CN101107316A - Resin composition and fiber structural product - Google Patents
Resin composition and fiber structural product Download PDFInfo
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- CN101107316A CN101107316A CNA2006800031272A CN200680003127A CN101107316A CN 101107316 A CN101107316 A CN 101107316A CN A2006800031272 A CNA2006800031272 A CN A2006800031272A CN 200680003127 A CN200680003127 A CN 200680003127A CN 101107316 A CN101107316 A CN 101107316A
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Abstract
To provide a resin composition and fiber structure that are free from material drip at combustion and excel in flame retardant performance in usages as a flame retardant material, in particular, fiber products, film products, resin molding products, etc. [MEANS FOR SOLVING PROBLEMS] There is provided a polyester resin composition containing a polyester resin and a silicone compound wherein the silicone compound comprises a silicone compound containing at least a structural unit of the formula RSiO1.5 (R: organic group), and wherein the weight ratio of silanol groups of the silicone compound is in the range of 2 to 10% based on the total weight of the silicone compound, and wherein the blending ratio of silicone compound to polyester resin in terms of weight ratio is =100:0.1 but <100:10.
Description
Technical Field
The present invention relates to a flame retardant material, and particularly to a flame retardant material which does not drip (melt drip) when a thermoplastic material is burned and can exhibit flame retardancy.
Background
Conventionally, as a method for imparting flame retardancy to a material such as a flammable resin or a flammable fiber, a material containing a halogen flame retardant such as a chlorine-containing flame retardant or a bromine-containing flame retardant, or a material containing a halogen flame retardant and an antimony flame retardant has been proposed in many cases. However, although these materials have excellent flame retardancy, there is a problem that a halogen-based flame retardant may generate a halogenated gas during combustion, and many studies have been made to solve the problem.
For example, many materials containing a phosphorus flame retardant using a phosphorus compound containing no halogen or antimony element have been proposed, but the flame retardancy is lower than that of halogen or antimony flame retardants, and the flame retardancy is insufficient.
In order to solve the above problems, use of a polysiloxane compound containing no halogen, antimony element, or phosphorus element has been studied.
The polysiloxane compound is represented by R with 1 functionality 3 SiO 0.5 (M units), 2 functional R 2 SiO 1.0 (D Unit), 3-functional RSiO 1.5 (T Unit), 4-functional SiO 2.0 (Q unit) is any one of the structural units shown in the following groups.
As an example of imparting flame retardancy by the polysiloxane compound, a melt-processable polymer composition formed from a kneaded product of a non-polysiloxane polymer and a monoorganosiloxane has been proposed (see patent document 1).
Indeed, these examples do not contain halogen, antimony, or phosphorus, and can exhibit flame retardancy to a certain extent, but in order to exhibit flame retardancy, the blending ratio of the non-silicone polymer and the monoorganosiloxane needs to be in the range of 10: 1 to 1: 5, and the amount of monoorganosiloxane added is large, which causes problems of high cost and deterioration of the physical properties of the non-silicone polymer. Further, there is a problem that dripping cannot be suppressed.
In addition, a flame-retardant thermoplastic molding composition containing a flame-retardant amount of a copolymer of polyetherimide and organosiloxane in a linear polyester having a high molecular weight has been proposed (see patent document 2).
This example can certainly exhibit a certain degree of flame retardancy, but has a problem of low flame retardancy and a low effect of suppressing dripping because of low heat resistance.
Further, there has been proposed a polyester-based resin composition for fibers which contains 4% by weight or less of a silicone oil having a functional group in a side chain thereof and which does not melt and drip during combustion (see patent document 3).
Although this example can certainly exhibit flame retardancy and a certain degree of effect of suppressing dripping, it has a problem of low flame retardancy due to low heat resistance, and a technique for suppressing dripping and sufficiently exhibiting flame retardancy has not yet been established at present.
