CN101305056A - Liquid crystalline resin composition for use in injection molding - Google Patents
Liquid crystalline resin composition for use in injection molding Download PDFInfo
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- CN101305056A CN101305056A CNA2006800372525A CN200680037252A CN101305056A CN 101305056 A CN101305056 A CN 101305056A CN A2006800372525 A CNA2006800372525 A CN A2006800372525A CN 200680037252 A CN200680037252 A CN 200680037252A CN 101305056 A CN101305056 A CN 101305056A
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- 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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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- 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
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
- C08L23/0884—Epoxide containing esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
Abstract
The present invention provides a liquid crystalline resin composition which retains mechanical properties inherent in a liquid crystalline resin (particularly, fluidability and elastic modulus) and also has improved surface impact strength. The liquid crystalline resin composition can be produced by melt-kneading a liquid crystalline resin (A) or a resin composition comprising the liquid crystalline resin (A) and a specific inorganic filler (C) together with a component (B), wherein the component (B) is an olefin copolymer (1B) composed of an a-olefin and an a,ss-unsaturated acid glycidyl ester or a styrene copolymer (2B) composed of a styrene and an a,ss-unsaturated acid glycidyl ester, and the component (1B) is used in an amount of 0.2 to 0.7% by weight in terms of the glycidyl ester component and the component (2B) is used in an amount of 0.1 to 1.1% by weight in terms of the glycidyl ester component, both relative to the amount of the liquid crystalline resin (A) or the resin composition.
Description
Technical field
The present invention relates to useful novel liquid crystalline resin composition for use in injection molding such as casing, automobile exterior panel with excellent surface impacts intensity as electric and electronic parts, mobile phone.
Background technology
The liquid crystal liquid crystal property resin of liquid crystalline polyester resin representative has excellent physical strength, thermotolerance, chemical resistant properties, electrical property etc. well owing to balanced, and is widely used as high performance engineering plastics.Yet, the molecular orientation when known liquid crystal liquid crystal property resin utilizes moulding and in Cha Erbei (charpy) test, show high impact, but the surface impacts intensity of drop impact etc. is low.
Up to now, motion the technology of various mixed olefins based copolymers with the surface impacts intensity of improvement liquid crystal liquid crystal property resin.
For example, a kind of liquid crystalline polyester resin composition is disclosed among the JP-A 8-12862, said composition is with respect to containing the ethene improved based copolymer that the grafting of unsaturated carboxylic acid or derivatives thereof is obtained that ethene and carbonatoms are olefin copolymer mixing 0.01～10% weight of the alpha-olefin more than 3, perhaps with respect to containing ethene, carbonatoms is that the multipolymer of alpha-olefin more than 3 and non-conjugated diene mixes the ethene improved based copolymer that the grafting of unsaturated carboxylic acid or derivatives thereof is obtained of 0.01～10% weight, to improve the surface impacts intensity of liquid crystalline polyester resin.
Equally, disclose among the JP-A 7-316402 and be mixed with, the liquid crystalline polyester resin composition of the olefin copolymer that the beta-unsaturated acid glycidyl ester forms by alpha-olefines and α.
But, above-mentioned composition all can not substantially improve the surface impacts intensity of liquid crystalline polyester resin, also add the reactive olefin based copolymer, and undermined original flowability that has of liquid crystalline polyester resin and Young's modulus, be difficult in thin-walled injection molding moulding product, use owing to excessive.
Summary of the invention
The invention provides mechanical-physical character, the particularly flowability and Young's modulus and the improved liquid crystalline resin composition of surface impacts intensity that keep the liquid crystal liquid crystal property resin to be had.
The inventor etc. further investigate repeatedly, found that: only in liquid crystal liquid crystal property resin (A), mixing as the specific olefin copolymer (1B) of B composition or specific styrene based copolymer (2B), the specific inorganic filler (C) that according to circumstances mixes specified quantitative, and carry out under the situation of melting mixing, can be met excellent surface impacts intensity and resin combination mobile, Young's modulus, thereby finish the present invention.
The present invention relates to liquid crystalline resin composition for use in injection molding, it is characterized in that: mixing element (B) is carried out melting mixing and is formed in liquid crystal liquid crystal property resin (A), mentioned component (B) is: contain alpha-olefin and α, the olefin copolymer of beta-unsaturated acid glycidyl ester (1B), its consumption is for to count 0.2～0.7% weight with respect to liquid crystal liquid crystal property resin (A) with the glycidyl ester composition; Or contain 40～98% weight styrene classes, 20～2% weight α, the styrene based copolymer of beta-unsaturated acid glycidyl ester, 0～40% other vinyl monomers of weight (2B), its consumption is for to count 0.1～1.1% weight with respect to liquid crystal liquid crystal property resin (A) with the glycidyl ester composition.
