Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

• the present invention relates to a liquid crystal polymer composition and a liquid crystal polymer molded article using the liquid crystal polymer composition.
• Liquid crystal polymers are used in various parts due to their excellent mechanical strength, moldability, dimensional accuracy, chemical resistance, moisture resistance, and electrical properties.
• its use in electronic components such as precision equipment is being studied, and its use in camera modules, for example, is being studied.
• the optical characteristics deteriorate when small particles of dirt, dust, dust, etc. adhere to the lens or image sensor. Therefore, in order to prevent such degradation of optical characteristics, camera module parts are usually ultrasonically cleaned before assembly to remove small dirt, dust, dust, etc. adhering to the surface.
• a molded body made of a liquid crystal polymer liquid crystal polymer molded body
• the surface of the molded body tends to peel off due to the high crystal orientation of the liquid crystal polymer. is known to occur. It is known that small particles are likely to be generated from this fibrillated part, and with the increase in the number of pixels that accompanies the high performance of camera modules, even minute foreign matter of less than 1 ⁇ m can cause defects. may become
• Patent Document 1 discloses a composition containing a thermotropic liquid crystal polymer and inorganic particles having a Mohs hardness of 2.5 or more. disclosed.
• the adhesive that bonds the parts to each other lacks the adhesive strength between the parts, causing the parts to peel off.
• detachment of parts due to dropping directly affects product performance, such as affecting the operation of camera modules. Improving the adhesive force between the adhesive and the part is a major issue.
• the liquid crystal polymer molded body that constitutes the parts of these mechanisms is required to have improved adhesiveness to adhesives such as epoxy resin.
• Patent Document 1 there is no description or suggestion of problems related to the improvement of adhesiveness with an adhesive. There was a problem that the sex was not enough.
• the present invention provides a liquid crystal polymer composition and a liquid crystal which is a molded product of the liquid crystal polymer composition, which can improve the adhesion between parts used therein. It was completed for the purpose of providing a polymer molding.
• an object of the present invention is to solve such problems, and it is possible to obtain a molded article having excellent adhesiveness to an adhesive such as an epoxy resin, and to improve the adhesiveness between parts made of the molded article, or to improve the adhesion from the molded article.
• An object of the present invention is to provide a liquid crystal polymer composition and a liquid crystal polymer molded product which is a molded product of the liquid crystal polymer composition, which is capable of improving adhesion between a part and other parts.
• the present inventors have found that a liquid crystal polymer (A), an epoxy compound (B) having less than 3 epoxy groups in the molecule, and barium sulfate (C)
• a liquid crystal polymer composition obtained by blending (1) and (2) can obtain an excellent effect in terms of adhesion to an adhesive agent such as an epoxy resin when formed into a molded article, and have completed the present invention. That is, the gist of the present invention is as follows.
• Item 1 A liquid crystal polymer composition characterized by blending a liquid crystal polymer (A), an epoxy compound (B) having less than 3 epoxy groups in the molecule, and barium sulfate (C) .
• Item 2 The liquid crystal polymer composition according to Item 1, wherein the epoxy compound (B) is a biphenyl-type epoxy monomer represented by the following general formula (I).
• n and m each represent an arbitrary integer selected from 0 to 2 (except when both n and m are 0).
• R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms and may have a substituent; R 1 and R 2 may be the same or different; good.
• a and b each represent an arbitrary integer selected from 0 to 2;
• the phenyl structures on the left and right sides of the biphenyl skeleton may be the same or different.
• Item 3 The liquid crystal polymer composition according to item 1 or 2, wherein in the general formula (I), n and m are each 1, and R 1 and R 2 each represent a methyl group.
• Item 4 Items 1 to 3, characterized in that the content of the epoxy compound (B) is 0.1% by mass to 5.0% by mass in the total amount of 100% by mass of the liquid crystal polymer composition.
• Item 5 The liquid crystal polymer composition according to any one of Items 1 to 4, wherein the liquid crystal polymer (A) is a wholly aromatic liquid crystal polymer.
• Item 6 The liquid crystal polymer composition according to any one of Items 1 to 5, further comprising a reinforcing material (D).
• Item 7 The liquid crystal polymer composition according to Item 6, wherein the reinforcing material (D) is treated with a hydrophobic surface treatment agent.
• Item 8 The liquid crystal polymer composition according to Item 7, wherein the hydrophobic surface treating agent is an alkoxysilane represented by the following general formula (II).
• n represents an arbitrary integer selected from 1 to 3
• R 1 represents an alkyl group, alkenyl group or aryl group
• R 2 represents an alkyl group.
• Item 9 The liquid crystal polymer composition according to any one of Items 6 to 8, wherein the reinforcing material (D) has an average fiber length of 1 ⁇ m to less than 300 ⁇ m.
• Item 10 The liquid crystal polymer composition according to any one of Items 6 to 9, wherein the reinforcing material (D) is at least one of potassium titanate fiber and wollastonite fiber.
• Item 11 Any one of Items 6 to 10, wherein the content of the reinforcing material (D) is 0.1% by mass to 40% by mass in the total amount of 100% by mass of the liquid crystal polymer composition. 1. The liquid crystal polymer composition according to item 1.
• Item 12 The liquid crystal polymer composition according to any one of Items 1 to 11, characterized by being used in a camera module.
• Item 13 A liquid crystal polymer molded article, characterized by being a molded article of the liquid crystal polymer composition according to any one of items 1 to 12.
• a molded article having excellent adhesion to an adhesive such as an epoxy resin, and the adhesion between parts made of the molded article, or the adhesion between parts made of the molded article and other parts. It is possible to provide a liquid crystal polymer composition and a liquid crystal polymer molded article that is a molded article of the liquid crystal polymer composition, which can improve the properties.
• the liquid crystal polymer composition of the present invention comprises a liquid crystal polymer (A), an epoxy compound (B) having less than 3 epoxy groups in the molecule, and barium sulfate (C).
• the liquid crystal polymer composition of the present invention may further contain reinforcing material (D), particulate carbon material (E), fluororesin (F), solid lubricant, and other additives as required. good too.
• the liquid crystal polymer composition of the present invention has the above structure, it is possible to obtain a molded article having excellent adhesion to an adhesive such as an epoxy resin, and the adhesion between parts made of the molded article, or the adhesion of the molded article to each other. It is possible to improve the adhesion between the part made of and other parts.
• the liquid crystal polymer composition of the present invention contains a liquid crystal polymer (A) (hereinafter sometimes referred to as "component (A)").
• the liquid crystal polymer (A) is a melt-processable polymer having properties capable of forming an optically anisotropic melt phase, and is not particularly limited as long as it is called a thermotropic liquid crystal polymer in the technical field.
• Optically anisotropic melt phases can be identified by conventional polarimetry using crossed polarizers.
• the liquid crystal polymer (A) has an elongated and flat molecular shape and a highly rigid molecular chain (referred to as a "mesogenic group") along the long molecular chain.
• the liquid crystal polymer (A) may have mesogenic groups in either or both of its main chain and side chains. It is preferable to have a mesogenic group in the molecular main chain.
• component (A) examples include liquid crystalline polyesters, liquid crystalline polyester amides, liquid crystalline polyester ethers, liquid crystalline polyester carbonates, liquid crystalline polyester imides, and liquid crystalline polyamides.
• liquid crystal polyesters, liquid crystal polyesteramides, and liquid crystal polyamides are preferred as the component (A) from the viewpoint of obtaining a liquid crystal polymer molded article having superior strength.
• the component (A) is preferably a liquid crystal polyester or a liquid crystal polyesteramide, more preferably a liquid crystal polyester.
