surface of the camera module member from adhering to the lens is highlighted, and the correspondence is reviewed.

When most of these reviews are performed by the autofocus function, the camera module member and the lens are slid, and the particles that are separated from the surface of the component are evaluated as the center (Patent Documents 1 to 4).

However, in recent years, with the change of lifestyles, the weight reduction of smart phones and portable terminal devices, the carrying frequency of such devices has increased, and when the design, miniaturization, and thinning of machines and components have progressed, In addition to the particles generated during the sliding, the particles generated during the impact of the machine and falling (hereinafter referred to as "particle separation resistance") are also The new topic is highlighted.

Advanced technical literature Patent literature

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-242453

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-242454

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-242455

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-242456

In view of the above circumstances, the inventors and the like have an object of obtaining a liquid crystal polyester guanamine resin composition capable of molding a camera module member, or when it is impacted by a portable terminal device such as a smart phone equipped with a camera. When falling, the number of particles generated by the aforementioned camera module components is very small.

Accordingly, an object of the present invention is to provide a liquid crystal polyester guanamine resin composition which can obtain an injection molded body excellent in particle detachment resistance required for a camera module member in recent years.

In order to achieve the above object, the inventors of the present invention have conducted an intensive review and found that by injecting and molding a liquid crystal polyester guanamine resin composition comprising a specific liquid crystal polyester phthalamide resin, whiskers, and carbon black, The injection molded body of "particles detachment resistance" was completed to complete the present invention.

A first aspect of the present invention relates to a liquid crystal polyester guanamine resin composition characterized by comprising 50 to 80% by mass of a liquid crystal polyester decylamine, 10 to 30% by mass of whiskers, and 1 to 5% by mass of carbon black. 0 to 20% by mass of talc and 0 to 20% by mass of precipitated barium sulfate (100% by mass or more in total) are obtained by melt mixing and stirring, and the load deflection temperature is 220 ° C or more, and the shear rate is 100 sec ^{- 1.} The melting viscosity at a temperature of 370 ° C is 10 to 100 Pa ‧ S.

A second aspect of the present invention relates to a liquid crystal polyester guanamine resin composition characterized by comprising a liquid crystal polyester guanamine resin composed of a liquid crystal polyester decylamine and a wholly aromatic liquid crystal polyester having a melting point of 320 ° C or higher. The total amount of the mixture is 50 to 80% by mass (wherein the mass of the wholly aromatic liquid crystal polyester resin is equal to or less than the mass of the liquid crystal polyester decylamine), the whisker is 10 to 30% by mass, the carbon black is 1 to 5% by mass, and the talc is used. 0 to 20% by mass, and 0 to 20% by mass of the precipitated barium sulfate (100% by mass or more in total) are obtained by melt-mixing and stirring, and the load deflection temperature is 220 ° C or more, and the shear rate is 100 sec ^-1 . The melt viscosity at a temperature of 370 ° C was 10 to 100 Pa ‧ S.

Further, the melting point is measured in accordance with ISO11357-3 and ASTM D3418 (the same applies hereinafter).

A third aspect of the present invention relates to a liquid crystal polyester guanamine resin composition according to the first or second aspect, characterized in that the liquid crystal polyester decylamine comprises: a structural unit represented by the following formula (1): ~65 mol%; the structural unit represented by the following formula (2) is 3 to 17.5 mol%; the structural unit represented by the following formula (3) is 5 to 20 mol%; the following formula (4-1) At least one of the structural unit shown and the structural unit represented by the following formula (4-2), which is 7.5 to 42 mol% in total; and the structural unit represented by the following formula (5-1) and the following formula ( 5-2) at least one of the structural units shown, a total of 2.5 to 40 mol%; and a melting point of 300 ° C or more.

A fourth aspect of the present invention is the liquid crystal polyester guanamine resin composition according to any one of the first to third aspects, characterized in that the whiskers are potassium titanate, calcium silicate, and carbonic acid. At least one of calcium and zinc oxide.

A fifth aspect of the invention relates to a camera module component comprising the injection molded body of the liquid crystal polyester guanamine resin composition according to any one of claims 1 to 4 as a constituent component.

The liquid crystal polyester guanamine resin composition of the present invention has good rigidity, heat resistance, mechanical strength, thin layer processability of a resin composition, mold shape transferability, and surface adhesion (SMT) resistance of a molded article. And "particle detachment resistance", it is possible to provide a camera module assembly having extremely excellent characteristics by injection molding. In particular, a molded article having good toughness can be obtained as compared with the wholly aromatic liquid crystal polyester resin composition which has been advanced in the field.

