Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
  • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
  • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
• • 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
  • C08K7/06—Elements
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
  • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

• the present invention relates to composites containing polyamide and continuous fibers.
• the polyamide is a composite containing a specific diamine unit having a branched chain and a dicarboxylic acid unit.
• thermosetting resins are commonly used as matrix resins for FRP, but thermosetting resins have a long molding cycle and are difficult to recycle and post-processing such as welding with other parts. be.
• thermoplastic resin as a matrix resin have been actively made.
• Patent Documents 1 and 2 polyamides are widely studied because of their excellent heat resistance and mechanical properties.
• Patent Document 3 discloses a prepreg using a polyamide as a matrix resin, and it is said that high bending strength and fluidity can be achieved because the crystallization speed of the polyamide from the molten state is within a specific range.
• Patent Document 4 discloses a unidirectional fiber reinforced tape with a polyamide as a matrix resin, and the initial crystallinity and relative viscosity of the polyamide are within a specific range, so that the physical properties and productivity of the base material are improved. is considered possible.
• an object of the present invention is to provide a composite that achieves both a short molding cycle and excellent heat resistance and mechanical properties.
• the present invention is as follows.
• a composite comprising a polyamide (A) and a continuous fiber (B),
• the polyamide (A) contains diamine units (X) and dicarboxylic acid units (Y),
• the diamine unit (X) contains 0.1 mol% or more and less than 36 mol% of the diamine unit (X1),
• the diamine unit (X1) has 6 to 10 carbon atoms, and when the carbon atom to which any one amino group is bonded is the 1st position, the carbon atom at the 2nd position has 2 carbon atoms or A structural unit derived from an aliphatic diamine to which 3 alkyl groups are bonded, Complex.
• the diamine unit (X) further includes a diamine unit (X2) which is a diamine unit other than the diamine unit (X1), and the diamine unit (X2) is a linear aliphatic diamine, the diamine unit A structural unit derived from at least one selected from the group consisting of branched aliphatic diamines other than the aliphatic diamines constituting (X1), alicyclic diamines, and aromatic diamines, above [1] to The complex according to any one of [4]. [6] The above [ 1] to the complex according to any one of [5].
• the diamine unit (X2) is 1,6-hexanediamine, 1,9-nonanediamine, 1,10-decanediamine, 2-methyl-1,5-pentanediamine, and 2-methyl-1,8 -
• the dicarboxylic acid unit (Y) contains a structural unit derived from at least one selected from the group consisting of aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids.
• the dicarboxylic acid unit (Y) contains a structural unit derived from at least one selected from the group consisting of terephthalic acid, cyclohexanedicarboxylic acid, and naphthalenedicarboxylic acid.
• the continuous fibers (B) are at least one selected from the group consisting of carbon fibers, glass fibers, aramid fibers, wholly aromatic polyester fibers, ceramic fibers, and metal fibers.
• the complex according to any one of [10].
• this embodiment an embodiment of the present invention (hereinafter sometimes referred to as "this embodiment") will be described based on an example.
• the embodiments shown below are examples for embodying the technical idea of the present invention, and the present invention is not limited to the following description.
• preferred forms of embodiments are indicated herein, and combinations of two or more of the individual preferred forms are also preferred forms.
• the lower and upper limits thereof can be selectively combined to form a preferred form.
• a numerical range is described as "XX to YY"
• unit means "a structural unit derived from”
• dicarboxylic acid unit means "to a dicarboxylic acid.
• a "structural unit derived from a diamine” means a “structural unit derived from a diamine”.
• the polyamide (A) used in the present invention contains diamine units (X) and dicarboxylic acid units (Y).
• the diamine unit (X) has 6 to 10 carbon atoms, and when the carbon atom to which any one amino group is bonded is the 1st position, the carbon atom at the 2nd position has 2 carbon atoms or It is characterized by containing a specific amount of a diamine unit (X1) derived from an aliphatic diamine to which three alkyl groups are bonded.
• a component such as a branched chain having a large excluded volume is contained in the polymer skeleton, the molecular chains become difficult to arrange regularly, so the crystallization rate of the polymer tends to be slow.
• the polyamide (A) contains a specific amount of a diamine component having an alkyl group having 2 or 3 carbon atoms such as an ethyl group or a propyl group as a branched chain, so that the crystallization rate is unexpectedly high. became.
• a polyamide has a bulky substituent such as a branched chain, it becomes difficult to take a crystal structure, and the melting point tends to be lowered.