• liquid crystal polymers (A1) to (A6) can be mentioned, preferably a wholly aromatic liquid crystal polymer using only an aromatic compound as a raw material monomer.
• a liquid crystal polymer selected from these may be used alone as component (A), or two or more of them may be used in combination as component (A).
• a liquid crystal polymer such as a liquid crystal polyester amide can be mentioned, and
• Ar 1 and Ar 4 each independently represent a 1,4-phenylene group, a 2,6-naphthalenediyl group or a 4,4-biphenylylene group
• Ar 2 , Ar 3 , Ar 5 and Ar 6 are Each independently represents a 1,4-phenylene group, a 2,6-naphthalenediyl group, a 1,3-phenylene group or a 4,4-biphenylylene group
• Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar Part or all of the hydrogen atoms on the aromatic ring of 5 and Ar 6 may be substituted with a halogen atom, an alkyl group, or an aryl group.
• the repeating unit represented by formula (1) is a repeating unit derived from an aromatic hydroxycarboxylic acid
• the aromatic hydroxycarboxylic acid include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy -2-naphthoic acid, 7-hydroxy-2-naphthoic acid, 6-hydroxy-1-naphthoic acid, 4-hydroxybiphenyl-4-carboxylic acid, or one of the hydrogens on the aromatic ring in these aromatic hydroxycarboxylic acids
• Aromatic hydroxycarboxylic acids partially or wholly substituted with an alkyl group, an aryl group, or a halogen atom can be mentioned.
• the repeating unit represented by formula (2) is a repeating unit derived from an aromatic dicarboxylic acid.
• aromatic dicarboxylic acid examples include terephthalic acid, phthalic acid, 4,4-diphenyldicarboxylic acid, 2,6 -Naphthalenedicarboxylic acid, isophthalic acid, or aromatic dicarboxylic acids in which some or all of the hydrogen atoms on the aromatic rings of these aromatic dicarboxylic acids are substituted with alkyl groups, aryl groups, or halogen atoms.
• the repeating unit represented by formula (3) is a repeating unit derived from an aromatic diol.
• the aromatic diol include hydroquinone, resorcinol, naphthalene-2,6-diol, 4,4-biphenylenediol, 3,3-biphenylenediol, 4,4-dihydroxydiphenyl ether, 4,4-dihydroxydiphenyl sulfone, or aromatic diols in which some or all of the hydrogen atoms on the aromatic ring are substituted with an alkyl group, an aryl group, or a halogen atom. and aromatic diols.
• the repeating unit represented by formula (4) is a repeating unit derived from an aromatic aminocarboxylic acid.
• aromatic aminocarboxylic acid examples include 4-aminobenzoic acid, 3-aminobenzoic acid, 6-amino -2-naphthoic acid, and aromatic aminocarboxylic acids in which some or all of the hydrogen atoms on the aromatic rings of these aromatic aminocarboxylic acids are substituted with alkyl groups, aryl groups, or halogen atoms.
• the repeating unit represented by formula (5) is a repeating unit derived from an aromatic amine having a hydroxy group, such as 4-aminophenol, 3-aminophenol, 4-amino-1-naphthol, 4-amino- Examples include 4-hydroxydiphenyl, and aromatic hydroxyamines in which some or all of the hydrogen atoms on the aromatic rings of these aromatic amines having hydroxy groups are substituted with alkyl groups, aryl groups, or halogen atoms.
• the repeating unit represented by formula (6) is a structural unit derived from an aromatic diamine, and is 1,4-phenylenediamine, 1,3-phenylenediamine, or hydrogen atoms on the aromatic rings of these aromatic diamines.
• Aromatic diamines partially or wholly substituted with an alkyl group, an aryl group, or a halogen atom can be mentioned.
• Alkyl groups exemplified as substituents in the above structural units include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, cyclohexyl, octyl, and decyl groups. , linear, branched or alicyclic alkyl groups having 1 to 10 carbon atoms.
• the aryl group includes aryl groups having 6 to 10 carbon atoms such as phenyl group and naphthyl group.
• Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
• At least one liquid crystalline polyester selected from the group consisting of (A1) to (A3) is preferable in terms of obtaining a liquid crystalline polymer molded article having excellent heat resistance and dimensional stability. Liquid crystalline polyesters A1) or (A3) are particularly preferred.
• the liquid crystal polymer (A) used in the present invention preferably has a melting point of 150°C or higher from the viewpoint of further suppressing deformation, discoloration, etc. and further increasing the heat resistance of the resulting molded product.
• the melting point is preferably 350° C. or lower, more preferably 330° C. or lower, in order to further suppress thermal decomposition of the liquid crystal polymer (A) during melt processing such as extrusion, molding, and spinning.
• the melting point can be measured according to JIS-K7121.
• a liquid crystal polymer having a melt viscosity of 1.0 ⁇ 10 3 mPa ⁇ s to 1.0 ⁇ 10 5 mPa ⁇ s measured at a temperature 20° C. to 40° C. higher than the melting point is preferred.
• a liquid crystal polymer having a deflection temperature under load of 260° C. or more is called type I
• a liquid crystal polymer having a deflection temperature under load of 210° C. or more and less than 260° C. is called type II, depending on the difference in heat distortion temperature.
• Type I liquid crystal polymers are measured at 30° C. above the melting point
• type II liquid crystal polymers are measured at 40° C. above the melting point.
• the melt viscosity can be obtained by measuring the viscosity when passing through an orifice with a diameter of 1 mm and a length of 10 mm at a shear rate of 1.0 ⁇ 10 3 sec ⁇ 1 using a capillary rheometer. .
• component (A) is not particularly limited as long as melt-kneading is possible, and for example, any of powder, granules, and pellets can be used.
• the content of component (A) in the liquid crystal polymer composition of the present invention is preferably 40% by mass to 98% by mass, more preferably 50% by mass to 94% by mass, based on the total amount of 100% by mass of the liquid crystal polymer composition. is more preferable, and 60% by mass to 90% by mass is even more preferable.
• Epoxy compound (B) having less than 3 epoxy groups in the molecule contains an epoxy compound (B) having less than 3 epoxy groups in the molecule (hereinafter sometimes referred to as "component (B)").
• the epoxy compound (B) having less than 3 epoxy groups in the molecule preferably contains 2 or less, more preferably 1 or 2, and still more preferably 2 epoxy functional groups in the same molecule.
• Epoxy compounds that The skeleton of the epoxy compound (B) is not particularly limited, but is preferably a biphenyl-type epoxy monomer represented by the following general formula (I).
• n and m each represent an arbitrary integer selected from 0 to 2 (except when both n and m are 0).
• R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms and may have a substituent; R 1 and R 2 may be the same or different; good.
• a and b each represent an arbitrary integer selected from 0 to 2;
• the phenyl structures on the left and right sides of the biphenyl skeleton may be the same or different.
• the mechanism by which the adhesiveness of the liquid crystal polymer molded body to an adhesive such as an epoxy resin is further enhanced is not clear, but it is possible to bond parts made of the liquid crystal polymer molded body via an adhesive such as an epoxy resin.
• the epoxy group or glycidyl group in the component (B) and the adhesive When bonding the same parts to each other or to other parts, by containing the component (B) in the liquid crystal polymer composition constituting the molded product, the epoxy group or glycidyl group in the component (B) and the adhesive The chemical reaction with the terminal groups (amide group, amino group, carboxyl group, aminocarboxyl group, etc.) of the curing agent contained in is promoted, and the adhesiveness between the molded parts and the adhesive is improved, and the equipment and parts This is thought to be due to the fact that it is possible to suppress the adhesion peeling of the parts at the time of collision or drop. It is preferable that the other parts have excellent adhesiveness with the epoxy adhesive.