1‧‧‧gate

2‧‧‧Fusing Department

Fig. 1 is a plan view and a side view of a test piece for measuring the strength of a welded portion 2 (weld).

Fig. 2 is a plan view and a side view of a test piece for measurement of particle detachment resistance.

Form for implementing the invention

The liquid crystal polyester guanamine resin used in the present invention exhibits melt anisotropy. Specifically, it is preferably a liquid crystal polyester decylamine which is a p-hydroxybenzoic acid (HBA), acetaminophen (AAP), 1,4-cyclohexanedicarboxylic acid (CHDA), a specific aromatic diol, and a specific one. The aromatic dicarboxylic acid is obtained as a constituent monomer by a polycondensation reaction of the monomers.

In particular, it is preferably a liquid crystal polyester decylamine obtained by a polycondensation reaction of the following components: the structural unit of the hydroxybenzoic acid (HBA) represented by the following formula (1) is 10 to 65 mol%; The structural unit of acetaminophen (AAP, also known as p-acetamidophenol) represented by formula (2) is 3 to 17.5 mol%; 1,4-cyclohexanedicarboxylic acid represented by the following formula (3) CHDA) origin of the construction order 5 to 20 mol%; at least one of the structural unit represented by the following formula (4-1) and the structural unit derived from the aromatic diol represented by the following formula (4-2), in total 7.5 to 42 mol %; and at least one of the structural unit represented by the following formula (5-1) and the structural unit derived from the aromatic dicarboxylic acid represented by the following formula (5-2), in a total amount of 2.5 to 40 mol% (to 1) ~ (5-2) in total is 100%); and the melting point is 300 ° C or more.

[Chemistry 13]

In the resin composition of the present invention, the mass % of the mixture of the liquid crystal polyester guanamine resin or the liquid crystal polyester phthalamide resin and the wholly aromatic liquid crystal polyester resin is in the range of 50 to 80% by mass. If it is out of this range, it is difficult to obtain sufficient injection molding characteristics.

The structural unit of the wholly aromatic liquid crystal polyester resin which may be contained in the liquid crystal polyester guanamine resin composition of the present invention may, for example, be an aromatic dicarboxylic acid, an aromatic diol, or an aromatic hydroxycarboxylic acid. a combination of heterocyclic aromatic hydroxycarboxylic acids; a combination of an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and an aromatic diol; A polyester such as ethylene dicarboxylate is obtained by reacting an aromatic hydroxycarboxylic acid; and the specific structural unit is, for example, the following.

Structural unit derived from aromatic hydroxycarboxylic acid: [Chemical 15]

Construction unit from aromatic dicarboxylic acid: [Chem. 16]

Repetitive structural units derived from aromatic diols: [Chem. 17]

From the viewpoint of heat resistance, mechanical properties, and molding processability, the wholly aromatic liquid crystal polyester resin is preferably used in the + wholly aromatic liquid crystal polyester resin, and has the above structural unit (A1) of 30 mol% or more, more preferably (A1) and (B1) have a total of 60 mol% or more.

Particularly suitable liquid crystal polyesters are as follows: 80-100 mole of p-hydroxybenzoic acid (I), terephthalic acid (II), 4,4'-dihydroxybiphenyl (III) (including derivatives thereof) % (wherein the total of (I) and (II) is 60 mol% or more), and other aromatic compounds which can be decondensed with one of (I), (II) and (III) ~20 mol% of polyaromatic liquid crystal polyester having a melting point of 320 ° C or higher; or p-hydroxybenzoic acid (I), terephthalic acid (II), 4,4'-dihydroxybiphenyl (III) (including derivatives thereof) 90 to 99 mol% (wherein the total of (I) and (II) is 60 mol% or more), and may be combined with (I), (II), III) A wholly aromatic liquid crystal polyester having a melting point of 320 ° C or more, which is obtained by polycondensation of 1 to 10 mol% of other aromatic compounds subjected to decondensation reaction (to a total of 100 mol%).

The combination of the above structural units is preferably as follows: (A1) (A1), (B1), (C1) (A1), (B1), (B2), (C1) (A1), (B1), (B2), ( C2) (A1), (B1), (B3), (C1) (A1), (B1), (B3), (C2) (A1), (B1), (B2), (C1), (C2) (A1), (A2), (B1), (C1), especially suitable monomer composition ratio, in the wholly aromatic liquid crystal polyester resin, hydroxybenzoic acid, terephthalic acid, 4,4'- Dihydroxybiphenyl (including derivatives thereof) 80 to 100 mol%, and a wholly aromatic group selected from the group consisting of aromatic diols, aromatic hydroxy dicarboxylic acids and aromatic dicarboxylic acids The compound is also 0 to 20 mol% in the wholly aromatic liquid crystal polyester resin (to make it equal to 100 Mole %), a liquid crystal polyester guanamine resin which is obtained by polycondensation. When the hydroxybenzoic acid, terephthalic acid or 4,4'-dihydroxybiphenyl is 80 mol% or less, the heat resistance tends to be lowered, which is not preferable.