Patent document 1: japanese patent laid-open No. 54-36365
Patent document 2: japanese unexamined patent publication Hei 7-166040
Patent document 3: japanese unexamined patent publication Hei 8-209446
Disclosure of Invention
In view of the above-described situation, an object of the present invention is to provide a thermoplastic material which is improved in dripping during combustion of the thermoplastic material and which can exhibit flame retardancy.
In order to solve the above problems, the present invention employs the following configuration:
(1) A polyester resin composition comprising a polyester resin and a polysiloxane compound, wherein the polysiloxane compound contains at least RSiO 1.5 (R is an organic group), wherein the amount of silanol groups in the polysiloxane compound is 2to 10% by weight based on the total polysiloxane compound, and the mixing ratio of the polysiloxane compound to the polyester resin is 100: 0.1 or more and less than 100: 10 by weight.
(2) A fiber structure comprising the polyester resin composition according to (1).
(3) A resin composition comprising: base resin containing at least RSiO 1.5 (R is an organic group) and a compound having an imide structure.
(4) A fiber structure comprising the polyester resin composition according to (3).
(5) A polyester fiber structure comprising a polyester resin, a polysiloxane compound,And a flame retardant element, the polysiloxane compound at least containing RSiO 1.5 (R is an organic group), the content of the polysiloxane compound in the resin composition is 0.5-30% by weight, and the content of the flame-retardant element in the resin composition is 1000-50000 ppm.
The present invention also includes a resin molded article comprising any of the above resin compositions, and a fiber product comprising any of the above fiber structures.
The present invention can provide a flame retardant material which is useful as a flame retardant resin material and a flame retardant fiber material, specifically, which is useful for industrial use, clothing use, non-clothing use, and the like, does not drip when melted, and can exhibit flame retardancy.
Detailed Description
The present invention will be described in detail below.
The present invention is a polyester resin composition comprising a polyester resin and a polysiloxane compound, wherein the polysiloxane compound contains at least RSiO 1.5 (R is an organic group) in a weight ratio of 2to 10% based on the total amount of the polysiloxane compound, and a mixing ratio of the polysiloxane compound to the polyester resin is 100: 0.1 or more and less than 100: 10 based on the weight ratio.
As mentioned above, the so-called polysiloxane compounds are represented by R 3 SiO 0.5 (M Unit), R 2 SiO 1.0 (D Unit), RSiO 1.5 (T Unit), siO 2.0 (Q Unit) and the polysiloxane-based compound of the present invention as used herein means a compound containing at least RSiO 1.5 The polysiloxane compound of the structural unit (T unit) may be composed of a single unit or may be composed of a plurality of structural units such as MT unit, DT unit, TQ unit and the like.
From the viewpoint of heat resistance of the silicone-based compound, it is preferable that RSiO is contained in a molar ratio of 87.5% or more with respect to the entire silicone-based compound 1.5 (T unit), more preferably 90% or more. When the T unit is contained in the polysiloxane compound in such a range, the heat resistance of the polysiloxane compound can be improved, and the decomposition of the polysiloxane compound during combustion can be suppressed to improve the flame retardancy of the resin composition.
The amount of silanol groups in the polysiloxane compound is 2to 10% by weight, preferably 3 to 8% by weight, based on the total polysiloxane compound. The amount of silanol groups herein is the weight of OH groups bonded to Si in the polysiloxane compound.
When the amount of the silanol group is within the range of the present invention, the polyester-based resin and the polysiloxane-based compound can form a crosslinked structure during combustion, and carbonization of the polyester-based resin is promoted, whereby dripping can be suppressed.
When the amount of silanol groups is less than the range of the present invention, the effect of suppressing dripping is small, which is not preferable. On the other hand, when the amount of silanol groups is more than the range of the present invention, not only the effect of suppressing dripping is balanced but also gelation occurs at the time of melt-kneading with a polyester resin to cause deterioration in physical properties and processability, which is not preferable. Further, when used in a fiber structure, gelation occurs during melt spinning, and physical properties and processing characteristics are deteriorated.