• the types of hydrocarbon groups for R 1 and R 2 in the above general formula (I) of component (B) are determined by the glycidyl ether group of component (B) in the liquid crystal polymer composition of the present invention and the adhesive agent such as epoxy resin. From the standpoint of promoting the curing reaction of and further improving the adhesiveness between parts, when it has a substituent, it is preferably a methyl group (--CH 3 group) with little steric hindrance.
• the position of the glycidyl ether group of the above general formula (I) of component (B) is not particularly limited, but the position of the glycidyl ether group of component (B) in the liquid crystal polymer composition of the present invention and an adhesive such as an epoxy resin From the viewpoint of promoting the curing reaction and further improving the adhesion between parts, when two glycidyl ether groups are contained in the component (B), the chemical reaction within the molecule of the component (B) is further enhanced.
• glycidyl ether groups are 3,3′, 3,4′, 3,5′, 4,3′, 4,4′, 4,5′, 3,4′. , or preferably at the 5,4′ positions, more preferably at the 4,4′ positions.
• R 1 and R 2 are, for example, 2,2′-position, 2,6′-position or 6,2′-position, 2,3′-position or 3,2′-position when the glycidyl ether group is in 4,4′-position. 2,5′ or 5,2′, 6,6′, 6,3′ or 3,6′, 6,5′ or 5,6′, 3,3′, It may be provided at any one of the 3,5′ positions or the 5,3′ and 5,5′ positions. However, R 1 and R 2 are preferably provided at any one of 3,3′-position, 3,5′-position or 5,3′-position and 5,5′-position, and 3,3 It is particularly preferred to be provided at both the '-position and the 5,5'-position.
• Examples of the epoxy compound (B) having glycidyl ether groups at the 4,4' positions include biphenyl-type epoxy monomers represented by the following formula (III).
• both R 1 and R 2 are methyl groups. Also, R 1 and R 2 are provided at the 3,3′ and 5,5′ positions.
• the epoxy compound (B) is contained from the viewpoint of further lowering the coefficient of dynamic friction and/or the coefficient of static friction while enhancing the adhesiveness of the epoxy compound (B) having less than 3 epoxy groups in the molecule.
• the amount is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 0.8% by mass or more based on the total amount of 100% by mass of the liquid crystal polymer composition. It is more preferably 0.95% by mass or more, particularly preferably 1.2% by mass or more, and most preferably 1.2% by mass or more.
• the content of the epoxy compound (B) is , preferably 5.0% by mass or less, more preferably 4.5% by mass or less, and even more preferably 3.8% by mass or less with respect to 100% by mass of the total amount of the liquid crystal polymer composition , is particularly preferably 3.5% by mass or less, and most preferably 3.2% by mass or less.
• the epoxy equivalent of component (B) is preferably from 140 g/eq to 210 g/eq from the viewpoint of further improving adhesiveness while further suppressing deterioration in mechanical strength due to component (B). , more preferably 145 g/eq to 205 g/eq, and particularly preferably 150 g/eq to 200 g/eq.
• the melting point of component (B) is preferably 100°C or higher and preferably 200°C or lower.
• the method for producing component (B) is not particularly limited, and it can be produced using a conventionally known method.
• polyvalent hydroxybiphenyl containing less than 3 hydroxyl groups in the molecule is reacted with epihalohydrin to obtain the biphenyl-type epoxy of general formula (I).
• polyhydric hydroxybiphenyl as a raw material can be produced by carrying out a cross-coupling reaction.
• the selectivity of the cross-coupling reaction is not particularly limited. It is preferable from the viewpoint of production efficiency and purity.
• the method for producing the biphenyl-type epoxy monomer of general formula (I) by reacting polyvalent hydroxybiphenyl containing less than 3 hydroxyl groups in the molecule with epihalohydrin is not particularly limited as long as it is a conventionally known method. However, for example, a method of reacting highly pure polyvalent hydroxybiphenyl synthesized by a regioselective coupling reaction of a phenol derivative with epihalohydrin as described above may be used.
• the biphenyl-type epoxy monomer represented by the above general formula (I) may be added to a high-purity polyhydroxybiphenyl synthesized by a regioselective coupling reaction of a phenol derivative, to the extent that it does not impair the effects of the present invention.
• the polyhydric phenol obtained by the method may be used in combination and reacted with epihalohydrin to obtain a biphenyl-type epoxy monomer.
• component (B) a commercially available product may be used as the component (B).
• barium sulfate (C) The liquid crystal polymer composition of the present invention contains barium sulfate (C) (hereinafter sometimes referred to as "component (C)").
• component (C) include elutriated barium sulfate (barite powder) obtained by pulverizing a mineral called barite, deironizing, washing, and elutriating, and artificially synthesized precipitated barium sulfate.
• component (C) include elutriated barium sulfate (barite powder) obtained by pulverizing a mineral called barite, deironizing, washing, and elutriating, and artificially synthesized precipitated barium sulfate.
• the particle size can be controlled by the conditions during synthesis, and fine barium sulfate with a small content of coarse particles can be produced. From the viewpoint of further reducing impurities and making the particle size distribution more uniform, it is preferable to use precipitated barium
• Component (C) is preferably a powder, and its average particle size is preferably 0.1 ⁇ m to 50 ⁇ m, more preferably 0.1 ⁇ m to 30 ⁇ m, still more preferably 0.1 ⁇ m to 5 ⁇ m. , still more preferably 0.15 ⁇ m to 1.2 ⁇ m, particularly preferably 0.2 ⁇ m to 0.8 ⁇ m, most preferably 0.2 ⁇ m to 0.5 ⁇ m.
• the average particle size of component (C) can be measured by a laser diffraction/scattering method. More specifically, the average particle size of the component (C) is the particle size at 50% cumulative volume (volume-based cumulative 50% particle size) in the particle size distribution measured by a laser diffraction/scattering method, that is, D 50 ( median diameter).
• D 50 median diameter
• This volume-based cumulative 50% particle diameter (D 50 ) is obtained by determining the particle size distribution on a volume basis, counting the number of particles from the smallest particle size on the cumulative curve with the total volume as 100%, and the cumulative value is It is the particle diameter at the 50% point.
• the particle shape of component (C) is not particularly limited as long as it is non-fibrous particles such as spherical, columnar, plate-like, rod-like, columnar, block-like, and irregularly shaped particles, but is preferably spherical or irregularly shaped.
• the particle shape of component (C) can be analyzed, for example, by scanning electron microscope (SEM) observation.
• Component (C) may be surface-treated, and examples of treatment agents include coating agents, dispersants, and modifiers.
• the treatment agent includes fatty acids, waxes, nonionic surfactants, epoxy compounds, isocyanate compounds, silane compounds, titanate compounds, phosphorus compounds, aluminum salts such as alumina, and silicon dioxide. Titanium salts such as silicates and titanium dioxide are included. Although these may be used individually by 1 type, they can also be used in combination of 2 or more types.
• the content of component (C) in the liquid crystal polymer composition of the present invention is preferably 1% by mass to 30% by mass, more preferably 1% by mass to 20% by mass, in 100% by mass of the total amount of the liquid crystal polymer composition. more preferably 1% by mass to 15% by mass, most preferably 1.5% by mass to 2.5% by mass.
• the liquid crystal polymer composition of the present invention can contain a reinforcing material (D) (hereinafter sometimes referred to as “component (D)”), if necessary.