The method for producing a liquid crystal polyester guanamine resin used in the present invention can be carried out according to a method for producing a liquid crystal polyester resin by a conventional method, and can be carried out by a production method by only melt polymerization or by melt polymerization and solid phase. A manufacturing method carried out by two-stage polymerization of polymerization.

When the polymer obtained by melt polymerization is further subjected to solid phase polymerization, the polymer obtained by melt polymerization is solidified and then pulverized to form a powder or a sheet, and then a conventional solid phase polymerization method is preferably selected. For example, a method of heat treatment for 1 to 30 hours in a temperature range of 200 to 350 ° C in an inert gas atmosphere such as nitrogen. The solid phase polymerization may be carried out while stirring, or may be carried out without being stirred.

It is possible to use or not use a catalyst in the polymerization reaction. As the catalyst to be used, a catalyst for polycondensation of polyester can be used, and examples thereof include metal salts such as magnesium acetate, tin acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide. Catalyst, organic compound catalyst such as N-methylimidazole, etc.

The polymerization apparatus in the melt polymerization is not particularly limited, and a reaction apparatus for a general high viscosity fluid reaction is preferably used. Examples of such a reaction apparatus include, for example, a stirred tank type polymerization apparatus having an anchor type, a multi-layer type, a spiral belt type, a spiral shaft type, or the like, or a stirring device for stirring the impellers of various shapes, or A kneading machine, a roll mill, a Banbury compact kneader, and the like are generally used in a mixing device for resin mixing and the like.

In the present invention, the liquid crystal polyester phthalamide resin and the liquid crystal polyester have good affinity, and the liquid crystal polyester resin is blended by melt mixing and stirring (so-called polymer blending). Combined). It is preferred to blend the wholly aromatic liquid crystal polyester resin into an amount equal to or less than the equivalent amount. By this blending, the good toughness of the liquid crystal polyester decylamine can be maintained as it is, and the heat resistance can be complemented as needed. As a blending method, each resin is dry-blended, melt-mixed and stirred. When the ratio of the blended wholly aromatic liquid crystal polyester resin exceeds 50% by mass of the total amount, the toughness of the liquid crystal polyester decylamine cannot be sufficiently exhibited, which is not preferable because it does not satisfy the object of the present invention.

The liquid crystal polyester decylamine used in the present invention and the wholly aromatic liquid crystal polyester resin which is mixed as needed may have any shape of powder, granules or pellets, but are dispersed from the filler material. From a point of view, it should be in the form of powder or granules.

<About whiskers (needle-shaped single crystal)>

The liquid crystal polyester guanamine resin sometimes contains various kinds of fibrous fillers, and it is known that it exhibits good heat resistance and rigidity due to its shape. In the present invention, as the fibrous filler, a needle-like single crystal, that is, a so-called "whisker" is contained, and further, a filler different from the filler is contained in a specific blending ratio.

The "particle release resistance" of the liquid crystal polyester amide resin composition for a camera module is markedly enhanced by containing whiskers as a fibrous filler in the resin composition composed of the above specific composition.

The reason why the inventors of the present invention have not yet reached a clear explanation is conceivable in comparison with a representative glass fiber of a fibrous filler.

The particles of the liquid crystal polyester guanamine resin composition containing various filler materials in the event of a drop impact have been known mainly from the fragments of various fibrous filler materials, and the filaments destroyed by the liquid crystal polyester guanamine matrix.

The formation of particles is mainly caused by the aspect ratio and size ratio of the filler. A (large) fibrous filler material and a liquid crystal polyester decylamine interfacial peeling failure pattern.

Between the melt-spinning, the surface shape produced by melt-blowning and the glass fiber having a rough cross-sectional shape, and the surface shape and the needle-shaped single crystal which are smoothed by crystal growth, and as a matrix The interface structure of the liquid crystal polyester decylamine is microscopically different, and the damage pattern of the predicted interface will be different.