• the above polyamide (A) has a relatively bulky substituent group having 2 or 3 carbon atoms such as an ethyl group or a propyl group as a branched chain, the melting point is less lowered, and excellent heat resistance is obtained. can be expressed.
• the glass transition temperature generally tends to be low when a component with high molecular mobility such as a branched chain is contained.
• the above-mentioned polyamide (A) unexpectedly shows little decrease in the glass transition temperature and can exhibit excellent heat resistance.
• one of the reasons why the above effect is obtained is that the number of carbon atoms in the branched chain, the position of the branched chain, and the amount of the branched chain in the diamine unit (X1) contained in the polyamide (A) are , is considered to have an effect on the improvement of the crystallization rate while maintaining excellent heat resistance.
• the detailed reason is unknown.
• the diamine unit (X) has 6 to 10 carbon atoms, and when the carbon atom to which any one of the amino groups is bonded is the 1st position, the carbon atom at the 2nd position has 2 or 3 carbon atoms. contains a diamine unit (X1) derived from an aliphatic diamine to which an alkyl group of is bonded.
• the diamine unit (X1) is assumed to be a linear aliphatic chain with the carbon atoms to which two amino groups are respectively bonded as the carbon atoms at both ends, and any one amino group is bonded to 1
• It is a structural unit derived from an aliphatic diamine having a structure in which one of the hydrogen atoms on the 2-position carbon atom adjacent to the 2-position carbon atom is substituted with an alkyl group having 2 or 3 carbon atoms.
• a structural unit derived from an aliphatic diamine having a structure in which one of the hydrogen atoms on the carbon atom at the 2-position is substituted with an alkyl group having 2 or 3 carbon atoms is also referred to as a "branched aliphatic diamine unit". If the number of carbon atoms in the alkyl group is 1 or 4 or more, the crystallization rate may not be improved and the heat resistance may be lowered.
• the branched aliphatic diamine unit forming the diamine unit (X1) preferably has 8 to 10 carbon atoms, more preferably 9 carbon atoms. If the number of carbon atoms is within the above range, the polymerization reaction between the dicarboxylic acid and the diamine proceeds favorably, and the physical properties of the polyamide (A) are likely to be improved.
• the alkyl group having 2 or 3 carbon atoms is preferably at least one selected from the group consisting of an ethyl group, a propyl group, and an isopropyl group, More preferably, it is at least one selected from the group consisting of ethyl and propyl groups.
• the branched aliphatic diamine that forms the diamine unit (X1) has a branched chain such as a methyl group (referred to as "another branched chain”) at a carbon other than the 2-position as long as the effect of the present invention is not impaired. may have The number of other branched chains is preferably one or less, and more preferably the diamine unit (X1) does not contain other branched chains.
• Examples of the diamine unit (X1) include 2-ethyl-1,4-butanediamine, 2-ethyl-1,5-pentanediamine, 2-ethyl-1,6-hexanediamine, 2-ethyl-1,7 -heptanediamine, 2-ethyl-1,8-octanediamine, 2-propyl-1,5-pentanediamine, 2-propyl-1,6-hexanediamine, 2-propyl-1,7-heptanediamine, and 2 ,4-diethyl-1,6-hexanediamine. Only one type of these structural units may be contained, or two or more types may be contained.
• the diamine unit (X1) is selected from the group consisting of 2-ethyl-1,7-heptanediamine and 2-propyl-1,6-hexanediamine from the viewpoint of anticipating an even better improvement in crystallization rate. It preferably contains a structural unit derived from at least one kind of
• the content of the diamine unit (X1) in the diamine unit (X) is 0.1 mol% or more and less than 36 mol%. If it is less than 0.1 mol %, it is difficult to improve the crystallization speed. If the content is 36 mol % or more, the heat resistance may be lowered. From the viewpoint of making the polyamide (A) excellent in balance between heat resistance and crystallization speed, the content of the diamine unit (X1) in the diamine unit (X) is preferably 0.5 mol% or more, more preferably 1 It is mol % or more, more preferably 3 mol % or more, and even more preferably 5 mol % or more.
• the content of the diamine unit (X1) in the diamine unit (X) is preferably 35 mol% or less, more preferably 30 mol% or less, even more preferably 25 mol% or less, and even more preferably 20 mol% or less.
• mol % or less more preferably 18 mol % or less, even more preferably 15 mol % or less, and even more preferably 10 mol % or less.