The present invention also provides liquid crystalline resin composition for use in injection molding, it is characterized in that: be to be selected from average fiber by 100 weight part liquid crystal liquid crystal property resins (A) and 1～100 weight part directly be below the 15 μ m and average fiber length is fibrous filler below the 100 μ m, maximum particle diameter is that the following and length-to-diameter ratio of 20 μ m is 3～8 tabular weighting agent, median size is that mixing element (B) is carried out melting mixing and formed in the resin combination that forms of one or more the inorganic filler (C) in the powder shape weighting agent of 0.2～2 μ m, mentioned component (B) is: contain alpha-olefin and α, the olefin copolymer of beta-unsaturated acid glycidyl ester (1B), its consumption is with respect to above-mentioned resin combination, counts 0.2～0.7% weight with the glycidyl ester composition; Or contain 40～98% weight styrene classes, 20～2% weight α, the styrene based copolymer of beta-unsaturated acid glycidyl ester, 0～40% other vinyl monomers of weight (2B), its consumption is with respect to above-mentioned resin combination, counts 0.1～1.1% weight with the glycidyl ester composition.
The present invention also provides: by the wall thickness that above-mentioned liquid crystalline resin composition injection moulding is obtained is injection moulding product and the casing by above-mentioned liquid crystalline resin composition injection moulding is obtained below the 2mm.
Detailed description of the invention
Liquid crystalline resin composition for use in injection molding of the present invention is compared with liquid crystalline resin composition in the past, the tremendous raising of surface impacts intensity, and rigidity, mobile excellent, the injection moulding product that therefore can provide the externally mounted part product etc. of mobile phone, digital camera etc. in various fields, to use.
Below, the constituent of the present composition is elaborated.The liquid crystal liquid crystal property resin (A) that uses among the present invention is the anisotropic nematic liquid crystal resin of display optical when being fusion, and in the present invention, it is indispensable key element having concurrently aspect thermotolerance and the workability.The anisotropic character of fusion can be confirmed by the polarized light detection checking method of habitual use crossed nicols light microscopic.Particularly, use the Leitz polarization microscope,, under nitrogen atmosphere, observe, thereby can confirm the fusion anisotropy with about 40 times multiplying power with the sample fusion that is placed on the hot worktable of Leitz.Even above-mentioned optically anisotropic polymkeric substance is the static liquid status of fusion when being inserted between the crossed nicols light microscopic, polarized light also can see through.
Liquid crystal liquid crystal property resin used in the present invention (A), be preferably the aromatic polyester that contains the aromatic hydroxycarboxylic acids group that forms by following general formula (1) more than at least 30% mole, also comprise other and contain the dicarboxylic acid group shown in the general formula (2) below 35% mole respectively and the aromatic polyester of the repeating unit that forms by the glycol shown in the general formula (3).
(3)-O-R-O-(0～35% mole)
Constitute use preferred for this invention liquid crystalline polyester main repeating unit (1) formula-Ar
1-forming by phenylene and/or naphthylidene, the polycondensation that forms the property compound by above-mentioned aromatic hydroxycarboxylic acids or its ester obtains.The example of above-mentioned aromatic hydroxy carboxylic acid compound has: aromatic hydroxycarboxylic acids or its ester formation property compounds such as 4-hydroxy-benzoic acid, 6-hydroxyl-2-naphthoic acid, 7-hydroxyl-2-naphthoic acid, 4-(4-hydroxyphenyl) phenylformic acid can be one or more mixtures.Particularly constitute the unit, preferably based on 4-hydroxy-benzoic acid group, also comprise the unit of a part of hydroxynaphthoic acid group as (1) formula.Particularly as the formation unit of the polyester that uses, when (2) described later formula constituted that the unit does not exist or be few, preferred especially (1) formula constituted the unit and contains above-mentioned two kinds of groups aspect formability.
Secondly, constitute use preferred for this invention polyester (A) (2) formula-Ar
2-be phenylene, naphthylidene, two phenylene, in the scope that keeps liquid crystal liquid crystal property, also can be aliphatic group.(3) formula-R-is phenylene, naphthylidene, biphenylene etc., also can be that carbonatoms is 2～8 aliphatic group.(2) formula and (3) formula constitute the unit by the dicarboxylic acid (HOOC-Ar as raw material
2-COOH) or its ester forms property compound and glycol (HO-R-OH) forms, carry out polycondensation and import by above-mentioned sour composition and diol component are formed the property compound with above-mentioned aromatic hydroxycarboxylic acids or its ester.Constitute the unitary dicarboxylic acid composition of (2) formula as being used for, for example have: terephthalic acid, 2,6-naphthalic acid, m-phthalic acid, 2,7-naphthalic acid, 4, known aromatic dicarboxylic acid such as 4 '-phenylbenzene carboxylic acid or its ester formation property compound.As being used for constituting the unitary glycol of (3) formula, for example have: quinhydrones, nuclear replace quinhydrones, 4,4 '-bis-phenol, 2, known aromatic diol or aliphatic diols such as 6-dihydroxy naphthlene, dihydroxyphenyl propane for example can use one or more to contain the glycol of ethylene glycol, cyclohexanedimethanol.