For example, a needle-like single crystal interface having a relatively smooth surface and a liquid crystal polyester resin are easily peeled off to form a plurality of fine voids, and the voids are formed to absorb impact energy and suppress damage of the matrix portion, which is derived from liquid crystal polyester decylamine. The matrix causes fibrils (one of the main components of the "particles") to form.

The whiskers used in the present invention are not limited. It is preferable that the whiskers have an average diameter of 5 μm or less with toughness. Specifically, (i) potassium titanate (chemical formula: K ₂ O‧nTiO ₂ (n is 6 or 8), true specific gravity of 3.4 to 3.6, and average fiber diameter of 0.3 to 0.6 μm. For example, it is commercially available. Product name "Tismo" (made by Otsuka Chemical Co., Ltd.); (ii) Calcium citrate (chemical formula: CaSiO ₃ , true specific gravity 2.5 to 2.6, fiber diameter 1 to 5 μm. For example, "Wollastonite is available from the market" (iii) Calcium carbonate (chemical formula: CaCO ₃ , true specific gravity 2.8, average fiber diameter 0.5 to 1 μm. For example, the product name "WHISCAL" (manufactured by MARUO CALCIUM Co., Ltd.) can be obtained from the market; and (iv) Zinc oxide (chemical formula: ZnO, true specific gravity 5.78, average fiber diameter 0.2 to 3 μm. For example, the product name "Panatetra" (manufactured by Panasonic Co., Ltd.) is commercially available; among these, it is easy to operate from the mixing and stirring step. From the viewpoint of the ease of dispersion in the liquid crystal polyester constituting the matrix, it is preferable that the fiber diameter is large, and the difference in specific gravity from the liquid crystal polyester is small, and it is easy to achieve good dispersion (ii) and (iii). The whiskers may be used singly or in combination of two or more kinds in any combination. Resin composition, the content of the whisker should be provided in the range of 10 to 30 mass%. If less than 10 mass%, the addition effect is insufficient. If it exceeds 30% by mass, it is difficult to obtain a good flowability.

<precipitated barium sulfate>

The liquid crystal polyester guanamine resin composition of the present invention contains precipitated barium sulfate. Precipitated barium sulfate is a substantially spherical filler material, which has a low probability of causing interfacial peeling failure patterns of particle formation, and due to its specific high specific gravity (about 4.5), it is possible to improve the liquid crystal polyester guanamine composition. The impact energy absorption efficiency is given to suppress the generation of particles. Moreover, it is amorphous, very fine, soft and not easily damaged, which should also be related to the inhibition of particle formation. When the precipitated barium sulfate is added to the resin composition of the present invention, the content thereof is preferably in the range of 0 to 20% by mass. If it exceeds 20% by mass, it is difficult to obtain good fluidity.

<talc>

In the present invention, the liquid crystal polyester guanamine resin composition preferably contains talc. Since talc is a filling material having an ellipsoidal shape and a smooth surface, dimensional stability is imparted to the molded body by reducing anisotropy, so that the camera module component can improve particle particle detachment even under long-term use. Reliability and other reliability. When the talc is added to the resin composition of the present invention, the content thereof is preferably in the range of 0 to 20% by mass. If it exceeds 20% by mass, it is difficult to obtain good fluidity.

<carbon black>

The carbon black used in the present invention is used for the purpose of ensuring the light-shielding property of the camera module member, and is generally applicable to resin coloring, and is not particularly limited.

In the resin composition of the present invention, the content of carbon black is preferably in the range of 1 to 5% by mass. Further, it is preferably 2 to 4% by mass. When the blending amount of the carbon black is less than 1% by mass, the blackening property of the obtained resin composition is lowered, and the light-shielding property cannot be sufficiently ensured. When the amount is more than 5% by mass, the possibility of generation of particles (fine particles of carbon black-condensed particles) becomes variable. high.

Further, in the composition of the present invention, an antioxidant and a thermal stabilizer (for example, a hindered phenol, a hydroquinone, a phosphite, and the like) may be added to the extent that the object of the present invention is not impaired. , UV absorbers (such as resorcinol, salicylate, benzotriazole, benzophenone, etc.), slip agents and mold release agents (such as octadecanoic acid and its salts, esters, and parts thereof) Higher fatty acids such as esters and stearic acids and their salts, esters thereof, higher alcohols such as stearyl alcohol, stearin and polyethylene waxes and polyolefin waxes, etc., plasticizers, antistatic agents, flame retardants, etc. General additives, other filler materials other than the above, or other thermoplastic resins also impart predetermined characteristics. Further, the number of fine particles of the glass fiber is large, which is not suitable for the purpose of the present invention (refer to Comparative Example 6).