• the diamine unit (X1) is at least one selected from the group consisting of 2-ethyl-1,7-heptanediamine and 2-propyl-1,6-hexanediamine.
• An example of the content of each structural unit when the derived structural unit is included is as follows.
• the content of structural units derived from 2-ethyl-1,7-heptanediamine in the diamine unit (X) is preferably 0.5 mol % or more, more preferably 2 mol % or more.
• the content is preferably 20 mol % or less, preferably 16 mol % or less, more preferably 10 mol % or less, and more preferably 5 mol % or less.
• the content of structural units derived from 2-ethyl-1,7-heptanediamine in the diamine units (X) is preferably 0.5 mol % or more and 20 mol % or less.
• the content of structural units derived from 2-propyl-1,6-hexanediamine in the diamine unit (X) is preferably 0.1 mol% or more, more preferably 0.5 mol% or more. preferable.
• the content is preferably 5 mol % or less, more preferably 2 mol % or less. That is, the content of structural units derived from 2-propyl-1,6-hexanediamine in diamine units (X) is preferably 0.1 mol % or more and 5 mol % or less.
• Polyamide (A) contains diamine units (hereinafter also referred to as "diamine units (X2)") other than diamine units (X1) as diamine units (X).
• the diamine unit (X2) is preferably a structural unit derived from a diamine having 6 to 10 carbon atoms, more preferably derived from a diamine having 8 to 10 carbon atoms, from the viewpoint of good progress of the polymerization reaction between the dicarboxylic acid and the diamine. more preferably a structural unit derived from a diamine having 9 carbon atoms.
• the diamine unit (X2) is selected from the group consisting of linear aliphatic diamines, branched aliphatic diamines other than the aliphatic diamines constituting the diamine unit (X1), alicyclic diamines, and aromatic diamines. Structural units derived from at least one species are included.
• Linear aliphatic diamines such as ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8 - octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15- pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine.
• Examples of branched aliphatic diamines other than the aliphatic diamines constituting the diamine unit (X1) include 1,2-propanediamine, 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-Butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4- butanediamine, 2-methyl-1,3-propanediamine, 2-methyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1,5-pentanediamine, 3 -methyl-1,5-pentanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,4-dimethyl-1,6-hexanediamine , 3,3-dimethyl-1,6-hexanedia
• Alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine, norbornanedimethylamine, tricyclodecanedimethyldiamine, bis(4-amino-3-ethylcyclohexyl)methane, bis(4-amino-3-ethyl-5- methylcyclohexyl)methane.
• aromatic diamines examples include p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4' -diaminodiphenyl ether, 4,4'-methylenedi-2,6-diethylaniline. Only one type of structural unit derived from the diamine may be used, or two or more types thereof may be used.
• diamine units (X2) structural units derived from at least one selected from the group consisting of linear aliphatic diamines and branched aliphatic diamines having a methyl group are more preferred.
• the other diamine units (X2) are 1,6-hexanediamine, 1,9-nonanediamine, 1,10-decanediamine, 2-methyl-1, Structural units derived from at least one selected from the group consisting of 5-pentanediamine and 2-methyl-1,8-octanediamine are more preferred.
• dicarboxylic acid unit (Y) Any dicarboxylic acid unit can be included as the dicarboxylic acid unit (Y).
• the dicarboxylic acid unit (Y) can contain a structural unit derived from, for example, at least one selected from the group consisting of aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids.
• aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, dimethylmalonic acid, 2, 2-diethylsuccinic acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, trimethyladipic acid.
• aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, diphenic acid, 4,4′-biphenyldicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, 1, 2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8- Naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-furandicarboxylic acid, 2,4-furandicarboxylic acid, 2,5-furandicarboxylic acid
• alicyclic dicarboxylic acids examples include 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cycloheptanedicarboxylic acid, cyclooctanedicarboxylic acid, and cyclodecanedicarboxylic acid. mentioned. Only one kind of structural unit derived from the dicarboxylic acid may be contained, or two or more kinds thereof may be contained.
• the dicarboxylic acid unit (Y) may contain a structural unit derived from at least one selected from the group consisting of aromatic dicarboxylic acids and alicyclic dicarboxylic acids. More preferably, it contains a structural unit derived from at least one selected from the group consisting of terephthalic acid, cyclohexanedicarboxylic acid, and naphthalenedicarboxylic acid.
• the molar ratio [diamine unit (X)/dicarboxylic acid unit (Y)] of the diamine unit (X) and the dicarboxylic acid unit (Y) in the polyamide (A) is preferably 45/55 to 55/45.