The liquid crystalline polyester of use preferred for this invention (A), wherein (1) formula constitutes that the unit is at least more than 30% mole, (2) formula and (3) formula unit be respectively below 35% mole, preferably (1) formula unit is more than 40% mole, (2) formula and (3) formula unit be respectively below 30% mole, and more preferably (1) formula unit is more than 50% mole, (2) formula and (3) formula unit be respectively below 25% mole.Still it should be noted that, liquid crystal liquid crystal property resin used in the present invention (A), above-mentioned except containing (1) formula unit and (2), (3) formula unit, can also when fusion, show to import comonomer composition in the scope of liquid crystal liquid crystal property, and can import in the scope that keeps liquid crystal liquid crystal property that various multi-functional esters such as tetramethylolmethane, trimellitic acid, trimesic acid, 4 hydroxyisophthalic acid form monomers or sulfoisophthalic acid sodium, ester that hydroxyethylbenzene sodium sulfonate etc. is had an ionic group forms the property monomer with ehter bond or amido linkage.Particularly preferred liquid crystalline polyester resin (A) is for the copolymerization aromatic polyester and the sour composition that further will comprise terephthalic acid, m-phthalic acid in addition that are formed by 4-hydroxy-benzoic acid, 6-hydroxyl-2-naphthoic acid and comprise quinhydrones, 4, the aromatic copolyesters that the rmc monomer copolymerization of the diol component of 4 '-bis-phenol, ethylene glycol obtains.
Liquid crystal liquid crystal property thermoplastic resin used in the present invention (A) can use direct polymerization method or ester-interchange method, is prepared by above-mentioned monomeric compound according to known method, but uses melt phase polycondensation or slurry polymerization process etc. usually.Above-claimed cpd class with ester formation energy can be directly used in polymerization, can also become this to have the derivative that ester forms energy by the precursor modification in the polymeric last stage.Can use various catalyzer when carrying out above-mentioned polymerization, the example of representational catalyzer has: the basic metal of dialkyl tin oxide, diaryltin oxide compound, titanium dioxide, titan-alkoxide silicates, titanium alcoholate class, carboxylic acid and alkaline-earth metal salt, BF
3Deng lewis acid etc.With monomeric gross weight is benchmark, and the usage quantity of catalyzer is generally about 0.001～1% weight, preferred especially about 0.01～0.2% weight.Utilize the polymkeric substance of above-mentioned polymerization process preparation, if necessary can be further in decompression or rare gas element heating carry out that solid polycondensation is incompatible seeks to increase molecular weight.The melt viscosity of the liquid crystal liquid crystal property resin (A) that uses among the present invention needn't limit especially, as long as can injection moulding, can be arbitrary melt viscosity.Usually can use the liquid crystal liquid crystal property resin of melt viscosity more than velocity of shear 1000 seconds-1 time is as 10MPa, below the 600MPa under the mold temperature.But the liquid crystal liquid crystal property resin that oneself viscosity is too high is because mobile non-constant is therefore not preferred.Still it should be noted that above-mentioned liquid crystal liquid crystal property resin (A) can be the mixture of two or more liquid crystal liquid crystal property resin.
Next, composition (B) among the present invention is described.
The olefin copolymer of composition among the present invention (1B), it is blended in the matrix liquid crystal liquid crystal property resin (A), and performance significantly improves the effect of surface impacts intensity.The olefin copolymer of mentioned component (1B) is meant by alpha-olefin and α, the multipolymer that the beta-unsaturated acid glycidyl ester forms.
The object lesson of the alpha-olefin of mentioned component (1B) has: ethene, propylene, butylene etc., wherein preferably use ethene.In addition, another constituent-α of composition (1B), beta-unsaturated acid glycidyl ester are the material shown in the following general formula (4).
(in the formula, R ' is hydrogen or low alkyl group.)
α, beta-unsaturated acid Racemic glycidol ester units for example has: glycidyl acrylate, glycidyl methacrylate, ethyl propylene acid glycidyl ester, glycidyl itoconate etc., special preferable methyl glycidyl acrylate.
The olefin copolymer that uses among the present invention (1B), except containing above-mentioned two kinds of compositions, in not undermining scope of the present invention, with respect to the above-mentioned two kinds of compositions of 100 weight parts, can contain one or more ethylene series unsaturated ester such as vinyl cyanide, acrylate, methacrylic ester, alpha-methyl styrene, maleic anhydride of 0～48 weight part as the third composition.
One of feature of the present invention is: the glycidyl ester component proportions of olefin copolymer in the composition (1B) is limited in the specified range.Promptly, total addition level less than 0.2% weight of glycidyl ester or when surpassing 0.7% weight, the effect of the surface impacts that can't improve intensity, so the olefin copolymer combined amount of composition (1B) is limited to 0.2～0.7% weight in the total addition level (% weight) of glycidyl ester.Most preferably be 0.2～0.6% weight.
In addition, the α in the olefin copolymer of composition (1B), when beta-unsaturated acid Racemic glycidol ester content was too low, in order to improve surface impacts intensity, essential heavy addition composition (1B) caused rigidity (Young's modulus) to descend.Therefore, the α in the olefin copolymer of composition (1B), beta-unsaturated acid Racemic glycidol ester content must be for more than 2% weight.