The liquid crystal polyester guanamine resin composition of the present invention is a liquid crystal polyester decylamine which is obtained by mixing and stirring with other components, and is used for a mixing and stirring machine and a running method, and is a user of a general liquid crystal polyester melt mixing and agitating. Yes, there are no special restrictions.

Preferably, a liquid crystal polyester, whiskers, carbon black, and precipitated barium sulfate are placed in a mixing agitator having a pair of screws, and then talc is added as needed, and the mixture is melted, stirred, and pelletized.

This type of machine is called a two-axis extruder. In this type of machine, it is preferable to have a switching mechanism, which can uniformly disperse the filler material and suppress the local heat generation.

<Melt viscosity range>

In the present invention, the liquid crystal polyester guanamine resin composition thus obtained has a melt viscosity measured at a shear rate of 100 sec ^-1 and 370 ° C of 10 to 100 Pa‧S, more preferably in the range of 20 to 100 Pa‧S. When the viscosity of the resin is out of this range, the surface properties of the injection molded body are deteriorated, and as a cause, it is feared that fine particles are generated. The melt viscosity was measured by a capillary rheometer (Model 2010) manufactured by INTESCO Co., Ltd., and the capillary tube was a capillary having a diameter of 1.00 mm, a length of 40 mm, and an inflow angle of 90° at a shear rate of 100 sec ^-1 and a temperature of 320 ° C at +4 ° C / The temperature rise rate of the fraction was measured while the isothermal heating was performed, and the apparent viscosity was measured, and the number of digits was rounded off to obtain the apparent viscosity at 370 °C.

<load deflection temperature>

Further, in the present invention, the weight deflection temperature of the injection molded body of the liquid crystal polyester guanamine resin composition thus obtained must be 220 ° C or higher. Here, the load deflection temperature means the load deflection temperature (DTUL) as determined by ASTM D648. If the load deflection temperature is lower than 220 ° C, it is unfavorable that the heat resistance at the time of solder reflow of the surface is problematic.

The resin composition of the present invention exhibits various characteristics and good fluidity of the constituent materials in the injection molding step, particularly in the molding of an injection molded body having a thin-walled structural portion having a thickness in the range of 0.3 to 0.9 mm. Provides camera module parts with good "particle breakaway resistance". In addition, the injection molded body used for injection molding may be any conventionally used for liquid crystal polyester molding, and is not particularly limited.

[Examples]

The present invention will be further specifically described by the following examples and comparative examples, but the present invention is not limited by the following examples.

[Example 1]

<Manufacture of Liquid Crystalline Polyester Amine (A)>

SUS316 was used as a material, and a polymerization tank (manufactured by Nitto High Pressure Co., Ltd.) having a 6-liter internal volume of a herringbone impeller was charged with 1325.95 g (9.6 m) of hydroxybenzoic acid (manufactured by Ueno Pharmaceutical Co., Ltd.). (Mellinckrodt) 120.94 g (0.80 mol), 4,4'-dihydroxybiphenyl (manufactured by Honshu Chemical Industry Co., Ltd.) 446.90 g (2.40 mol), 1,4-cyclohexanedicarboxylic acid ( 275.49g (1.60m), terephthalic acid (manufactured by Eastman Chemical Co., Ltd.) 186.07 g (1.12 mol), isophthalic acid (manufactured by AG International Chemical Co., Ltd.), 79.74 g (0.48 mol), and potassium acetate (manufactured by Kishida Chemical Co., Ltd.) 0.16 g as a catalyst. And 0.48 g of magnesium acetate (manufactured by Kishida Chemical Co., Ltd.), and the pressure-reduction of the polymerization tank was carried out three times, and nitrogen substitution was carried out, and then 1,621.36 g (15.96 mol) of acetic anhydride was further added, and the stirring impeller rotation speed was set to The temperature was raised to 150 ° C over 1.5 hours at 70 rpm, and the oximation reaction was carried out for 2 hours under reflux.

After completion of the acetylation, the acetic acid was distilled off, and the temperature was raised at 0.5 ° C /min. When the reactor temperature was 305 ° C, the polymer was taken out from the discharge port at the lower portion of the reactor and cooled and solidified. The obtained polymer was pulverized into a sieve which passed through a pore of 2.0 mm by a pulverizer manufactured by Hosokawa Micron Co., Ltd. to obtain a prepolymer.