• Component (D) is a powdery reinforcing material composed of particles, and the particle shape is not particularly limited as long as it improves the strength and rigidity of the polymer composition.
• a fibrous reinforcing material (D1) that is a powder composed of fibrous particles (hereinafter sometimes referred to as “component (D1)"), or a powder composed of plate-like particles
• component (D2) hereinafter sometimes referred to as "component (D2)
• fibrous reinforcing materials (D1) and plate-like reinforcing materials (D2) are preferred.
• the particle shape of component (D) can be analyzed, for example, by scanning electron microscope (SEM) observation.
• a fibrous particle is defined as a rectangular parallelepiped having the smallest volume among the rectangular parallelepipeds circumscribing the particle (circumscribing rectangular parallelepiped), with the longest side having the major axis L, the next longest side having the minor axis B, and the shortest side having the thickness.
• T rectangular parallelepiped having the smallest volume among the rectangular parallelepipeds circumscribing rectangular parallelepiped
• both L/B and L/T are particles of 3 or more
• the major axis L corresponds to the fiber length
• the minor axis B corresponds to the fiber diameter.
• Plate-like particles refer to particles having an L/B of less than 3 and an L/T of 3 or more.
• the fibrous reinforcing material (D1) include carbon fiber, glass fiber, potassium titanate fiber, wollastonite fiber, aluminum borate, magnesium borate, xonotlite, zinc oxide, basic magnesium sulfate, alumina fiber, Inorganic fibers such as silicon carbide fibers and boron fibers; organic fibers such as aramid fibers and polyphenylenebenzoxazole (PBO) fibers; inorganic fibers are preferred.
• One of these fibrous reinforcing materials (D1) may be used alone, or two or more of them may be used in combination.
• the fibrous reinforcing material (D1) is preferably particles having a Mohs hardness of 2.5 or more and 5 or less.
• a Mohs hardness is an index that indicates the hardness of a substance, and a substance with a lower hardness is obtained when the minerals are rubbed against each other and damaged.
• the average fiber length of the fibrous reinforcing material (D1) is preferably 1 ⁇ m to 300 ⁇ m, more preferably 1 ⁇ m or more and less than 300 ⁇ m, still more preferably 1 ⁇ m to 200 ⁇ m, from the viewpoint of further reducing particle generation. Especially preferred is 3 ⁇ m to 100 ⁇ m, most preferred is 5 ⁇ m to 50 ⁇ m.
• the average aspect ratio of the fibrous reinforcing material (D1) is preferably 3-200, more preferably 3-100, still more preferably 3-50, and particularly preferably 3-40.
• the potassium titanate fiber conventionally known ones can be widely used, and examples thereof include potassium tetratitanate fiber, potassium hexatitanate fiber, potassium octatitanate fiber, and the like.
• the dimensions of the potassium titanate fibers are not particularly limited as long as they are within the above dimensions, but the average fiber length is preferably 1 ⁇ m to 50 ⁇ m, more preferably 3 ⁇ m to 30 ⁇ m, still more preferably 3 ⁇ m to 20 ⁇ m.
• the average fiber diameter of the potassium titanate fibers is preferably 0.01 ⁇ m to 1 ⁇ m, more preferably 0.05 ⁇ m to 0.8 ⁇ m, still more preferably 0.1 ⁇ m to 0.7 ⁇ m.
• the average aspect ratio of the potassium titanate fibers is preferably 10 or more, more preferably 10-100, still more preferably 15-35.
• These fibrous reinforcing materials (D1) can also be used as commercially available products. 15 ⁇ m, average fiber diameter 0.5 ⁇ m), etc. can be used.
• Wollastonite fiber is an inorganic fiber made of calcium metasilicate.
• the dimension of the wollastonite fiber is not particularly limited as long as it is within the dimension range of the fibrous reinforcing material (D1) described above. ⁇ 40 ⁇ m.
• the average fiber diameter of the wollastonite fibers is preferably 0.1 ⁇ m to 15 ⁇ m, more preferably 1 ⁇ m to 10 ⁇ m, still more preferably 2 ⁇ m to 7 ⁇ m.
• the average aspect ratio of the wollastonite fibers is preferably 3 or more, more preferably 3-30, and even more preferably 3-15.
• These fibrous reinforcing materials (D1) can also be used as commercially available products, for example, "Bistal W” (average fiber length: 25 ⁇ m, average fiber diameter: 3 ⁇ m) manufactured by Otsuka Chemical Co., Ltd. can be used.
• the above average fiber length and average fiber diameter can be measured by observation with a scanning electron microscope (SEM), and the average aspect ratio (average fiber length/average fiber diameter) is calculated from the average fiber length and average fiber diameter.
• SEM scanning electron microscope
• a plurality of fibrous reinforcing materials are photographed with a scanning electron microscope (SEM), 300 fibrous reinforcing materials are arbitrarily selected from the observed image, and their fiber lengths and fiber diameters are measured.
• An average fiber length can be obtained by accumulating all the fiber lengths and dividing by the number, and an average fiber diameter can be obtained by accumulating all the fiber diameters and dividing by the number.
• the plate-shaped reinforcing material (D2) include mica, mica, sericite, illite, talc, kaolinite, montmorillite, boehmite, smectite, vermiculite, titanium dioxide, potassium titanate, lithium potassium titanate, and magnesium titanate. Potassium, boehmite and the like can be mentioned.
• These plate-shaped reinforcing materials (D2) may be used alone or in combination of multiple types.
• the term "plate-like" includes not only the shape of a plate but also the shape of flakes, scales, and the like.
• the plate-shaped reinforcing material (D2) is preferably particles having a Mohs hardness of 1 or more and less than 2.5, and is more preferably talc.
• Talc is a hydrous magnesium silicate chemically, generally represented by the chemical formula 4SiO 2 .3MgO.2H 2 O, and is usually scaly particles having a layered structure. These talcs can also be used as commercial products.
• the average particle size of the plate-shaped reinforcing material (D2) is preferably 1 ⁇ m to 50 ⁇ m, more preferably 3 ⁇ m to 30 ⁇ m, still more preferably 3 ⁇ m to 25 ⁇ m, from the viewpoint of further reducing particle generation, Especially preferred is 5 ⁇ m to 25 ⁇ m.
• the average particle size of component (D2) can be measured by a laser diffraction/scattering method.
• the average particle size of the component (D2) is the particle size when the volume-based cumulative 50% in the particle size distribution measured by the laser diffraction/scattering method (volume-based cumulative 50% particle size), that is, D 50 (median diameter).
• This volume-based cumulative 50% particle diameter (D 50 ) is obtained by determining the particle size distribution on a volume basis, counting the number of particles from the smallest particle size on the cumulative curve with the total volume as 100%, and the cumulative value is It is the particle diameter at the 50% point.
• component (D) is preferably a reinforcing material at least part of the surface of which is covered with a treated layer composed of a hydrophobic surface treating agent.
• the treated layer preferably covers 50% or more, more preferably 80% or more, of the surface of the reinforcing material (D). However, it is particularly preferred that the treated layer covers the entire surface of the reinforcing material (D).
• component (D) is composed of a reinforcing material whose surface is at least partially covered with a treated layer composed of a hydrophobic surface treatment agent, and a hydrophobic surface treatment agent, as long as the preferred physical properties are not impaired. Mixtures with uncovered untreated reinforcements may also be used.
• hydrophobic surface treatment agents examples include silane coupling agents, titanium coupling agents, and aluminate coupling agents. Among these, silane coupling agents are preferred, and hydrophobic alkyl-based silane coupling agents are more preferred.