The amount of silanol groups can be determined according to 29 SiO produced by silanol-free Structure in Si-NMR 2.0 、RSiO 1.5 、R 2 SiO 1.0 、R 3 SiO 0.5 And Si (OH) generated from a silanol group-containing structure 4 、SiO 0.5 (OH) 3 、SiO 1.0 (OH) 2 、SiO 1.5 (OH)、RSi(OH) 3 、 RSiO 0.5 (OH) 2 、RSiO 1.0 (OH)、R 2 Si(OH) 2 、R 2 SiO 0.5 (OH)、R 3 The ratio of the peak area (integrated value) of Si (OH) was calculated.
For example, in the case of polysiloxanes consisting only of RSiO 1.5 And RSiO 1.0 In the case of (OH) formation, if RSiO 1.5 And RSiO 1.0 The ratio of the integrated values of (OH) was 1.5 (RSiO) 1.5 )∶1.0 (RSiO 1.0 (OH)), it can be obtained by the following formula 1.
[ number 1]
In addition, except the case where the polysiloxane-based compound is composed of only the structural unit of the Q unit, the polysiloxane-based compound contains an organic group bonded to the Si element. Examples of the organic group include a hydrogen group, a hydroxyl group, a hydrocarbon group, and an aromatic hydrocarbon group.
Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, an allyl group, a methallyl group, and a cyclohexyl group. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
From the viewpoint of versatility and heat resistance of the polysiloxane compound, the organic group is preferably a group selected from a hydroxyl group, a methyl group, and a phenyl group, and more preferably a phenyl group. The content of the phenyl group is preferably 85% or more in terms of a molar ratio with respect to all organic groups contained in the polysiloxane-based compound.
The polysiloxane compound has a weight average molecular weight determined by polystyrene calibration by GPC measurement, in the range of preferably 500 to 100000, more preferably 1000 to 10000, from the viewpoint of dispersibility in the polyester resin composition. When the weight average molecular weight is more than this range, the viscosity of the silicone compound during melt kneading may be high, and the dispersibility of the silicone compound may be deteriorated. If the weight average molecular weight is less than this range, the dispersibility of the silicone compound may deteriorate. If the dispersibility is deteriorated, the fiber-forming property may be deteriorated when the composition is used for a fiber structure.
The mixing ratio of the silicone compound to the polyester resin is preferably 100: 0.1 or more and less than 100: 10, more preferably 100: 1 or more and less than 100: 7, in terms of the weight ratio, from the viewpoint of the dripping prevention effect and the flame retardancy.
The polyester-based resin of the present invention is preferably selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polylactic acid. The polylactic acid includes poly-L-lactic acid, and poly-D-lactic acid. These may be used alone, or 2 or more of them may be used in combination.
The resin composition preferably contains a polyester resin as a main component, and more preferably contains 70% by weight or more of the polyester resin relative to the resin composition. However, a mixture, an alloy, a composite or the like with other organic polymers or inorganic compounds may be used within the range where the dripping suppressing effect, flame retardancy, physical properties of the resin composition, processability and the like are not deteriorated. When used in a fiber structure, the fiber may be blended or mixed with other resin fibers.
The polyester resin composition of the present invention may contain additives such as antioxidants such as hindered phenols, amines, phosphites and thioesters, ultraviolet absorbers such as benzotriazoles, benzophenones and cyanoacrylates, organic pigments such as infrared absorbers, cyanines, stilbenes, phthalocyanines, anthraquinones, orange (perinone) and quinacridones, inorganic pigments, fluorescent whiteners, particles such as calcium carbonate, silica and titanium dioxide, antibacterial agents and antistatic agents.
The polyester resin composition of the present invention is preferably in the form of chips, flakes or powder. By forming the polyester resin composition into such a shape, the polyester resin composition can be preferably used and efficiently used in transportation and supply to a melt molding machine or the like.