Next, 1000 g of the prepolymer obtained above was filled in a solid phase polymerization apparatus obtained from the company, and nitrogen was passed at a flow rate of 0.1 Nm ³ /hr, and the heater temperature was raised from room temperature over 45 minutes at a rotation speed of 5 rpm. After the temperature reached 150 ° C, the temperature was raised to 250 ° C over 4 hours, and further, after 3 hours, the temperature was raised to 300 ° C at the end temperature, and then maintained at 300 ° C for 1 hour to carry out solid phase polycondensation. Thus, about 970 g of a powdery thermotropic liquid crystal polyester guanamine (A) was obtained. The obtained thermotropic liquid crystal polyester guanamine (A) had a melting point of 325 °C.

<Manufacture of Liquid Crystalline Polyamide (B)>

SUS316 was used as a material, and a polymerization tank (manufactured by Nitto High Pressure Co., Ltd.) having a 6-liter internal volume of a herringbone impeller was charged with p-hydroxybenzoic acid (manufactured by Ueno Pharmaceutical Co., Ltd.) 1325.95 g (9.60 mol), acetaminophen. (manufactured by Mallinckrodt Co., Ltd.) 193.50 g (1.28 mol), 4,4'-dihydroxybiphenyl (manufactured by Honshu Chemical Industry Co., Ltd.) 357.52 g (1.92 mol), 1,4-cyclohexanedicarboxylic acid ( 275.49g (1.60m), terephthalic acid (manufactured by Eastman Chemical Co., Ltd.) 132.90 g (0.80 mol), and 0.10 g (0.80 mol) of isophthalic acid (manufactured by AG International Chemical Co., Ltd.), and potassium acetate (manufactured by Kishida Chemical Co., Ltd.) 0.16 g as a catalyst. And 0.48 g of magnesium acetate (manufactured by Kishida Chemical Co., Ltd.), and the pressure-reduction of the polymerization tank was carried out three times, and after nitrogen substitution, 1577.90 g (15.46 mol) of acetic anhydride was further added, and the stirring impeller rotation speed was set to The temperature was raised to 150 ° C over 1.5 hours at 70 rpm, and the oximation reaction was carried out for 2 hours under reflux.

Subsequently, in the same manner as in Example 1 (the reactor temperature at the time of removal was 300 ° C), a prepolymer was obtained, and solid phase polymerization (end temperature: 300 ° C) was carried out to obtain a thermotropic liquid crystal polyester guanamine (B). The resulting thermotropic liquid crystal polyester guanamine had a melting point of 335 °C.

(Manufacture of liquid crystal polyester)

SUS316 was used as a material, and a polymerization tank (manufactured by Kobe Steel Co., Ltd.) having a volume of 1700 liters of a herringbone impeller was charged with 298 kg (2.16 kmol) of p-hydroxybenzoic acid (manufactured by Ueno Pharmaceutical Co., Ltd.). , 4'-dihydroxybiphenyl (manufactured by Honshu Chemical Industry Co., Ltd.) 134kg (0.72 kmol), terephthalic acid (manufactured by Mitsui Chemicals, Inc.) 90kg (0.54 kmol), isophthalic acid ( 30 kg (0.18 kg) manufactured by AG International Chemical Co., Ltd., and a polymerization tank was charged with 0.04 kg of potassium acetate (manufactured by Kishida Chemical Co., Ltd.) and 0.10 kg of magnesium acetate (manufactured by Kishida Chemical Co., Ltd.) as a catalyst. The pressure-reducing-nitrogen injection was performed twice, and after nitrogen substitution, 386 kg (3.78 kg) of acetic anhydride was added, and the impellerization reaction was carried out under reflux at a stirring speed of 45 rpm for 1.5 hours. 2 hours. After the completion of the acetylation, the acetic acid was distilled off, and the temperature was raised at 0.5 ° C /min. When the reactor temperature was 305 ° C, the polymer was taken out from the discharge port at the lower portion of the reactor and cooled and solidified by a cooling device. With the crusher made by Hosokawa Micron Co., Ltd. The resulting polymer was pulverized into a sieve which passed through a pore of 2.0 mm to obtain a prepolymer.

The obtained prepolymer was subjected to solid phase polymerization using a rotary kiln manufactured by Takasago Industrial Co., Ltd. The kiln was filled with a prepolymer, nitrogen was passed at a flow rate of ¹⁶ Nm ³ /hr, and the heater temperature was raised from room temperature to 350 ° C at a rotation speed of 2 rpm for 1 hour, and maintained at 350 ° C for 10 hours. It was confirmed that the temperature of the resin powder in the kiln reached 295 ° C, and the heating was stopped, and while rotating the rotary kiln, it was cooled for 4 hours to obtain a powdery liquid crystal polyester. The melting point is 360 ° C and the melt viscosity is 70 Pa‧S.