On the other hand, the α in the olefin copolymer of composition (1B), when beta-unsaturated acid Racemic glycidol ester content surpassed 13% weight, the effect of improving surface impacts intensity descended.
Therefore, the α in the olefin copolymer of composition (1B), beta-unsaturated acid Racemic glycidol ester content is 2～13% weight, and preferred alpha-olefin is 87～98% weight, α, and the beta-unsaturated acid glycidyl ester is the olefin copolymer of 13～2% part by weight.
For the total addition level that makes glycidyl ester in the composition is 0.2～0.7% weight, for example preferably with respect to 97.5～92% weight liquid crystal liquid crystal property resins (A), be 2.5～8% weight by 87～98% weight alpha-olefins, 13～2% weight α, the ratio of the olefin copolymer (1B) that the beta-unsaturated acid glycidyl ester forms.
As the olefin copolymer of composition of the present invention (1B), can use catalysts for radical polymerization, utilize common radical polymerization to make each composition monomer polymerization and easily be prepared.More specifically, usually in the presence of free radical generating agent, in the existence of 500～4000 air pressure, 100～300 ℃, appropriate solvent or chain-transfer agent or not, according to making alpha-olefin and α, the method for beta-unsaturated acid glycidyl ester copolymerization is prepared.Can also be according to alpha-olefin, α, beta-unsaturated acid glycidyl ester and free radical generating agent mix, and the method that makes it fusion-grafting copolymerization in forcing machine is prepared.
In addition, in order to give the mechanical-physical character of liquid crystalline resin composition for use in injection molding of the present invention with the moulding product, particularly intensity and rigidity, must be used in combination specific fibrous filler, tabular weighting agent, powder shape weighting agent, must be to containing 100 weight part liquid crystal liquid crystal property resins (A) and 1～100 weight part to be selected from average fiber directly be below the 15 μ m and average fiber length being fibrous filler below the 100 μ m, maximum particle diameter is that the following and length-to-diameter ratio of 20 μ m is 3～8 tabular weighting agent, median size is to mix by alpha-olefin and α in one or more the resin combination of inorganic filler (C) in the powder shape weighting agent of 0.2～2 μ m, the olefin copolymer (1B) that the beta-unsaturated acid glycidyl ester forms carries out melting mixing, wherein, count 0.2～0.7% weight with the glycidyl ester composition with respect to above-mentioned resin combination.
Promptly, with respect to the resin combination that contains liquid crystal liquid crystal property resin (A) and inorganic filler (C), total addition level less than 0.2% weight of glycidyl ester or when surpassing 0.7% weight, the effect of the surface impacts that can't improve intensity, therefore the combined amount of the olefin copolymer of composition (1B) is with respect to the resin combination that contains liquid crystal liquid crystal property resin (A) and inorganic filler (C), total addition level (% weight) with glycidyl ester is counted 0.2～0.7% weight, is preferably 0.2～0.6% weight.
Reason according to above-mentioned record, with respect to the resin combination that contains liquid crystal liquid crystal property resin (A) and inorganic filler (C), preferably with the mixed of 2.5～8% weight by 87～98% weight alpha-olefins, 13～2% weight α, the olefin copolymer (1B) that the beta-unsaturated acid glycidyl ester forms.
As mentioned above, by alpha-olefin and α, the olefin copolymer (1B) that the beta-unsaturated acid glycidyl ester forms certainly contains the third composition.
Secondly, the styrene based copolymer of composition among the present invention (2B), it is blended in the matrix liquid crystal liquid crystal property resin (A), and performance significantly improves the effect of surface impacts intensity.The styrene based copolymer of mentioned component (2B) is by 40～98% weight styrene classes and 20～2% weight α, and the beta-unsaturated acid glycidyl ester forms.
Styrenic as the constituent of mentioned component (2B) for example has: vinylbenzene, alpha-methyl styrene, brominated styrene, Vinylstyrene etc., preferably use vinylbenzene.
In addition, as the α of the constituent of mentioned component (2B), the beta-unsaturated acid glycidyl ester is the material shown in the following general formula (4).
(in the formula, R ' is hydrogen or low alkyl group.)
α, the unitary example of beta-unsaturated acid glycidyl ester has: glycidyl acrylate, glycidyl methacrylate, ethyl propylene acid glycidyl ester, glycidyl itoconate etc., special preferable methyl glycidyl acrylate.
The styrene based copolymer that uses among the present invention (2B) can be except above-mentioned two kinds of compositions, the multiple copolymer that uses more than one other vinyl monomers to carry out copolymerization as the third composition.The third composition is preferably ethylene series unsaturated ester such as one or more vinyl cyanide, acrylate, methacrylic ester, maleic anhydride, is improving the multiple copolymer that has preferably imported the above-mentioned ethylene series unsaturated ester below 40% weight aspect the surface impacts intensity.