The polyester resin composition of the present invention can be preferably molded and used as a resin molded article. Particularly, it is preferably used for molded articles requiring a dripping suppressing effect and flame retardancy, for example, interior and exterior materials of vehicles, housings of electric appliances, and covers of circuits, but the use is not limited to these applications.
The polyester-based resin composition of the present invention can be preferably used as a fiber structure.
The fibrous structure of the present invention may be in the form of a filament (filament) or a staple (staple). For example, as the filaments for clothing use, multifilaments having a single-filament fineness in the range of 0.1dtex to several tens of dtex, a total fineness of 50dtex to 300dtex, and a number of single filaments of 10 to 100 are preferably used.
For example, as a filament for industrial use, a multifilament having a single yarn fineness in the range of ten and several dtex to several hundred dtex, a total yarn fineness in the range of several hundred dtex to several thousand dtex, and a number of single yarns in the range of 10 to 100 is preferably used.
The fiber structure may be in the form of a fabric such as a woven fabric, a knitted fabric, or a nonwoven fabric.
For example, in the case of clothing applications, the filaments may be woven into a woven fabric having a triple or modified structure as a single structure, or a weft double or warp double structure as a double structure. The mass of the fabric at this time is preferably 50g/m 2 ～500g/m 2 The range of (1).
Further, the filament for industrial use may be woven into a fabric as in clothing use. The mass of the fiber structure is 300g/m 2 Above 1500g/m 2 The following ranges.
In addition, various post-processes may be performed in order to prevent the polyester-based fiber structure of the present invention from being affected by the post-process. For example, the functions such as hydrophobicity, hydrophilicity, antistatic property, deodorizing property, antibacterial property, and deep color property can be imparted by in-bath processing, suction processing, coating processing, roll-dry (Pad-dry) processing, roll-steam (Pad-steam) processing, and the like.
The polyester-based fiber structure of the present invention is preferably used as a fiber product particularly requiring a dripping suppressing effect and flame retardancy, and can suppress dripping and exhibit flame retardancy in, for example, vehicle interior materials such as a seat and a foot pad, interior materials such as a curtain, a carpet and a chair cover material (chair covering material), and clothing materials.
Another aspect of the present invention is a resin composition containing: base resin containing at least RSiO 1.5 (R is an organic group) or a polysiloxane compound having an imide structure.
The base resin used herein is a resin other than the silicone resin and the resin having an imide structure. As the base material resin, a thermoplastic resin is preferable from the viewpoint of processability, and for example, a resin selected from the group consisting of polyester, polyimide, and polyolefin can be preferably used.
As the polyester, it is preferably selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polylactic acid including poly-L-lactic acid, poly-D-lactic acid. These may be used alone, or 2 or more of them may be used in combination.
Examples of the polyimide include nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, and nylon 12 having a-CONH-repeating structure.
Examples of the polyolefin include polyethylene and polypropylene.
The base resin is preferably contained as a main component in the resin composition, more preferably 50% or more, and still more preferably 70% or more by weight of the resin composition. However, a mixture, an alloy, a composite or the like with other organic polymers or inorganic compounds may be used as long as the dripping suppressing effect, flame retardancy, physical properties of the resin composition, processability and the like are not deteriorated. When used for a fiber structure, the fiber may be blended or mixed with other resin-forming fibers.
Polysiloxane compound means containing at least RSiO 1.5 (T unit) structural unit. From the viewpoint of heat resistance of the polysiloxane compound, it is preferable that the molar ratio is set to the total polysiloxane compoundContaining over 30% of RSiO 1.5 The structural unit is more preferably contained at 60% or more. By incorporating a T unit in the polysiloxane compound, the heat resistance of the polysiloxane compound can be improved, the decomposition of the polysiloxane compound during combustion can be suppressed, and the flame retardancy can be improved.
The amount of silanol groups in the polysiloxane compound is preferably 2% to 10%, more preferably 3% to 8%, and still more preferably 3% to 7% by weight based on the total polysiloxane compound. The silanol group amount herein means the weight of the OH group bonded to Si in the polysiloxane compound.