The characteristics of various fillers used in the examples and comparative examples of the present invention are shown below.

(1) Whiskers:

(i) Potassium titanate: chemical formula; K ₂ O‧nTiO ₂ :n is 6 or 8, true specific gravity is 3.4 to 3.6, and fiber diameter is 0.3 to 0.6 μm (trade name "Tismo", manufactured by Otsuka Chemical Co., Ltd.)

(ii) Calcium citrate: chemical formula; CaSiO ₃ , true specific gravity 2.5~2.6, average fiber diameter 1~5μm (from the market name "Wollastonite")

(iii) Calcium carbonate: chemical formula; CaCO ₃ , true specific gravity 2.8, average fiber diameter 0.5 to 1 μm (trade name "WHISCAL", manufactured by MARUO CALCIUM Co., Ltd.)

(iv) Zinc oxide: chemical formula; ZnO, true specific gravity 5.78, average fiber diameter 0.2 to 3 μm (trade name "Panatetra", manufactured by Amtec Co., Ltd.)

(2) Carbon black (CB): manufactured by Cabot Co., Ltd., "REGAL 660" (first order particle size 24 nm)

(3) Precipitated barium sulfate: BChemical Industries, Ltd., "BMH-40" (average particle size 1 μm, specific gravity 4.5)

(4) Talc: manufactured by Japan Talc Co., Ltd., "MS-KY" (quantitative average particle size 23 μm)

(5) Glass fiber

Made by Nitto Spin Co., Ltd., PF100E-001SC (number average fiber length 100μm, number average fiber diameter 10μm)

(experiment method)

(1) Determination of melt viscosity

The melt viscosity of the liquid crystal polyester guanamine resin composition was measured by a capillary rheometer (2010, manufactured by INTESCO Co., Ltd.), and a capillary having a diameter of 1.00 mm, a length of 40 mm, and an inflow angle of 90° was used at a shear rate of 100 sec ^-1 . The apparent viscosity was measured while heating at a rate of +4 ° C /min at 300 ° C at a constant temperature, and the apparent viscosity at 370 ° C was determined, and the number of digits of the obtained numerical value was rounded off to obtain a measured value. Further, the test was carried out using a resin composition which was previously dried in an air oven at 150 ° C for 4 hours.

(2) Strength measurement of the sintered portion 2

(test piece molding)

Using the injection molding machine (UH-1000, manufactured by Nissei Resin Co., Ltd.), the pellet of the obtained resin composition was obtained at a maximum cylinder temperature of 370 ° C, an injection speed of 300 mm/sec, and a mold temperature of 80 ° C to obtain a test piece. The injection of the resin was carried out at a 2-point gate 1. The mold is formed by a cavity having a size of 48 mm × 15 mm × 0.3 mm, which is substantially in the center of the melt wave front of the resin injected from the different gates 1 to form a mold which spans the sintered portion 2 of the molded body. Fig. 1 is a plan view and a side view showing the test piece obtained by the present mold.

(Strength of strength of the fusion joint 2)

Five test pieces were prepared for each brand, and the resin frame was arranged such that both ends were located on the side of the frame, and the central portion having the sintered portion 2 was placed on the frame window, and the frame was adhered by adhesive tape. Both ends are fixed to the frame. The frame of the test piece is held by the adhesive, and is dropped 5 times from a height of 1.5 m to be placed The large mirror confirms whether or not the sintered portion 2 is broken. A test piece in which no crack occurred was regarded as "○", and a test piece in which cracking occurred was regarded as "x".

(3) Determination of load deflection temperature (DTUL)

Using the injection molding machine, the pellet of the obtained resin composition was obtained at a maximum cylinder temperature of 370 ° C, an injection speed of 100 mm/sec, and a mold temperature of 80 ° C to obtain an injection of 13 mm (width) × 130 mm (length) × 3 mm (thickness). The molded body was used as a test piece for measuring the deflection temperature of the load. For each test piece, the load deflection temperature was measured in accordance with ASTM D648. Based on the applicable surface adhesive work, 220 °C or more is regarded as "○", and less than 220 °C is regarded as "X".