• the molar ratio between the diamine units (X) and the dicarboxylic acid units (Y) can be adjusted according to the compounding ratio (molar ratio) between the raw material diamine and the raw material dicarboxylic acid.
• Total ratio of diamine units (X) and dicarboxylic acid units (Y) in polyamide (A) is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and even more preferably 95 mol% or more. , or even 100 mol %. Further, the total proportion of the diamine units (X) and the dicarboxylic acid units (Y) in the polyamide (A) may be 100 mol% or less, or 99.5 mol% or less.
• the total proportion of diamine units (X) and dicarboxylic acid units (Y) in polyamide (A) is preferably 70 mol % or more and 100 mol % or less.
• the polyamide (A) can have more excellent physical properties than desired.
• the polyamide (A) may further contain aminocarboxylic acid units in addition to the diamine units (X) and the dicarboxylic acid units (Y).
• aminocarboxylic acid units include structural units derived from lactams such as caprolactam and lauryllactam; aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid.
• the content of aminocarboxylic acid units in the polyamide (A) is 40 mol% or less with respect to the total 100 mol% of the diamine units (X) and the dicarboxylic acid units (Y) constituting the polyamide (A). Preferably, it is 20 mol % or less.
• the content of aminocarboxylic acid units in the polyamide (A) is preferably 0 to 40 mol% with respect to the total 100 mol% of the diamine units (X) and dicarboxylic acid units (Y) constituting the polyamide. .
• Polyvalent carboxylic acid unit Polyamide (A) is a range that does not impair the effects of the present invention, trimellitic acid, trimesic acid, pyromellitic acid, etc. Polyvalent carboxylic acid with a valence of 3 or more, a structural unit derived from, melt molding is possible can also contain
• the polyamide (A) may contain structural units derived from a terminal blocker (terminal blocker units).
• the content of the terminal blocker unit is preferably 1.0 mol % or more, more preferably 2.0 mol % or more, relative to 100 mol % of the diamine unit (X).
• the content of the terminal blocker unit is preferably 10 mol % or less, more preferably 5.0 mol % or less, relative to 100 mol % of the diamine unit (X). That is, the content of the terminal blocker unit is preferably 1.0 mol % or more and 10 mol % or less with respect to 100 mol % of the diamine unit (X).
• the content of the terminal blocker unit is within the above range, it is easy to obtain a polyamide (A) having desired excellent physical properties.
• the content of the terminal blocking agent unit can be set within the above desired range by appropriately adjusting the amount of the terminal blocking agent when charging the polymerization raw material. Considering volatilization of the monomer components during polymerization, the charging amount of the terminal blocker should be finely adjusted so that the desired amount of terminal blocker units are introduced into the resulting polyamide (A). is desirable.
• a method for determining the content of terminal blocker units in the polyamide (A) for example, as shown in JP-A-7-228690, the solution viscosity is measured, and the number average molecular weight is calculated.
• a monofunctional compound having reactivity with a terminal amino group or a terminal carboxyl group can be used as the terminal blocking agent.
• Specific examples include monocarboxylic acids, acid anhydrides, monoisocyanates, monoacid halides, monoesters, monoalcohols, and monoamines. From the viewpoint of reactivity and stability of the terminal to be blocked, monocarboxylic acid is preferable as the terminal blocking agent for the terminal amino group, and monoamine is preferable as the terminal blocking agent for the terminal carboxyl group. From the standpoint of ease of handling, etc., monocarboxylic acids are more preferable as terminal blocking agents.
• the monocarboxylic acid used as a terminal blocking agent is not particularly limited as long as it is reactive with amino groups, and examples thereof include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, and laurin.
• acids tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, aliphatic monocarboxylic acids such as isobutyric acid; alicyclic monocarboxylic acids such as cyclopentanecarboxylic acid and cyclohexanecarboxylic acid; benzoic acid, toluic acid, aromatic monocarboxylic acids such as ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid; and any mixture thereof.
• acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, and stearic acid are preferred in terms of reactivity, stability of blocked ends, and price.
• benzoic acid are preferred.
• the monoamine used as the terminal blocking agent is not particularly limited as long as it has reactivity with carboxyl groups. Examples include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, and stearyl. Aliphatic monoamines such as amine, dimethylamine, diethylamine, dipropylamine and dibutylamine; Alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; Aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine; is mentioned.