The amount of silanol groups, as stated above, can be in 29 Measured by Si-NMR.
When the amount of silanol groups is in the above range, the resin, the compound having an imide structure, and the polysiloxane compound form a crosslinked structure during combustion, and carbonization of the resin composition is promoted, whereby dripping can be suppressed.
When the silanol group content is less than the above range, the effect of suppressing dripping may be lowered, which is not preferable. On the other hand, when the amount of silanol groups is more than the above range, the dripping inhibition effect tends to be balanced. When the amount of silanol groups is more than the above range, gelation may occur during melt spinning when used for a fiber structure, and physical properties and processing characteristics may be deteriorated, which is not preferable.
In addition, except the case where the polysiloxane-based compound is formed only of the structural unit of the Q unit, the polysiloxane-based compound contains an organic group bonded to the Si element. Examples of the organic group include a hydrogen group, a hydroxyl group, a hydrocarbon group, and an aromatic hydrocarbon group.
Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, an allyl group, a methallyl group, and a cyclohexyl group. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
From the viewpoint of versatility and heat resistance of the polysiloxane compound, the organic group is preferably selected from a group consisting of a hydroxyl group, a methyl group, and a phenyl group, and more preferably a phenyl group. The content of the phenyl group is preferably 20% or more, more preferably 30% or more, and still more preferably 50% or more in terms of a molar ratio with respect to the total organic groups contained in the polysiloxane compound.
The polysiloxane compound has a weight average molecular weight determined by polystyrene calibration in GPC measurement, preferably in the range of 500 to 100000, more preferably in the range of 1000 to 10000, from the viewpoint of dispersibility in the polyester resin composition. When the weight average molecular weight is higher than this range, the viscosity of the polysiloxane compound during melt kneading may be high, and the dispersibility of the polysiloxane compound may be deteriorated. When the weight average molecular weight is less than this range, the dispersibility of the silicone compound may also deteriorate. If the dispersibility is deteriorated, the fiber-forming property may be deteriorated when the composition is used for a fiber structure.
The compound having an imide structure is a compound having a structure of-CO-NR '-CO- (R' is an organic group) in its molecular structure.
The compound having an imide structure preferably has thermoplasticity from the viewpoint of processability. The glass transition temperature is preferably 130 to 300 ℃ and more preferably 130 to 250 ℃.
Specific examples of the compound having an imide structure include polyimide, polyamideimide, and polyetherimide.
The compound having an imide structure preferably contains a structural unit represented by the following general formula, for example.
[ solution 1]
Ar in the above formula is an aromatic group having 6 to 42 carbon atoms, and R' is a 2-valent organic group selected from the group consisting of an aromatic group having 6 to 30 carbon atoms, an aliphatic group having 2to 30 carbon atoms, and an alicyclic group having 4 to 30 carbon atoms.
In the above general formula, ar includes, for example:
[ solution 2]
[ solution 3]
Examples of R' include:
[ solution 4]
[ solution 5]
(wherein n is 2to 30).
They may be present in the polymer chain in 1 or 2 or more species together within a range not impairing the effects of the present invention.
The compound having an imide structure is not particularly limited, but from the viewpoint of melt moldability with a thermoplastic resin, handling properties, and the like, a polyetherimide represented by the following general formula in which an ether bond is contained in a polyimide structural component is preferable.
[ solution 6]
Wherein, in the above formula, R 1 Is a 2-valent organic radical selected from the group consisting of aromatic, aliphatic, and alicyclic radicals having from 2to 30 carbon atoms, R 2 Is the same 2-valent organic group as R'.
As the above-mentioned R 1 、R 2 Preferable examples of the aromatic group include aromatic groups represented by the following group of formulae:
[ solution 7]
From the viewpoint of compatibility with the thermoplastic resin (A), melt moldability and the like, a condensate of 2, 2-bis [4- (2, 3-dicarboxyphenoxy) phenyl ] propane dianhydride and m-phenylenediamine or p-phenylenediamine having a structural unit represented by the following formula is preferred.