• Hydrophobic silane coupling agents include essentially hydrophobic functional groups such as alkyl groups and aryl groups, and hydrolyzable functional groups that generate groups capable of reacting with hydrophilic groups on the surface of the reinforcing material. Anything you have is fine.
• hydrophobic alkyl-based silane coupling agents include alkoxysilanes represented by the following general formula (II).
• n represents an arbitrary integer selected from 1 to 3
• R 1 represents an alkyl group, an alkenyl group or an aryl group, and these groups may have a substituent .
• R2 represents an alkyl group, these groups may have substituents, and when there are multiple R2s, they may be the same or different.
• Examples of the alkyl group represented by R 1 include alkyl groups such as heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group and icosyl group.
• the number of carbon atoms in the alkyl group is preferably 8 or more, more preferably 10 or more.
• the mechanical strength such as impact resistance of the obtained liquid crystal polymer molding can be further enhanced.
• the adhesiveness between parts made of the obtained liquid crystal polymer molded article or between parts made of the liquid crystal polymer molded article and other parts is further improved.
• the mechanism by which this is possible is not clear, it is thought to be due to the acceleration of the curing reaction with an adhesive such as an epoxy resin or the improvement in the elongation properties of the liquid crystal polymer molding itself.
• the upper limit of the number of carbon atoms in the alkyl group is not particularly limited, but can be, for example, 20 or less.
• alkyl groups may have a cyclic structure or a branched structure. Alkyl groups generally tend to have a higher degree of hydrophobicity as the number of straight-chain carbon atoms increases.
• the alkyl group may have 1 to 4 (preferably 1 to 3, more preferably 1) substituents described later at any position.
• alkenyl groups represented by R 1 include vinyl groups and butenyl groups. These may have a cyclic structure or a branched structure. In addition, the alkenyl group may have 1 to 4 (preferably 1 to 3, more preferably 1) substituents described later at any position.
• Examples of the aryl group represented by R 1 include a phenyl group and a naphthyl group.
• the aryl group may have 1 to 4 (preferably 1 to 3, more preferably 1) substituents described later at any position.
• Each group represented by R 1 may have a substituent as long as it does not interfere with its hydrophobicity.
• substituents include hydrophobic substituents such as fluorine atoms and (meth)acryloxy groups.
• alkyl group represented by R 1 may have the aryl group exemplified above as a hydrophobic substituent. Also, the aryl group represented by R 1 may have an alkyl group as a hydrophobic substituent.
• alkyl group represented by R2 examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and octadecyl. group, icosyl group, and the like.
• the alkoxy group (OR 2 ) in the alkoxysilane represented by the general formula ( II ) is a hydrolyzable group. is preferably a group, more preferably an ethyl group or a methyl group, and even more preferably a methyl group.
• n represents an arbitrary integer selected from 1 to 3. n is preferably 1 from the viewpoint of further increasing the reactivity with the reinforcing material particle surface and the hydrophobicity.
• alkoxysilanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane.
• hexadecyltrimethoxysilane, octadecyltrimethoxysilane, icosyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, octyltriethoxysilane, nonyltriethoxysilane, Ethoxysilane, decyltriethoxysilane, dodecyltriethoxysilane, hexadecyltriethoxysilane, octadecyltriethoxysilane, icosyltriethoxysilane, phenyltriethoxysilane and the like can be mentioned. These can also be used individually by 1 type, and can also be used in combination of 2 or more type.
• the degree of hydrophobicity of the surface treatment agent can be expressed by treating the glass plate surface with the surface treatment agent and measuring the surface free energy of the treated surface.
• the surface free energy is measured by uniformly applying a surface treatment agent diluted 10 times with methanol to a glass plate, heating at 85° C. for 1 hour, and then heat-treating at 110° C. for 1 hour to remove the surface treatment agent.
• the surface free energy of the coated surface can be obtained by measuring and calculating the two-liquid static contact angle between water and decane.
• decyltrimethoxysilane has a surface free energy of 28 mN/m
• ⁇ -glycidoxypropyltrimethoxysilane has a surface free energy of 55 mN/m
• 3-aminopropyltriethoxysilane has a surface free energy of 68 mN. /m.
• the surface treatment agent used in the present invention is not particularly limited. A surface free energy of 50 mN/m or less when uniformly treated is preferred. Although the lower limit of the surface free energy is not particularly limited, it is preferably 1 mN/m. Even if the surface treatment agent has a surface free energy of more than 50 mN/m, two or more of them may be mixed so that the surface free energy is 50 mN/m or less.
• the surface free energy of the surface treatment agent exceeds 50 mN/m, the surface free energy becomes higher than that of the liquid crystal polymer (A), and the metal ions eluted from the broken surface due to breakage of the reinforcing material (D) during kneading and molding. It may be uncontrollable, and hydrolysis of the liquid crystal polymer (A) may be accelerated. Therefore, it is preferable to fill the liquid crystal polymer (A) with a reinforcing material (D) prepared to have a surface free energy range of 50 mN/m or less.
• the oil absorption of the reinforcing material (D) after surface treatment is preferably 130 ml/100 g or less, more preferably 80 ml/100 g to 130 ml/100 g.
• the oil absorption of the reinforcing material (D) after surface treatment can be measured using the refined linseed oil method [JIS K5101-13-1].
• a dry method and a wet method are known as methods for previously treating the surface of the reinforcing material (D) with a coupling agent, and both methods are used. can do.
• the surface treatment concentration at that time is preferably 0.1% by mass to 3.0% by mass, more preferably 0.5% by mass to 1.5% by mass, relative to 100% by mass of the reinforcing material (D).
• a known surface treatment method can be used as a method for forming a treatment layer made of a surface treatment agent on the surface of component (D).
• a reinforcing material is placed in a device capable of high-speed stirring such as a Henschel mixer, and under stirring, a surface treatment agent (in the case of a liquid) or a solvent that promotes hydrolysis (such as water, alcohol, or these A dry method, etc., in which a solution in which a surface treatment agent is dissolved in a mixed solvent is sprayed onto the reinforcing material.
• the amount of the surface treatment agent when applying the surface treatment agent to the surface of the reinforcing material (D) used in the present invention is not particularly limited.
• the processing agent is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, still more preferably 0.5 to 5 parts by mass.
• the solution of the surface treatment agent may be sprayed in an amount of 3 parts by mass, particularly preferably 0.8 to 1.2 parts by mass.
• the adhesion with the component (A) can be further improved.
• the particle shape of the component (D) in the liquid crystal polymer composition of the present invention is not particularly limited. However, from the viewpoint of further reducing particle generation when used as a camera module member, the component (D) contains both the fibrous reinforcing material (D1) and the plate-like reinforcing material (D2).
• It preferably contains both a fibrous reinforcing material (D1) having a Mohs hardness of 2.5 or more and 5 or less and a plate-like reinforcing material (D2) having a Mohs hardness of 1 or more and less than 2.5 It is more preferable to be In this case, at least a portion of the surface of at least one of the fibrous reinforcing material (D1) and the plate-like reinforcing material (D2) may be covered with a treatment layer composed of a hydrophobic surface treatment agent.
• At least part of the surface of both the fibrous reinforcing material (D1) and the plate-like reinforcing material (D2) is preferably covered with a treatment layer composed of a hydrophobic surface treatment agent.
• the content of component (D) in the liquid crystal polymer composition of the present invention is preferably 0.1% by mass to 40% by mass, and 5% by mass to 35% by mass, based on the total amount of 100% by mass of the liquid crystal polymer composition. and more preferably 10% by mass to 30% by mass.