• the content of the polyamide (A) contained in the total amount of the composite excluding the continuous fiber (B) is preferably 80% by mass or more from the viewpoint of easily ensuring good heat resistance, mechanical properties, and moldability. It is more preferably 85% by mass or more, still more preferably 90% by mass or more, and may be 100% by mass. Moreover, the content of the polyamide (A) may be 100% by mass or less, but may be 99% by mass or less, or may be 95% by mass or less.
• the inherent viscosity of polyamide (A) is preferably 0.5 dl/g or more, more preferably 0.7 dl/g or more. Moreover, the inherent viscosity of the polyamide (A) is preferably 2.0 dl/g or less, more preferably 1.5 dl/g or less. That is, the melt viscosity of polyamide (A) is preferably 0.5 dl/g or more and 2.0 dl/g or less. When the inherent viscosity is within the above range, the polyamide (A) can have more excellent physical properties than desired.
• the inherent viscosity of the polyamide (A) can be determined by measuring the flowing time of a solution using concentrated sulfuric acid at a concentration of 0.2 g / dl and a temperature of 30 ° C. as a solvent, and more specifically described in the Examples. method.
• the melting point of the polyamide (A) is preferably 250°C or higher, more preferably 280°C or higher. When the melting point is within the above range, the polyamide (A) can have excellent heat resistance.
• the upper limit of the melting point of the polyamide (A) is not particularly limited, it is preferably 330° C. or less in consideration of moldability. That is, the melting point of the polyamide (A) is preferably 250°C or higher and 330°C or lower.
• the melting point of the polyamide (A) can be obtained as the peak temperature of the endothermic peak that appears when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimetry (DSC) device. It can be obtained by the method described.
• the glass transition temperature of the polyamide (A) is preferably 110°C or higher, more preferably 120°C or higher. When the glass transition temperature is within the above range, the polyamide (A) having excellent heat resistance can be obtained.
• the upper limit of the glass transition temperature of the polyamide (A) is not particularly limited, it is preferably 180° C. or less, more preferably 160° C. or less, more preferably 150° C. or less from the viewpoint of handleability and the like. good too. That is, the glass transition temperature of polyamide (A) is preferably 110°C or higher and 180°C or lower.
• the glass transition temperature of the polyamide (A) can be obtained as the temperature of the inflection point that appears when the temperature is raised at a rate of 20 ° C./min using a differential scanning calorimetry (DSC) device. It can be obtained by the method described in the example.
• DSC differential scanning calorimetry
• the difference between the melting point and the crystallization temperature of the polyamide (A) is preferably 20-40°C.
• the crystallization temperature of the polyamide (A) can be obtained as the peak temperature of the exothermic peak that appears when the temperature is lowered at a rate of 10 ° C./min using a differential scanning calorimetry (DSC) device. It can be obtained by the method described in .
• the crystallization rate of polyamide (A) is preferably 0.020° C. ⁇ 1 or higher, more preferably 0.040° C. ⁇ 1 or higher. When the crystallization rate is within the above range, the polyamide can have excellent productivity.
• Polyamide (A) can be produced using any known method for producing polyamides. For example, it can be produced by a method such as a melt polymerization method, a solid phase polymerization method, or a melt extrusion polymerization method using a dicarboxylic acid and a diamine as raw materials. Among these, the solid-phase polymerization method is preferable from the viewpoint of being able to better suppress thermal deterioration during polymerization.
• polyamide (A) for example, a diamine, a dicarboxylic acid, and, if necessary, a catalyst or a terminal blocking agent are added all at once to produce a nylon salt, and then heated and polymerized at a temperature of 200 to 250 ° C. It can be produced by preparing a prepolymer by heating and then solid-phase polymerizing it, or by polymerizing it using a melt extruder. When the final stage of polymerization is carried out by solid phase polymerization, it is preferably carried out under reduced pressure or under inert gas flow. Coloring and gelation can be effectively suppressed. When the final stage of polymerization is carried out using a melt extruder, the polymerization temperature is preferably 370° C. or less. Polymerization under such conditions yields a polyamide (A) with little degradation and little decomposition.
• Examples of catalysts that can be used when producing polyamide (A) include phosphoric acid, phosphorous acid, hypophosphorous acid, or salts or esters thereof.
• Examples of the above salts or esters include phosphoric acid, phosphorous acid, or hypophosphorous acid and potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, antimony, and the like.
• Salt with metal Ammonium salt of phosphoric acid, phosphorous acid or hypophosphite; Ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester of phosphoric acid, phosphorous acid or hypophosphorous acid , decyl ester, stearyl ester, phenyl ester, and the like.