[ solution 8]
Or
Polyetherimide having the structural element is available under the trade mark name of "1245312512\" (registered trademark), 12572511241257312481124124124125. For example, polyetherimides having a structural unit containing a unit derived from m-phenylenediamine (the former formula) include "125531252312486 (12512m (registered trademark) 1010" and "124531252312486 (12512m. Further, polyetherimides having a structural unit containing a unit derived from p-phenylenediamine (the latter formula) include "124531252312486\12512.
Further, as another preferable example of the compound having an imide structure, from the viewpoint of melt moldability with a thermoplastic resin, handling properties, and the like, ar in the above general formula [ formula 1] is selected from the following groups:
[ solution 9]
R' is selected from the following groups:
[ solution 10]
The polymer of (1).
The polyimide can be prepared by a known method. Can be obtained by dehydrating and condensing a raw material tetracarboxylic acid and/or an acid anhydride thereof from which the Ar can be derived, and 1 or 2 or more compounds selected from the group consisting of raw materials aliphatic primary diamines and/or aromatic primary diamines from which the R' can be derived. Specifically, a method of obtaining a polyamic acid and then heating to close the ring can be exemplified. Further, there may be mentioned a chemical ring-closure method using an acid anhydride and a chemical ring-closure agent such as pyridine or carbodiimide, a method of heating the tetracarboxylic anhydride and diisocyanate from which the R' is derived to decarbonylate and polymerize the same, and the like.
By containing the compound having an imide structure and the polysiloxane compound in the resin composition, the polysiloxane compound, the compound having an imide structure, and the thermoplastic resin as a base material can effectively form a carbonized layer during combustion, and the dripping suppressing effect and the flame retardancy can be remarkably improved as compared with the case where the polysiloxane compound or the compound having an imide structure are contained separately.
The content ratio of the polysiloxane compound and the compound having an imide structure is preferably in the range of 5 (polysiloxane compound) to 95 (compound having an imide structure) to 95: 5, more preferably in the range of 10: 90 to 90: 10 in terms of the weight ratio from the viewpoint of the dripping suppressing effect and the flame retardancy.
The composition ratio of the resin composition of the present invention is preferably in the range of 94 (base material resin), 1 (polysiloxane compound), 5 (compound having an imide structure) to 40: 20: 40, more preferably 90: 3: 7 to 70: 10: 20 in terms of weight ratio, from the viewpoint of the dripping suppressing effect and flame retardancy.
The polyester resin composition of the present invention may contain additives such as antioxidants such as hindered phenols, amines, phosphites, and thioesters, ultraviolet absorbers such as benzotriazoles, benzophenones, and cyanoacrylates, organic pigments such as infrared absorbers, cyanines, stilbenes, phthalocyanines, anthraquinones, oranges, and quinacridones, inorganic pigments, fluorescent brighteners, particles such as calcium carbonate, silica, and titanium dioxide, antibacterial agents, and antistatic agents.
The resin composition of the present invention is preferably in the form of a tablet, a sheet, or a powder. By forming the resin composition into such a shape, the resin composition can be preferably used and efficiently used in transportation and supply to a melt molding machine or the like.
The resin composition of the present invention is preferably used as a resin molded article after molding. Particularly, it is preferably used for molded articles requiring a dripping suppressing effect and flame retardancy, for example, interior and exterior materials of vehicles, housings of electric appliances, and covers of electric circuits, but the use is not limited to these applications.
The resin composition of the present invention can be preferably used as a fibrous structure.
The fiber structure of the present invention may be in the form of a filament or a staple. For example, as the filaments for clothing use, it is preferable to use multifilaments having a single-filament fineness in the range of 0.1dtex to ten-odd dtex, a total fineness of 50dtex to 300dtex, and a number of filaments of 10 to 100.