• component (D) By setting the content of component (D) in the range of 0.1% by mass to 40% by mass, it is possible to further suppress the generation of particles when used as a camera module member.
• the mass ratio of the plate-like reinforcing material (D2) to the fibrous reinforcing material (D1) is , preferably from 0 to 1, more preferably from 0.01 to 0.8, even more preferably from 0.1 to 0.7, particularly from 0.2 to 0.6 preferable.
• the liquid crystal polymer composition of the present invention can contain a particulate carbon material (E), if desired.
• the particulate carbon material (E) (hereinafter sometimes referred to as "component (E)") is not particularly limited, and is used, for example, for the purpose of ensuring light-shielding properties of liquid crystal polymer moldings such as parts for camera modules. A generally available one used for resin coloring can be preferably used.
• the particulate carbon material (E) for example, graphite; carbon blacks such as acetylene black, furnace black, lamp black, thermal black, channel black, roll black, disc black; carbon nanotubes; carbon fibrils; .
• the particulate carbon material (E) is preferably carbon black.
• One of these particulate carbon materials (E) may be used alone, or a plurality of them may be used in combination.
• the primary particle size of the particulate carbon material (E) is preferably 10 nm or more and 100 nm or less.
• the primary particle size of the particulate carbon material (E) is 10 nm or more and 100 nm or less
• the primary particle size of the particulate carbon material (E) is 10 nm or more and 100 nm or less
• the surface resistance value of the liquid crystal polymer molded article molded from the liquid crystal polymer composition of the present invention can be sufficiently lowered, the increase in charge amount in the liquid crystal polymer molded article can be further suppressed.
• the in-plane surface resistance value of the liquid crystal polymer molded article can be easily made uniform.
• the primary particle size of the particulate carbon material (E) is preferably 15 nm or more and 85 nm or less, more preferably 20 nm or more and 75 nm or less.
• the primary particle size of the particulate carbon material (E) an arithmetic mean particle size (number average), which is the average value of primary particle sizes measured with a transmission electron microscope, can be adopted.
• the DBP oil absorption of the particulate carbon material (E) is preferably 90 cm 3 /100 g or more and preferably 550 cm 3 /100 g or less.
• the liquid crystal polymer molded article molded from the liquid crystal polymer composition sufficiently conducts electricity at the connecting portions of the particulate carbon material (E). easier. As a result, the surface resistance value of the liquid crystal polymer molding can be further sufficiently lowered. Therefore, it is possible to more sufficiently suppress an increase in the amount of charge in the liquid crystal polymer molded article.
• the DBP oil absorption of the particulate carbon material (E) is too high, there are too many voids in the vicinity of the surface of the particulate carbon material (E), and the particulate carbon materials (E) are separated from each other in the liquid crystal polymer composition. Strong and easy to pull.
• the melt viscosity of the mixture may increase. As a result, it may become difficult to knead the mixture, making it difficult to produce the liquid crystal polymer composition.
• the DBP oil absorption of the particulate carbon material (E) is 550 cm 3 /100 g or less, the liquid crystal polymer (A), the reinforcing material (D), the particulate carbon material (E) and optional additives are melted. These mixtures should not become too viscous during kneading.
• the DBP oil absorption of the particulate carbon material (E) is preferably 90 cm 3 /100 g or more, more preferably 92 cm 3 /100 g or more, preferably 550 cm 3 /100 g or less, more preferably 525 cm 3 /100 g or less.
• a value measured according to JIS K 6221 by a dibutyl phthalate absorption meter can be adopted as the DBP oil absorption.
• the BET specific surface area of the particulate carbon material (E) is preferably 30 m 2 /g or more and 1500 m 2 /g or less, more preferably 40 m 2 /g or more and 1350 m 2 /g or less. It is preferably 45 m 2 /g or more and more preferably 1300 m 2 /g or less.
• the BET specific surface area adopts a value calculated by the BET method by using a BET specific surface area measuring instrument to adsorb nitrogen gas under liquid nitrogen temperature, measuring the amount of adsorption.
• a BET specific surface area measuring device for example, AccuSorb 2100E manufactured by Micromeritics can be used.
• the liquid crystal polymer molded article molded from the liquid crystal polymer composition of the present invention will conduct electricity at the connecting portions of the particulate carbon material (E). Easy enough to get through. As a result, the surface resistance value of the liquid crystal polymer molding can be further reduced. Therefore, it is possible to further suppress an increase in the amount of charge in the liquid crystal polymer molded article.
• the BET specific surface area of the particulate carbon material (E) is equal to or less than the above upper limit during the production of the liquid crystal polymer composition or the liquid crystal polymer molded article of the present invention, the liquid crystal polymer (A), the reinforcing material (D), the particulate When the carbon material (E) and optional additives are melt-kneaded, the melt viscosity of the mixture should not be too high. As a result, it becomes easier to knead the mixture, and it becomes even easier to produce the liquid crystal polymer composition of the present invention.
• the content of the component (E) in the liquid crystal polymer composition of the present invention is preferably in the range of 0.1% by mass to 5.0% by mass in 100% by mass of the total amount of the liquid crystal polymer composition, and 0.5% by mass. % to 4.5% by mass, more preferably 0.8% to 4.0% by mass. If the content of the component (E) is too low, the resulting liquid crystal polymer composition may be less jet-black, failing to ensure sufficient light-shielding properties.
• component (E) if the content of component (E) is too high, agglomerates (fine bumpy projections in which the particulate carbon material (E) aggregates in a resin composed of a molten liquid crystal polymer having a low viscosity during melt-kneading) ) drifts, making it difficult to apply shear during kneading, increasing the possibility of poor dispersion, and stress concentrates on aggregates, which become fracture starting points, resulting in a significant decrease in the mechanical strength of liquid crystal polymer moldings. It may become difficult to achieve the original purpose.
• agglomerates fine bumpy projections in which the particulate carbon material (E) aggregates in a resin composed of a molten liquid crystal polymer having a low viscosity during melt-kneading
• the content of the component (E) in the range of 0.1% by mass to 5.0% by mass By adjusting the content of the component (E) in the range of 0.1% by mass to 5.0% by mass, the dispersibility of the component (E) in the liquid crystal polymer composition is improved, and the resulting liquid crystal polymer molded article is obtained. It is possible to further improve mechanical strength, particularly impact resistance, while enhancing heat resistance and light shielding properties.
• the liquid crystal polymer composition of the present invention may optionally contain a fluororesin (F) (hereinafter sometimes referred to as "component (F)").
• Component (F) is a polymer having —(CF 2 —CF 2 )— repeating units, such as a perfluoroalkyl ether group —C p F 2p —O— (p is an integer of 1 to 4). can be used.
• Component (F) may be obtained by adopting either a suspension polymerization method for obtaining general molding powder or an emulsion polymerization method for obtaining fine powder.
• high-molecular-weight polytetrafluoroethylene resin may be reduced in molecular weight by thermal decomposition or radiation.
• Component (F) is preferably powder, and its average particle size is preferably 0.1 ⁇ m to 100 ⁇ m, more preferably 1 ⁇ m to 50 ⁇ m, still more preferably 5 ⁇ m to 20 ⁇ m. By setting the average particle size within the above range, the coefficient of friction during sliding can be further reduced.
• the average particle size of the component (F) can be measured by a laser diffraction/scattering method. diameter), or D 50 (median diameter). This volume-based cumulative 50% particle diameter (D 50 ) is obtained by determining the particle size distribution on a volume basis, counting the number of particles from the smallest particle size on the cumulative curve with the total volume as 100%, and the cumulative value is It is the particle diameter at the 50% point.