• the amount of the catalyst used is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 1.0% by mass or less with respect to 100% by mass of the total mass of the raw materials. and more preferably 0.5% by mass or less. If the amount of the catalyst used is at least the above lower limit, the polymerization proceeds satisfactorily. If the amount of the catalyst used is less than the above upper limit, impurities derived from the catalyst are less likely to occur, for example, when the polyamide (A) or the polyamide composition containing it is made into a film, problems due to the above impurities can be prevented.
• Continuous fiber (B) examples include carbon fibers, glass fibers, silicon carbide fibers, alumina fibers, potassium titanate fibers, aluminum borate fibers, ceramic fibers, metals (e.g., gold, silver, copper , iron, nickel, titanium, stainless steel, etc.) fibers; organic fibers such as wholly aromatic polyester fiber, polyphenylene sulfide fiber, aramid fiber, polysulfonamide fiber, phenolic resin fiber, polyimide fiber, fluorine fiber, etc. be done. These may be used individually by 1 type, and may use 2 or more types together.
• it is preferably at least one selected from the group consisting of carbon fiber, glass fiber, aramid fiber, wholly aromatic polyester fiber, ceramic fiber, and metal fiber. More preferably, it is at least one selected from the group consisting of fibers and glass fibers.
• the continuous fibers (B) may be treated with a surface treatment agent or a sizing agent, if necessary.
• agents used when the continuous fiber (B) is glass fiber include silane coupling agents and titanate-based coupling agents.
• the silane coupling agent include, but are not limited to, ⁇ - Aminosilane coupling agents such as aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane; ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyl mercaptosilane-based coupling agents such as triethoxysilane; epoxysilane-based coupling agents; and vinylsilane-based coupling agents.
• the continuous fiber (B) is a carbon fiber
• a carboxylic anhydride-containing unsaturated vinyl monomer unit and an unsaturated vinyl monomer other than the carboxylic anhydride-containing unsaturated vinyl monomer are used.
• the surface treatment agent and the sizing agent may be used alone, or two or more thereof may be used in combination.
• the continuous fibers (B) may be those obtained by removing the plastic resin material after being compounded once with a plastic resin material that is generally used industrially, that is, the so-called recycled or reused one.
• the method for producing recycled or reused continuous fibers is not particularly limited, but for example, a method in which a composite product is placed in a firing furnace and fired at a temperature equal to or higher than the decomposition temperature of the plastic resin material to take out continuous fibers, or electrolysis in the above firing method. and a method of dissolving the plastic resin material using an acid and an alkaline solvent.
• the continuous fibers (B) used in the composite are continuous fibers having an average fiber length of 100 mm or more.
• the upper limit of the length of the continuous fibers (B) is not particularly limited as long as the effects of the present invention are not impaired.
• the average fiber diameter of the continuous fibers (B) is not particularly limited, it is preferably 3 to 50 ⁇ m from the viewpoint of handleability.
• the average fiber diameter and average fiber length of the continuous fibers (B) can be observed and measured, for example, with a scanning electron microscope.
• Forms of continuous fibers (B) include strands, sheets in which strands are aligned in one direction, and woven or knitted fabrics in which strands are crossed or woven (for example, non-crimp fabric (NCF)).
• NCF non-crimp fabric
• the number of filaments of the continuous fibers (B) is not particularly limited, it is preferably 100 to 350,000, more preferably 1,000 to 100,000, from the viewpoint of productivity.
• the tensile strength of the monofilaments constituting the continuous fibers (B) is preferably 2000-8000 MPa, more preferably 3000-6000 MPa.
• the composite of the present embodiment preferably has a fiber volume content (Vf) of continuous fibers (B) of 10 to 80% by volume, more preferably 20 to 70% by volume. . Further, the fiber volume content of the continuous fibers (B) may be 20 to 50% by volume, or may be 20 to 30% by volume. If the fiber volume content of the continuous fibers (B) is 10% by volume or more, the composite can ensure sufficient mechanical properties. When the fiber volume content of the continuous fibers (B) is 80% by volume or less, the continuous fibers (B) are sufficiently impregnated with the polyamide (A).
• the fiber volume content means the ratio of the volume of the continuous fibers (B) to the total volume of the composite.
• the total volume of the composite is a value calculated from the specific gravity and the amount (weight) of the materials constituting the composite.