For example, as a filament for industrial use, a multifilament having a single yarn fineness in the range of ten and several Dtex to several hundred Dtex, a total fineness in the range of several hundred Dtex to several thousand Dtex, and a number of single yarns in the range of 10 to 100 is preferably used.
The fiber structure may be in the form of a fabric such as a woven fabric, a knitted fabric, or a nonwoven fabric.
For example, in the case of clothing applications, the filaments may be woven into a woven fabric having a triple or modified structure as a single structure, or a weft double or warp double structure as a double structure. The mass of the fabric at this time is preferably 50g/m 2 ～500g/m 2 In (c) is used.
Further, the filament for industrial use may be woven into a fabric as in clothing use. The mass of the fiber structure is 300g/m 2 ～1500g/m 2 In the presence of a surfactant.
In addition, various post-processing may be performed in order to prevent the fiber structure of the present invention from being affected by the post-processing. For example, functions such as hydrophobicity, hydrophilicity, antistatic property, deodorizing property, antibacterial property, and deep color property can be imparted by in-bath processing, suction processing, coating processing, pad-dry (Pad-dry) processing, pad-steam (Pad-steam) processing, and the like.
The fiber structure of the present invention is preferably used as a fiber product particularly requiring a dripping suppressing effect and flame retardancy, and is capable of suppressing dripping and exhibiting flame retardancy in, for example, vehicle interior materials such as a seat and a foot pad, interior materials such as a curtain, a carpet and a chair cover, and clothing materials.
Another embodiment of the present invention is a polyester fiber structure comprising a polyester resin, a polysiloxane compound and a flame retardant elementThe polysiloxane compound at least contains RSiO 1.5 (R is an organic group), the content of the polysiloxane compound in the resin composition is 0.5-30% by weight, and the content of the flame-retardant element in the resin composition is 1000-50000 ppm.
Polysiloxane compound means containing at least RSiO 1.5 (T unit) structural unit. From the viewpoint of heat resistance of the polysiloxane compound, it is preferable that the polysiloxane compound contains not less than 50% of RSiO in a molar ratio to the total polysiloxane compound 1.5 The structural unit is more preferably contained in an amount of 85% or more. By incorporating a T unit in the polysiloxane compound, the heat resistance of the polysiloxane compound can be improved, decomposition of the polysiloxane compound during combustion can be suppressed, and the flame retardancy can be improved.
The amount of silanol groups in the polysiloxane compound is preferably 2% to 10% by weight, more preferably 3% to 8% by weight, based on the total polysiloxane compound. The silanol group amount herein means the weight of the OH group bonded to Si in the polysiloxane compound.
The amount of silanol groups, as stated above, can be in 29 Measured by Si-NMR.
When the amount of the silanol group is within the above range, the polyester and the polysiloxane compound form a cross-linked structure during combustion, and carbonization of the polyester fiber is promoted, whereby dripping can be suppressed.
When the silanol group content is less than the above range, the effect of suppressing dripping may be lowered, which is not preferable. On the other hand, when the amount of silanol groups is more than the above range, the dripping inhibition effect tends to be balanced. When the amount of silanol groups is more than the above range, gelation may occur during melt spinning of the polyester fiber structure, and physical properties and processing characteristics may be lowered, which is not preferable.
In addition, except the case where the polysiloxane compound is composed of only the structural unit of the Q unit, the polysiloxane compound contains an organic group bonded to the Si element. Examples of the organic group herein include a hydrogen group, a hydroxyl group, a hydrocarbon group, and an aromatic hydrocarbon group.
Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, an allyl group, a methallyl group, and a cyclohexyl group.
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
From the viewpoint of versatility and heat resistance of the polysiloxane compound, the organic group is preferably a group selected from a hydroxyl group, a methyl group, and a phenyl group, and more preferably a phenyl group. The phenyl group content is preferably 20% or more, more preferably 50% or more, still more preferably 85% or more, and most preferably 99% or more in terms of a molar ratio with respect to the total organic groups contained in the polysiloxane compound.