One of feature of the present invention is: the glycidyl ester component proportions of styrene based copolymer in the composition (2B) is limited in the specified range.Promptly, total addition level less than 0.1% weight of glycidyl ester or when surpassing 1.1% weight, the effect of the surface impacts that can't improve intensity, so the styrene based copolymer combined amount of composition (2B) is limited to 0.1～1.1% weight in the total addition level (% weight) of glycidyl ester.Be preferably 0.2～1.1% weight.0.2～0.8% weight more preferably.
In addition, the α in the styrene based copolymer of composition (2B), when beta-unsaturated acid Racemic glycidol ester content was too low, in order to obtain desired result, essential heavy addition composition (2B) was though Young's modulus improves the surface impacts strength degradation.Therefore, the α in the styrene based copolymer of composition (2B), beta-unsaturated acid Racemic glycidol ester content must be for more than 2% weight.
On the other hand, the α in the styrene based copolymer of composition (2B), when beta-unsaturated acid Racemic glycidol ester content surpassed 20% weight, the effect of improving surface impacts intensity descended.
Therefore, α in the styrene based copolymer of composition (2B), beta-unsaturated acid Racemic glycidol ester content is 2～20% weight, and the optimization styrene class is 80～98% weight, α, and the beta-unsaturated acid glycidyl ester is the styrene based copolymer of 20～2% part by weight.
For the total addition level that makes glycidyl ester in the composition is 0.1～1.1% weight, for example with respect to 98～85% weight liquid crystal liquid crystal property resins (A), be preferably 2～15% weight by 80～98% weight styrene classes, 20～2% weight α, the ratio of the styrene based copolymer (2B) that the beta-unsaturated acid glycidyl ester forms, more preferably 4～15% weight, preferred especially 4～9% weight.
As the styrene based copolymer of composition of the present invention (2B), can use catalysts for radical polymerization, utilize common radical polymerization to make each composition monomer copolymerization and easily be prepared.More specifically, usually can be in the presence of free radical generating agent, in the existence of 500～4000 air pressure, 100～300 ℃, appropriate solvent or chain-transfer agent or not, according to making styrenic and α, the method for beta-unsaturated acid glycidyl ester copolymerization is prepared.Can also be according to styrenic, α, beta-unsaturated acid glycidyl ester and free radical generating agent mix, and the method that makes it fusion-grafting copolymerization in forcing machine is prepared.
In addition, in order to give mechanical-physical character, particularly intensity and the rigidity of liquid crystalline resin composition for use in injection molding of the present invention, must be used in combination specific fibrous filler, tabular weighting agent, powder shape weighting agent with the moulding product.Must be to containing 100 weight part liquid crystal liquid crystal property resins (A) and 1～100 weight part to be selected from average fiber directly be below the 15 μ m and average fiber length being fibrous filler below the 100 μ m, maximum particle diameter is that the following and length-to-diameter ratio of 20 μ m is 3～8 tabular weighting agent, median size is to mix by 40～98% weight styrene classes in one or more the resin combination of inorganic filler (C) in the powder shape weighting agent of 0.2～2 μ m, 20～2% weight α, the beta-unsaturated acid glycidyl ester, the styrene based copolymer (2B) that other vinyl monomers of 0～40% weight form carries out melting mixing, wherein, count 0.1～1.1% weight with the glycidyl ester composition with respect to above-mentioned resin combination.
Promptly, with respect to the resin combination that contains liquid crystal liquid crystal property resin (A) and inorganic filler (C), total addition level less than 0.1% weight of glycidyl ester or when surpassing 1.1% weight, the effect of the surface impacts that can't improve intensity, therefore the combined amount of the styrene based copolymer of composition (2B) is with respect to the resin combination that contains liquid crystal liquid crystal property resin (A) and inorganic filler (C), total addition level (% weight) with glycidyl ester is counted 0.1～1.1% weight, be preferably 0.2～1.1% weight, more preferably 0.2～0.8% weight.
Reason according to above-mentioned record, preferably with respect to the resin combination that contains liquid crystal liquid crystal property resin (A) and inorganic filler (C), with 2～15% weight, more preferably the mixed of 4～15% weight, preferred especially 4～9% weight is by 80～98% weight styrene classes, 20～2% weight α, the styrene based copolymer (2B) that the beta-unsaturated acid glycidyl ester forms.
As mentioned above, by styrenic and α, the styrene based copolymer (2B) that the beta-unsaturated acid glycidyl ester forms certainly contains the third composition.
As fibrous filler, using average fiber directly is that 15 μ m are following, average fiber length is the following weighting agents of 100 μ m.The long weighting agent that surpasses 100 μ m of average fibers such as the glass fibre of chopped strand can reduce surface impacts intensity.The example of above-mentioned fibrous filler has: the inorganic fibre shape materials such as fibrous material of metals such as the pulverized fiber of glass or carbon, fibrous magnesium silicate, silica fiber, silica alumina fiber, Zirconium oxide fibre, boron nitride fibre, silicon nitride fiber, boron fibre, potassium titanate fiber and stainless steel, aluminium, titanium, copper, brass.The most preferred fibrous filler that uses among the present invention is that average fiber directly is that 0.2～0.7 μ m, average fiber length are the weighting agent of 10～30 μ m.