• the particle shape of component (F) is not particularly limited as long as it is a non-fibrous particle such as spherical, columnar, plate-like, rod-like, columnar, block-like, and irregular shape.
• the particle shape of component (F) can be analyzed, for example, by scanning electron microscope (SEM) observation.
• a fibrous particle is defined as a rectangular parallelepiped having the smallest volume among the rectangular parallelepipeds circumscribing the particle (circumscribing rectangular parallelepiped), with the longest side having the major axis L, the next longest side having the minor axis B, and the shortest side having the thickness.
• T both L/B and L/T are particles of 3 or more, and the major axis L corresponds to the fiber length, and the minor axis B corresponds to the fiber diameter.
• both L/B and L/T are preferably 5 or more.
• Non-fibrous particles refer to particles with an L/B of less than 3.
• particles having an L/B of less than 3 and an L/T of 3 or more are referred to as plate-like particles.
• Polytetrafluoroethylene resin (hereinafter sometimes referred to as "PTFE") is classified as a thermoplastic resin, but generally cannot be injection molded due to its extremely high melt viscosity.
• the resin composition which is the main component, is produced by a method (compression molding) in which mixed powder of resin is compressed and heated to a melting point or higher to fuse the powders together.
• High-molecular-weight PTFE is used for compression molding.
• high-molecular-weight PTFE is blended with a general thermoplastic resin and melt-mixed, the PTFE fibrillates and aggregates, resulting in fluidity of the resin composition. , and cannot be melt-blended or injection-molded.
• PTFE with a low molecular weight is used as a solid lubricant for thermoplastic resins for injection molding.
• Liquid crystal polymers are generally melt-mixed at a temperature around the melting point of PTFE and have a low viscosity when melted.
• the PTFE used for component (F) preferably has an MFR value of 5 g/10 min or more, measured under conditions of 372° C. and a load of 5 kg, preferably 10 g/10 min or more. and more preferably greater than 35 g/10 min.
• the MFR value of component (F) can be measured according to JIS K7210.
• PTFE may be sintered to suppress fibrillation and aggregation. Although it varies depending on the molecular weight, the melting point of the sintered product is 320° C. to 330° C., and the melting point of the unsintered product is 330° C. to 350° C. Therefore, the degree of sintering can be estimated from the melting points.
• Component (F) preferably has a melting point of less than 330°C, and a lower limit of 320°C, from the viewpoint of further suppressing aggregation during molding.
• the melting point of PTFE can be measured according to JIS-K7121.
• the content of component (F) in the liquid crystal polymer composition of the present invention is preferably 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 20% by mass, based on the total amount of 100% by mass of the liquid crystal polymer composition.
• Solid lubricant The liquid crystal polymer composition of the present invention can contain a solid lubricant as long as it does not impair its preferred physical properties.
• Solid lubricants include polyolefin resins such as low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, and ultra-high molecular weight polyethylene, silicone resins, graphite, molybdenum disulfide, tungsten disulfide, boron nitride, A polytetrafluoroethylene resin, which is a polymer having repeating units of -(CF 2 -CF 2 )-, a perfluoroalkyl ether group -C p F 2p -O- (p is an integer of 1 to 4), etc.
• the content of the solid lubricant in the liquid crystal polymer composition of the present invention is preferably 0.5% by mass to 20% by mass, and 1% by mass to 15% by mass, based on the total amount of 100% by mass of the liquid crystal polymer composition. is more preferable.
• the liquid crystal polymer composition of the present invention may contain other additives as long as they do not impair its preferred physical properties.
• Other additives include inorganic fillers (e.g., calcium carbonate, mica, mica, sericite, illite, kaolinite, montmorillonite, boehmite, smectite, vermiculite, palygorskite, pyrophyllite , hylosite , diatomaceous earth, titanium dioxide, etc.); laser direct structuring additives (e.g.
• UV absorbers e.g. resorcinols, salicylates, benzotriazoles, benzophenones, triazines, etc.
• light stabilizers e.g.
• hindered phenols, hindered amines, etc. weathering agents; 10 to 25), fatty acids, fatty acid metal salts, etc.); lubricants; fluidity improvers; plasticizers, polyalkylene glycol plasticizers, epoxy plasticizers); impact modifiers; flame retardants (e.g., phosphazene compounds, phosphoric acid esters, condensed retardants, metal oxide flame retardants, metal hydroxide flame retardants, organic metal salt flame retardants, nitrogen flame retardants, boron compound flame retardants, etc.); anti-dripping agents; nucleating agents; Vibration agents; neutralizing agents; anti-blocking agents and the like can be mentioned, and one or more of these can be contained.
• flame retardants e.g., phosphazene compounds, phosphoric acid esters, condensed retardants, metal oxide flame retardants, metal hydroxide flame retardants, organic metal salt flame retardants, nitrogen flame retardants, boron compound flame retardants, etc.
• the liquid crystal polymer composition of the present invention contains a heat stabilizer and/or a light stabilizer from the viewpoint that the adhesiveness to adhesives such as epoxy resins is much more excellent, and the generation of particles is further suppressed. It preferably contains at least one compound selected from the group consisting of hindered phenols, hindered amines and thioethers, and the group consisting of hindered phenols and hindered amines. It is more preferable to contain at least one compound selected from The above compound preferably has an amide group and/or an amino group from the viewpoint of obtaining a molded article having even better adhesion to an adhesive such as an epoxy resin.
• the amount thereof is not particularly limited as long as it does not impair the preferable physical properties of the liquid crystal polymer composition of the present invention. It is preferably 10% by mass or less, more preferably 5% by mass or less, based on 100% by mass of the total amount of the liquid crystal polymer composition.
• the liquid crystal polymer composition of the present invention comprises a liquid crystal polymer (A), an epoxy compound (B) having less than 3 epoxy groups in the molecule, and barium sulfate (C).
• a liquid crystal polymer A
• an epoxy compound B
• barium sulfate C
• Manufactured by heating and mixing (in particular, melt-kneading) a mixture containing reinforcing material (D), particulate carbon material (E), fluororesin (F), solid lubricant, and other additives. can.
• melt-kneading for example, a known melt-kneading device such as a twin-screw extruder can be used. Specifically, (1) a method of premixing each component with a mixer (tumbler, Henschel mixer, etc.), melt-kneading with a melt-kneading device, and pelletizing with a pelletizing means (pelletizer, etc.); (2) A method of preparing a masterbatch of desired components, mixing other components if necessary, melt-kneading them in a melt-kneading device, and pelletizing; (3) a method of supplying each component to a melt-kneading device and pelletizing; can be manufactured by
• the processing temperature in melt-kneading is not particularly limited as long as it is a temperature at which the liquid crystal polymer (A) can be melted. Normally, the cylinder temperature of the melt-kneading device used for melt-kneading is adjusted within this range. Thus, the liquid crystal polymer composition of the present invention that exhibits desired effects is produced.
• the liquid crystal polymer composition of the present invention is molded by a known resin molding method such as injection molding, insert molding, compression molding, blow molding, inflation molding, etc., depending on the type, application, shape, etc. of the desired liquid crystal polymer molded article. By doing so, a liquid crystal polymer molding can be obtained.
• the molding method is preferably injection molding or insert molding. Also, a molding method that combines the above molding methods can be employed.
• a liquid crystal polymer molded article obtained by molding the liquid crystal polymer composition of the present invention can improve adhesion between parts used in precision instruments and electronic parts.