• the volume of the continuous fibers (B) is calculated from the specific gravity and weight of the continuous fibers (B) contained in the composite.
• the composite of this embodiment may contain other additives in addition to the polyamide (A) and the continuous fiber (B) as long as they do not impair the effects of the present invention.
• Other additives include, for example, heat stabilizers, light stabilizers, elastomers, lubricants, plasticizers, nucleating agents, crystallization retarders, hydrolysis inhibitors, antistatic agents, radical inhibitors, matting agents, It may contain an ultraviolet absorber, a flame retardant, a chain extender, a heat absorber, a thermally conductive substance, an inorganic substance other than the continuous fiber (B), and the like.
• inorganic substances include carbon nanotubes, fullerene, talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, silica, bentonite, alumina silicate, silicon oxide, magnesium oxide, alumina, zirconium oxide, oxide Titanium, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black, graphite and the like.
• Lubricants include, for example, metal soap, montanic acid wax, polyolefin wax, fatty acid amide wax, rice wax and the like.
• Crystallization retarders include, for example, azine-based dyes such as nigrosine and derivatives thereof.
• chain extender include compounds having a functional group that reacts with the terminal amino group or carboxyl group of the polyamide, such as oxazoline, imidazoline, epoxy, isocyanate, maleimide and acid anhydride, such as 1,3-phenylenebisoxazoline. 1 type of these other additives may be contained, and 2 or more types may be contained.
• the content of the other additives is not particularly limited as long as it does not impair the effects of the present invention, but it can be 0.02 to 200 parts by mass with respect to 100 parts by mass of polyamide (A).
• a known method can be used as a method for adding the other additives. For example, a method of adding other additives during polymerization of polyamide (A), a method of dry blending other additives into polyamide (A) and melt kneading, and a method of combining polyamide (A) and continuous fiber (B). and a method of adding other additives to.
• a known method can be used as a method for producing the composite of the present embodiment.
• methods for producing a composite include a method of drawing continuous fibers (B) into molten polyamide (A) and impregnating the fiber bundle with a resin, and a resin film obtained from polyamide (A) and continuous fibers (B).
• the method for producing the composite of this embodiment is not limited to these.
• an additive such as a chain extender may be added during the production of the composite, and a treatment such as heat treatment or electron beam cross-linking may be performed after the production.
• the complex of this embodiment can be shaped into an industrially useful shape using a known method.
• a method of press molding in which the material is sandwiched between molds and heated and pressed, a method of injection molding other materials at the same time as press molding and overmolding, filament winding and sheet winding molding in which the material is wound around a cylindrical mold and then heated and pressurized. etc. can be applied.
• the composite of this embodiment can be effectively used in a wide range of fields such as general industrial materials, electrical/electronics, civil engineering/construction, transportation equipment, and leisure.
• fields such as general industrial materials, electrical/electronics, civil engineering/construction, transportation equipment, and leisure.
• transportation equipment such as aircraft, automobiles, railroads, ships, etc.
• it can be effectively used as a member constituting the main structure.
• the glass transition temperature (° C.) was measured according to ISO 11357-2 (2nd edition, 2013). Specifically, in a nitrogen atmosphere, the sample (polyamide) was heated from 30 ° C. to 340 ° C. at a rate of 20 ° C./min, held at 340 ° C. for 5 minutes to completely melt the sample, and then heated to 20 ° C. /min to 50°C and held at 50°C for 5 minutes. The temperature at the inflection point when the temperature was again raised to 200°C at a rate of 20°C/min was taken as the glass transition temperature (°C).
• Vf ⁇ Fiber volume content
• Example 1 ⁇ Preparation of Polyamide>> 5400 g of terephthalic acid, 5260 g of a mixture of 2-ethyl-1,7-heptanediamine, 2-propyl-1,6-hexanediamine and 2-methyl-1,8-octanediamine [4/1/95 (molar ratio)] , 121 g of benzoic acid, 10 g of sodium diphosphite monohydrate (0.1% by mass with respect to the total mass of the raw materials) and 4.8 liters of distilled water were placed in an autoclave having an internal volume of 40 liters and purged with nitrogen. After stirring at 150°C for 30 minutes, the temperature inside the autoclave was raised to 220°C over 2 hours.
• the pressure inside the autoclave increased to 2 MPa. Heating was continued for 5 hours while maintaining the pressure at 2 MPa, and water vapor was gradually removed to allow the reaction to proceed. Next, the pressure was lowered to 1.3 MPa over 30 minutes, and the reaction was continued for 1 hour to obtain a prepolymer.