Tabular weighting agent uses that maximum particle diameter is that 20 μ m are following, length-to-diameter ratio is 3～8 weighting agent.Maximum particle diameter surpasses 20 μ m, length-to-diameter ratio less than 3 or surpasses 8 tabular weighting agent and reduces surface impacts intensity sometimes.The example of above-mentioned tabular weighting agent has: mica, sheet glass, various tinsels etc.The most preferred tabular weighting agent that uses among the present invention is that median size is that 3～12 μ m, maximum particle diameter are that 8～15 μ m, length-to-diameter ratio are 3～8 weighting agent.
It is the weighting agent of 0.2～2 μ m that powder shape weighting agent uses median size.Median size less than 0.2 μ m or the weighting agent that surpasses 2 μ m reduce surface impacts intensity sometimes.The example of above-mentioned powder shape weighting agent has: silicate such as carbon black, silicon-dioxide, quartz powder, granulated glass sphere, glass powder, Calucium Silicate powder, pure aluminium silicate, kaolin, talcum powder, clay, diatomite, wollastonite; Metal oxides such as ferric oxide, titanium oxide, zinc oxide, aluminum oxide; Metal carbonate such as lime carbonate, magnesiumcarbonate; Metal sulfate such as calcium sulfate, barium sulfate; Other silicon carbide, silicon nitride, boron nitride, various metal-powders etc.The most preferred powder shape weighting agent that uses among the present invention is that median size is the weighting agent of 0.2～1 μ m.
Above-mentioned inorganic filler can use a kind of or be used in combination two or more.At aspects such as physical strength that has the moulding product concurrently and dimensional precisioies, preferably fibrous filler and tabular weighting agent or powder shape weighting agent are used in combination, particularly effective to improving Young's modulus.
Combined amount to inorganic filler (C) is not particularly limited, and wishes with respect to 100 weight part liquid crystal liquid crystal property resins (A) to be 1～100 weight part.
In the liquid crystalline resin composition of the present invention, performance can also suitably be added the known material that is added in the common synthetic resins, i.e. tinting materials such as stablizer such as oxidation inhibitor or UV light absorber, static inhibitor, fire retardant, dyestuff or pigment, lubricant, releasing agent and crystallization promoter, nucleus agent etc. as requested.
Being prepared as follows of the present composition: add and mix mentioned component (A), (B), (C), and carry out melting mixing and handle, according to circumstances also mix other required compositions and carry out melting mixing, supply with injection moulding then.The melting mixing of above-mentioned each composition is generally: use single screw rod or twin screw extruder to make bead for the time being, supply with injection moulding afterwards.
Liquid crystalline resin composition of the present invention is suitable for injection moulding product such as the casing, automobile exterior panel of electric and electronic parts, mobile phone.Shaping thin wall excellence particularly, therefore to wall thickness such as casing be below the 2mm injection moulding product effectively.
The accompanying drawing summary
Fig. 1 is that the top of using in the expression drop weight test is the figure of hemispheric tool.
Embodiment
Illustrate in greater detail the present invention by the following examples, but the present invention is not limited to this.Each composition that uses is as follows.
Preparation example 1 (synthesizing of full-aromatic polyester liquid crystalline resin (composition (A)))
Add 345 weight parts (73% mole) P-hydroxybenzoic acid, 175 weight parts (27% mole) 6-hydroxyl-2-naphthoic acid, 0.02 weight part potassium acetate, 350 weight part diacetyl oxides in the reactor of pipe to possessing stirrer and distillating, after fully carrying out the nitrogen displacement, be warming up to 150 ℃ under the normal pressure, begin to stir.Stirred 30 minutes down at 150 ℃, slowly heat up again, heat up in a steamer by-product acetic acid.When temperature reaches 300 ℃, reactor is slowly reduced pressure, under the pressure of 5Torr (being 665Pa), continue to stir 1 hour, when reaching target stirring moment of torsion, open the outlet orifice of reactor lower part, use nitrogen pressure resin formation tow shape, discharge.The tow of discharging is made microgranular by tablets press.
The fusing point of this full-aromatic polyester liquid crystalline resin is at 280 ℃, and the melt viscosity under 300 ℃ is 50.1Pas.
Olefin copolymer (1B) uses following substances.
(1B-1) Sumitomo Chemical (strain) system, Bondfast 2C[ethylene-methyl methacrylate glycidyl ester copolymer (containing 6% weight methacrylic acid glycidyl ester)]
(1B-2) Sumitomo Chemical (strain) system, Bondfast E[ethylene-methyl methacrylate glycidyl ester copolymer (containing 12% weight methacrylic acid glycidyl ester)]
(1B-3) ア ト Off イ Na ジ ヤ パ Application (strain) system, LOTADAR AX8840[ethylene-methyl methacrylate glycidyl ester copolymer (containing 8% weight methacrylic acid glycidyl ester)]
Inorganic filler (C) uses following substances.