(4) Determination of particle detachment resistance as a component of a camera module

(test piece molding)

Using the injection molding machine (UH-1000, manufactured by Nissei Resin Co., Ltd.), the pellet of the obtained resin composition was obtained at a maximum cylinder temperature of 370 ° C, an injection speed of 300 mm/sec, and a mold temperature of 80 ° C to obtain a test piece. The injection of the resin was carried out at a 1-point gate 1 using a template having a circular recess of 6 mm in the center of a square shape of 8 mm, and further having a mold of a form of 3 mm in the center thereof. The minimum thickness is 0.9mm. Further, the window portion of the molded body corresponds to the lens insertion fixing portion of the actual camera module member, and the molded portion of the molded body inevitably generates the broken line portion welded portion 2. Fig. 2 is a plan view and a side view showing the test piece obtained by the present mold.

(particle detachment resistance assessment)

The SUS container was housed in 50 test pieces, and the container lid was closed. After the container was dropped 50 times from a height of 1.5 m, the container lid was opened, and the test piece was separated from the particles dropped from the test piece, and the number of particles was calculated by "FPIA-3000" manufactured by Sysmex.

The evaluation of particle resistance to detachment is carried out in the third stage, and the number of particles generated in the range of less than 100 is regarded as "◎", if it is 100 or more to less than 200, it is regarded as "○", and more than 200 is regarded as "X".

(5) Anisotropy evaluation

The difference in molding shrinkage ratio between the TD direction and the MD direction was evaluated. For each brand, five test pieces for measuring the "load deflection temperature" obtained in the above (3) were prepared, and after standing at room temperature for 24 hours or more, the length was measured as MD (molding) direction in units of mm. The width is measured as the TD (lateral side) direction to two decimal places. The average value of the dimensions was compared with the actual size of the mold ("length" = 130.02 mm, "width" = 13.02 mm), and the mold shrinkage ratio in the TD direction and the MD direction was determined.

The difference between the molding shrinkage ratio in the TD direction and the MD direction is less than 8 times as "○", and 8 times or more is regarded as "△".

[Table 1]

Industrial availability

The camera module component comprising the injection molded body of the liquid crystal polyester guanamine resin composition of the present invention as a component module has heat resistance against solder reflow and can be applied to injection molding of a member having a thin portion. In addition, since it is embedded in the product, it is used for mobile phones, notebook computers, digital cameras, digital cameras, smart phones, and tablet terminals. The lens barrel portion and the base frame portion of the camera and the like can be used for various purposes such as "CMOS (image sensor) housing", "shutter and shutter tube portion".

Claims (5)

A liquid crystal polyester guanamine resin composition characterized by comprising 50 to 80% by mass of liquid crystal polyester guanamine, 10 to 30% by mass of whiskers, 1 to 5% by mass of carbon black, 0 to 20% by mass of talc, and The precipitated barium sulfate is obtained by melt-mixing and stirring a mixture of 0 to 20% by mass (the total amount is 100% by mass or more), and the deflection temperature of the load is 220 ° C or higher, and the shear rate is 100 sec ^-1 , and the melting at a measurement temperature of 370 ° C is performed. The viscosity is 10~100Pa‧S. A liquid crystal polyester guanamine resin composition characterized in that a liquid crystal polyester guanamine resin mixture composed of a liquid crystal polyester decylamine and a wholly aromatic liquid crystal polyester having a melting point of 320 ° C or more is 50 to 80% by mass in total ( , the mass of the wholly aromatic liquid crystal polyester resin is equal to or less than the mass of the liquid crystal polyester guanamine), 10 to 30% by mass of whiskers, 1 to 5% by mass of carbon black, 0 to 20% by mass of talc, and precipitation 0 to 20% by mass of barium sulfate (100% by mass or more in total) is obtained by melt-mixing and stirring, and has a load deflection temperature of 220 ° C or more, a shear rate of 100 sec ^-1 , and a melt viscosity at a measurement temperature of 370 ° C. 10~100Pa‧S. The liquid crystal polyester guanamine resin composition according to claim 1 or 2, wherein the liquid crystal polyester decylamine comprises: 10 to 65 mol% of the structural unit represented by the following formula (1); The structural unit is 3 to 17.5 mol%; the structural unit represented by the following formula (3) is 5 to 20 mol%; the structural unit represented by the following formula (4-1) and the following formula (4-2) At least one of the structural units shown is 7.5 to 42 mol% in total; and at least one of the structural unit represented by the following formula (5-1) and the structural unit represented by the following formula (5-2), in total 2.5~40 mol%; and the melting point is above 300 °C [Chemistry 7] The liquid crystal polyester guanamine resin composition according to claim 1 or 2, wherein the whisker is at least one of potassium titanate, calcium silicate, calcium carbonate and zinc oxide. A camera module component comprising the injection molded body of the liquid crystal polyester guanamine resin composition according to any one of claims 1 to 4 as a constituent component.