• the resulting prepolymer was dried at 100° C. under reduced pressure for 12 hours and pulverized to a particle size of 2 mm or less. This was solid-phase polymerized at 230° C. and 13 Pa (0.1 mmHg) for 10 hours to obtain a polyamide.
• Example 2 A composite was obtained in the same manner as in Example 1, except that the fiber volume content (Vf) was 50% by volume.
• the diamine unit is a mixture of 2-ethyl-1,7-heptanediamine, 2-propyl-1,6-hexanediamine and 2-methyl-1,8-octanediamine [5.6/0.4/94 (molar ratio )] in the same manner as in Example 1, to obtain a polyamide and a composite.
• the diamine unit was a mixture of 2-ethyl-1,7-heptanediamine, 2-propyl-1,6-hexanediamine and 2-methyl-1,8-octanediamine [12/3/85 (molar ratio)]
• a polyamide and a composite were obtained in the same manner as in Example 1 except for the above.
• the diamine unit was a mixture of 2-ethyl-1,7-heptanediamine, 2-propyl-1,6-hexanediamine and 2-methyl-1,8-octanediamine [16/4/80 (molar ratio)]
• a polyamide and a composite were obtained in the same manner as in Example 1 except for the above.
• the diamine unit is a mixture of 2-ethyl-1,7-heptanediamine, 2-propyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine and 1,9-nonanediamine [4/1/20/ 75 (molar ratio)] in the same manner as in Example 1 to obtain a polyamide and a composite.
• the diamine unit is a mixture of 2-ethyl-1,7-heptanediamine, 2-methyl-1,8-octanediamine and 1,9-nonanediamine [0.5/14.5/85 (molar ratio)] Except for this, in the same manner as in Example 1, a polyamide and a composite were obtained.
• Example 1 A polyamide and a composite having a melting point of 285° C. were obtained in the same manner as in Example 1 except that 2-methyl-1,8-octanediamine was used as the diamine unit.
• Example 2 A polyamide and a composite were obtained in the same manner as in Example 1 except that the diamine unit was a mixture of 2-methyl-1,8-octanediamine and 1,9-nonanediamine [15/85 (molar ratio)]. .
• the dicarboxylic acid unit is 21.3 g of naphthalenedicarboxylic acid, and the diamine unit is 2-ethyl-1,7-heptanediamine, 2-propyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine and 1,8-octanediamine.
• a polyamide and a composite were obtained in the same manner as in Example 1 except that a mixture of 9-nonanediamine [4/1/20/75 (molar ratio)] was used.
• Example 3 Example 1 except that the dicarboxylic acid unit was 21.3 g of naphthalenedicarboxylic acid, and the diamine unit was a mixture of 2-methyl-1,8-octanediamine and 1,9-nonanediamine [15/85 (molar ratio)]. Polyamides and composites were obtained in the same manner as above.
• Example 10 A mixture of diamine units of 2-ethyl-1,7-heptanediamine, 2-propyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine and 1,10-decanediamine [4/1/20 /75 (molar ratio)] in the same manner as in Example 1 to obtain a polyamide and a composite.
• Example 5 A polyamide and a composite were obtained in the same manner as in Example 1 except that the diamine unit was a mixture of 2-methyl-1,8-octanediamine and 1,10-decanediamine [20/80 (molar ratio)]. rice field.
• Table 1 shows the compositions of Examples and Comparative Examples and their measurement results.
• Examples 1 to 10 are 2-ethyl
• containing a specific amount of -1,7-heptanediamine units and/or 2-propyl-1,6-hexanediamine units there is little decrease in the melting point and glass transition temperature of the polyamide, and the heat resistance is less likely to decrease.
• the flexural strength and flexural modulus of the composite are less lowered. Therefore, it can be seen that the composites of Examples have both a short molding cycle and excellent heat resistance and mechanical strength.
• the present invention makes it possible to provide composites with high heat resistance and mechanical properties and short molding cycle times.
• INDUSTRIAL APPLICABILITY The composite of the present invention is very useful because it can be used as various molded articles that require heat resistance and mechanical properties, and can improve productivity when manufacturing molded articles. This application is based on a Japanese patent application (Japanese Patent Application No. 2021-206185) filed on December 20, 2021, the entirety of which is incorporated by reference.

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• 2022
  • 2022-12-19 JP JP2023569423A patent/JPWO2023120462A1/ja active Pending
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