(C-1) silicon-dioxide [ア De マ テ Star Network ス (strain) system, ア De マ Off ア イ Application silicon-dioxide SOC-2 (median size is 0.5 μ m)]
(C-2) talcum powder [loose village industry (strain) system, Network ラ ウ Application talcum powder PP (maximum particle diameter is 11 μ m, and average aspect ratio is 6)]
(C-3) potassium titanate fiber is [big
Chemistry (strain) system, テ イ ス モ N-102 (average fiber directly is 0.3～0.6 μ m, and average fiber length is 10～20 μ m)]
(C-4) long glass fiber goods [rising sun Off ア イ バ-グ ラ ス (strain) system, Ge Lasi synthetic fibre (Glasron) chopped strand CS03JA416 (average fiber directly is 10 μ m, and chopped strand is long to be 3mm)]
Embodiment 1-4, comparative example 1-6
Use twin screw extruder (the system TEX30 α of (strain) JSW type), under 300 ℃ of cylinder (cylinder) temperature, mentioned component (A), (1B), (C) are carried out melting mixing in ratio shown in table 1-1, the 1-2, obtain the resin combination bead, supply with injection moulding, estimate.As the falling weight impact test test film, use Off ア Na Star Network corporate system Roboshot α-100iA shaper, be the thick flat board of 0.7mm at the condition compacted under of 300 ℃ of cylinder temperatures, 80 ℃ of die temperatures.As ISO pliability test test film, use a day steel J75SSII-A shaper, under the condition of 300 ℃ of cylinder temperatures, 90 ℃ of die temperatures, carry out molded.
Still it should be noted that the measuring method that is used to estimate characteristic value is as follows.
[melt viscosity]
Use capillary type rheometer (the smart machine-processed キ ヤ ピ ロ グ ラ Off 1B of Japan, piston diameter is 10mm), under temperature T 1 (melting point resin+20 ℃), 1000 seconds-1 condition of velocity of shear, measure apparent melt viscosity according to ISO 11443.Use the orifice plate of internal diameter 1mm, long 20mm during mensuration.
[ISO flexural strength and Young's modulus]
Measure according to ISO 178.
[drift test]
Use オ リ エ Application テ Star Network system Tensilon UTA-50kN trier, the treadmill test sheet thick to 0.7mm carries out drift test.Use the hemispherical punching tool of top end diameter, test with 100mm/ minute trial speed as 16mm.
[drop weight test]
Placing top shown in Figure 1 at fixed treadmill test sheet central part is the tool of hemispherical (spherical diameter is 12mm), and the weight of any weight is fallen from arbitrary height, and whether the validation test sheet ruptures.
Calculate 50% energy-to-break according to following calculating formula.
Height of the fall is to change at interval with 1cm, obtains the height (50% fracture height) of 50% test film fracture.50% fracture height that utilization is obtained is calculated 50% energy-to-break by following formula.
50% energy-to-break (E/ (J))=(quality of hammer (kg)) * (universal gravity constant (9.80665m/s
2)) * (50% fracture height (m))
The result is shown in table 1-1,1-2.
Embodiment 2-1～2-8, comparative example 2-1～2-3
Except use mentioned component (A), following compositions (2B), mentioned component (C) in ratio shown in table 2-1, the 2-2, operation obtains the resin combination bead similarly to Example 1, and operation is estimated similarly to Example 1.The result is shown in table 2-1,2-2.
Styrene based copolymer (2B) uses following substances.
(2B-1) Japanese grease (strain) system, マ-プ Le-Off G1005S[vinylbenzene-glycidyl methacrylate copolymer (containing 4.3% weight methacrylic acid glycidyl ester)]
(2B-2) Japanese grease (strain) system, マ-プ Le-Off G1010S[vinylbenzene-glycidyl methacrylate copolymer (containing 8.4% weight methacrylic acid glycidyl ester)]
Table 1-1
Table 1-2
Table 2-2
Claims (12)
1. liquid crystalline resin composition for use in injection molding, it is characterized in that: said composition mixing element (B) in liquid crystal liquid crystal property resin (A) is carried out melting mixing and is formed, mentioned component (B) is: contain alpha-olefin and α, the olefin copolymer of beta-unsaturated acid glycidyl ester (1B), its consumption is with respect to liquid crystal liquid crystal property resin (A), counts 0.2～0.7% weight with the glycidyl ester composition; Or contain 40～98% weight styrene classes, 20～2% weight α, the styrene based copolymer of beta-unsaturated acid glycidyl ester, 0～40% other vinyl monomers of weight (2B), its consumption is with respect to liquid crystal liquid crystal property resin (A), counts 0.1～1.1% weight with the glycidyl ester composition.
2. the liquid crystalline resin composition for use in injection molding of claim 1, said composition contains: 97.5～92% weight liquid crystal liquid crystal property resins (A); With 2.5～8% weight by 87～98% weight alpha-olefins and 13～2% weight α, the olefin copolymer (1B) that the beta-unsaturated acid glycidyl ester forms.