• liquid crystal polymer molded article obtained by molding the liquid crystal polymer composition of the present invention is expected to have excellent mechanical strength and light shielding properties by appropriately adding the above-described components to the composition before molding. It is possible to suppress the particles generated when colliding or falling.
• a liquid crystal polymer molded article molded using the liquid crystal polymer composition of the present invention is suitably used as a member for manufacturing electronic parts of precision equipment.
• the component comprising the liquid crystal polymer molded body is selected from the group consisting of electronic components for sliding members that slide with other members, such as connectors, antennas, switches, relays, and camera modules. It is preferably used for manufacturing parts.
• the liquid crystal polymer molded article of the present invention can be expected to prevent deterioration of optical properties caused by fibrillation of the surface of the liquid crystal polymer molded article.
• the optical electronic parts that make up the camera module include the lens barrel (the part where the lens is placed), spacer, mount holder (the part where the barrel is attached and fixed to the board), base, lens barrel, and CMOS (image sensor). Frames, shutters, shutter plates, shutter bobbies, diaphragm rings, stoppers (parts that hold down the lens), and the like.
• the liquid crystal polymer molded article of the present invention can be used in electrical and electronic equipment having a camera function.
• the liquid crystal polymer molded article of the present invention can be suitably used for smartphones or tablet terminals equipped with a camera function.
• Liquid crystal polymer (A) Liquid crystal polymer: wholly aromatic type I, melt viscosity 2.0 ⁇ 10 4 mPa ⁇ s (350° C.), melting point 320° C., trade name “UENO LCP A-6000” manufactured by Ueno Pharmaceutical Co., Ltd.
• Epoxy compound-1 triphenylmethane type, number of epoxy groups in the molecule: 3, manufactured by Nippon Kayaku Co., Ltd., trade name "EPPN-502H”
• Epoxy compound-2 naphthol cresol novolak type, number of epoxy groups in the molecule: 3, manufactured by Nippon Kayaku Co., Ltd., trade name "NC-7000L”
• barium sulfate (C) Precipitated barium sulfate: average particle size 0.28 ⁇ m, manufactured by Sakai Chemical Industry Co., Ltd., trade name “precipitated barium sulfate B-31”
• Carbon black Primary particle diameter 50 nm, BET specific surface area 50 m 2 /g, DBP oil absorption 175 cm 3 /100 g, manufactured by Mitsubishi Chemical Corporation, trade name "#3050B"
• melt viscosity of the liquid crystal polymer (A) was measured using a melt viscosity measuring device (manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name “Capilograph 1D”) at a temperature 30° C. higher than the melting point of the liquid crystal polymer (A) and shear rate 1. Measurement was performed using an orifice of 1.0 mm ⁇ 10 mm under the condition of 0 ⁇ 10 3 sec ⁇ 1 .
• the melting points of the liquid crystal polymer (A) and the epoxy compound (B) were measured according to JIS-K7121 using a differential calorimeter (manufactured by Hitachi High-Tech Science, trade name "DSC7000X"). Specifically, 10 mg of a sample was placed in an aluminum cell for measurement, heated from room temperature to 50° C. at a temperature elevation rate of 10° C./min under a nitrogen flow of 100 ml/min, and held at 50° C. for 5 minutes. The temperature was raised at a rate of temperature rise of 10°C/min and measured.
• Average particle size of barium sulfate (C) and plate-shaped reinforcing material (D2) The average particle size was measured with a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, trade name "SALD-2100").
• the average fiber length, average fiber diameter, and aspect ratio of the fibrous reinforcing material (D1) were obtained from arbitrary 1000 average values measured by observation with a scanning electron microscope (SEM).
• the primary particle size of carbon black was determined by the arithmetic mean particle size (number average), which is the average value of primary particle sizes measured by a transmission electron microscope (manufactured by JEOL Ltd., product number “JEM2010”).
• the DBP oil absorption was measured according to JIS K 6221 with a dibutyl phthalate absorption meter.
• the BET specific surface area was measured according to JIS K 6217.
• Synthesis example 2 A surface-treated talc was prepared in the same manner as in Synthesis Example 1, except that untreated wollastonite fibers were changed to untreated talc, and it was confirmed that the average particle size was the same as that of the untreated product.
• Examples 1 to 9 and Comparative Examples 1 to 4 The liquid crystal polymer composition was melt-kneaded using a twin-screw extruder at the compounding ratio shown in Table 1 to produce pellets.
• Table 1 the surface-treated products in Synthesis Example 1 and Synthesis Example 2 are described as surface-treated wollastonite fiber and surface-treated talc, respectively.
• those not surface-treated are described as untreated wollastonite fiber, untreated talc, and untreated potassium titanate fiber, respectively.
• the cylinder temperature of the twin-screw extruder was 340°C.
• the obtained pellets are molded into flat plate 1 (length 90 mm, width 50 mm, thickness 3 mm), flat plate 2 (length 126 mm, width 13 mm, thickness 1.6 mm), and JIS test pieces for measuring mechanical properties. , a flat plate 3 (length 110 mm, width 10 mm, thickness 4 mm) and a flat plate 4 (length 64 mm, width 13 mm, thickness 4 mm) to obtain evaluation samples (liquid crystal polymer moldings).
• the injection molding machine had a cylinder temperature of 340°C and a mold temperature of 130°C.
• tensile strength, tensile elongation The tensile strength and tensile elongation were measured using Autograph AG-5000 (manufactured by Shimadzu Corporation) in accordance with JIS K7162. Table 1 shows the results.
• Notched Izod (IZOD) impact value Notched Izod (IZOD) impact value was measured according to JIS K7110. Table 1 shows the results.
• molding shrinkage rate The longitudinal dimension of the JIS test piece for tensile test measurement was accurately measured using a micrometer, and the error rate with the mold dimension was taken as the molding shrinkage rate (%). That is, the molding shrinkage rate (%) was calculated according to formula (IV).
• Mold shrinkage rate (%) [(mold dimensions - molded product dimensions)/mold dimensions] x 100... formula (IV)
• the plate 2 was dried in a forced convection oven at 120° C. for 60 minutes. After drying, the test site was wiped with a solvent to thoroughly degrease. Apply an adhesive (manufactured by Ajinomoto Fine-Techno Co., Ltd., low elasticity fast curing type epoxy adhesive, product number “AE-740”) to the part 15 mm from the end of the test piece opposite to the gate (mold fixing surface), and fix the mold. The surfaces were overlapped by 15 mm and stuck together, fixed with a clip, and cured for 60 minutes in an oven preliminarily adjusted to 80°C. After curing, the adhesive protruding significantly from the adhesive surface was removed in advance with a cutter or the like.
• an adhesive manufactured by Ajinomoto Fine-Techno Co., Ltd., low elasticity fast curing type epoxy adhesive, product number “AE-740”
• the adhesive strength between the liquid crystal polymer molded body and the epoxy adhesive is improved when the liquid crystal polymer composition contains the epoxy compound (B), compared to the case where the epoxy compound is not contained. Understand. Further, it can be seen that the adhesive strength is in a relationship of increasing in proportion to the amount of the epoxy compound (B) added within the range of Examples 1 to 4.
• Example 1 when comparing Example 1 and Example 5, by using the reinforcing material (D) surface-treated with an alkyl-based alkoxysilane coupling agent having a hydrophobic alkyl group, there was no surface treatment. It can be seen that the adhesive strength between the liquid crystal polymer molding and the epoxy resin, the IZOD impact value, and the tensile elongation are further improved by comparison.

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  • 2022-06-16 WO PCT/JP2022/024120 patent/WO2023276699A1/ja active Application Filing
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