3. the liquid crystalline resin composition for use in injection molding of claim 1, said composition contains: 98～85% weight liquid crystal liquid crystal property resins (A); With 2～15% weight by 40～98% weight styrene classes, 20～2% weight α, the styrene based copolymer (2B) that other vinyl monomers of beta-unsaturated acid glycidyl ester, 0～40% weight form.
4. liquid crystalline resin composition for use in injection molding, it is characterized in that: said composition is to be selected from average fiber by 100 weight part liquid crystal liquid crystal property resins (A) and 1～100 weight part directly be below the 15 μ m and average fiber length is fibrous filler below the 100 μ m, maximum particle diameter is that the following and length-to-diameter ratio of 20 μ m is 3～8 tabular weighting agent, median size is that mixing element (B) is carried out melting mixing and formed in the resin combination that forms of one or more the inorganic filler (C) in the powder shape weighting agent of 0.2～2 μ m, mentioned component (B) is: contain alpha-olefin and α, the olefin copolymer of beta-unsaturated acid glycidyl ester (1B), its consumption is with respect to above-mentioned resin combination, counts 0.2～0.7% weight with the glycidyl ester composition; Or contain 40～98% weight styrene classes, 20～2% weight α, the styrene based copolymer of beta-unsaturated acid glycidyl ester, 0～40% other vinyl monomers of weight (2B), its consumption is with respect to above-mentioned resin combination, counts 0.1～1.1% weight with the glycidyl ester composition.
5. the liquid crystalline resin composition for use in injection molding of claim 4, said composition contains: the resin combination that 97.5～92% weight are formed by 100 weight part liquid crystal liquid crystal property resins (A) and 1～100 weight part inorganic filler (C); With 2.5～2% weight by 87～98% weight alpha-olefins, 13～2% weight α, the olefin copolymer (1B) that the beta-unsaturated acid glycidyl ester forms.
6. the liquid crystalline resin composition for use in injection molding of claim 4, said composition contains: the resin combination that 98～85% weight are formed by 100 weight part liquid crystal liquid crystal property resins (A) and 1～100 weight part inorganic filler (C); With 2～15% weight by 40～98% weight styrene classes, 20～2% weight α, the styrene based copolymer (2B) that other vinyl monomers of beta-unsaturated acid glycidyl ester, 0～40% weight form.
7. each liquid crystalline resin composition for use in injection molding in the claim 1,2,4 and 5, wherein composition (1B) is by 87～98% weight ethene, 13～2% weight α, the vinyl copolymer that the Beta-methyl glycidyl acrylate forms.
8. each liquid crystalline resin composition for use in injection molding in the claim 1,3,4 and 6, wherein composition (2B) is by 80～98% weight styrene classes, 20～2% weight α, the styrene based copolymer that the Beta-methyl glycidyl acrylate forms.
9. each liquid crystalline resin composition for use in injection molding in the claim 1,2,4,5 and 7 is characterized in that: composition (1B) contains and is selected from vinyl cyanide, (methyl) acrylate, alpha-methyl styrene, the maleic anhydride one or more as the third composition.
10. each liquid crystalline resin composition for use in injection molding in the claim 1,3,4,6 and 8 is characterized in that: composition (2B) contains and is selected from vinyl cyanide, (methyl) acrylate, the maleic anhydride one or more as the third composition.
11. the injection moulding product, it is to be moulding product below the 2mm by the wall thickness that each liquid crystalline resin composition injection moulding in the claim 1～10 is obtained.
12. casing, it is by each liquid crystalline resin composition injection moulding in the claim 1～10 is obtained.
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| JP298996/2005 | 2005-10-13 | ||
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| JP2005314641 | 2005-10-28 | ||
| PCT/JP2006/320800 WO2007043701A1 (en) | 2005-10-13 | 2006-10-12 | Liquid crystalline resin composition for use in injection molding |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH07304936A (en) * | 1994-03-16 | 1995-11-21 | Sumitomo Chem Co Ltd | Liquid-crystalline polyester resin composition |
| JP3399120B2 (en) * | 1994-11-10 | 2003-04-21 | 住友化学工業株式会社 | Liquid crystal polyester resin composition |
| JP3170555B2 (en) * | 1995-07-05 | 2001-05-28 | ポリプラスチックス株式会社 | Injection molding |
| JP3326480B2 (en) * | 1996-03-19 | 2002-09-24 | 住友化学工業株式会社 | Container made of liquid crystal polyester resin composition |
| JPH10330602A (en) * | 1997-05-29 | 1998-12-15 | Sumitomo Chem Co Ltd | Liquid crystal polyester resin composition, injection molding product and film comprising the same |
| US20070190346A1 (en) * | 2004-03-10 | 2007-08-16 | Matsushita Electric Works, Ltd. | Metal-coated resin molded article and production method therefor |
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2006
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| Publication number | Publication date |
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| JP5107048B2 (en) | 2012-12-26 |
| WO2007043701A1 (en) | 2007-04-19 |
| JPWO2007043701A1 (en) | 2009-04-23 |
| CN101305056B (en) | 2011-09-14 |
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