The polysiloxane compound has a weight average molecular weight determined by polystyrene calibration as measured by GPC preferably in the range of 500 to 100000, more preferably in the range of 1000 to 10000, from the viewpoint of dispersibility in the polyester-based resin composition. When the weight average molecular weight is higher than this range, the viscosity of the silicone compound during melt kneading may be high, and the dispersibility of the silicone compound may be deteriorated. When the weight average molecular weight is less than the above range, dispersibility of the polysiloxane compound may be deteriorated, and thus, the yarn formability may be lowered.
From the viewpoint of the dripping suppressing effect and the flame retardancy, the content of the silicone compound is preferably 0.5 to 30% by weight, more preferably 1 to 10% by weight, based on the polyester fiber structure.
The flame retardant element of the present invention is an element selected from alkali metal elements such as halogen, sodium and potassium, alkaline earth metal elements such as Mg and Ca, and Zn, B, al, N, P and Sb.
From the viewpoint of flame retardancy, elements selected from the group consisting of halogen, N, P, and Sb are preferable, and from the viewpoint of environment, N or P is more preferable. The flame retardant element may be used alone or in combination of two or more.
Specific examples of the compound containing P include phosphates, phosphoric acids, phosphates, phosphines, phosphazenes, and inorganic phosphorus compounds.
Specific examples of the phosphate esters include trialkyl phosphates such as trimethyl phosphate and triethyl phosphate, triaryl phosphates such as triphenyl phosphate and tricresyl phosphate, alkylaryl phosphates such as octyldiphenyl phosphate and lauryl diphenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol bis (di-2, 6-dimethylphenyl phosphate) and bisphenol A bis (diphenyl phosphate).
Examples of the phosphoric acid include phosphoric acid, phosphorous acid, pyrophosphoric acid, polyphosphoric acid, and metaphosphoric acid. Examples of the phosphate salts include metal salts selected from group I to IV elements in the periodic Table of elements such as potassium salt, calcium salt, magnesium salt, zinc salt, and lithium salt, and amine salts of ammonia, ethylenediamine, melamine, guanidine, urea, thiocarbazone, and amino acids. Examples of the phosphine include triethylphosphine, triphenylphosphine, triethylphosphine oxide, and triphenylphosphine oxide. Examples of the phosphazenes include amide phosphazene oligomers and phenoxyphosphazene oligomers. Examples of the inorganic phosphorus compound include red phosphorus and phosphorus pentasulfide. The phosphorus-containing compound may be used alone or in combination of two or more.
As the compound containing a flame retardant element, various known compounds can be used. Examples of the compound containing a P element include compounds such as compounds produced by the chemical industries of asahi electric & chemical industries, vol.124491248712459124591247920 (registered trademark) PFR, vol.1244912487591241241241245912412412479500, cyclic phosphonate esters (product name K-19A) produced by the chemical industries of Minghua (strain), sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium pyrophosphate, sodium tripolyphosphate, phosphoric acid salts of phosphoric acid compounds (strain) three and 24124124592360 (strain) of phosphoric acid chemical industries, guanylurea phosphate (strain) of phosphoric acid chemical industries (strain 24124125125, melamine polyphosphate (strain), and phosphoric acid amide oligomers of phosphazenes (product name: AP-12457125120, manufactured by the chemical industries (strain) and the industrial phosphoric acid salts thereof (product name: pp-1245796120.
By containing the flame retardant element and the polysiloxane compound in the range of the present invention, it is possible to provide a very excellent polyester fiber structure which can remarkably improve the effect of suppressing dripping and the effect of flame retardancy without dripping in the burning test of JIS L1091A-4 method (vertical method).
The JIS L1091A-4 method (vertical method) is a combustion test method in which a test piece is held vertically and combustion evaluation is performed. The JIS L1091A-4 method (vertical method) is very likely to cause dripping as compared with a test method for evaluating combustion by holding a test piece at 45 °, such as JIS L1091D method, and requires a very high dripping-suppressing effect, and thus the effect of the present invention is very excellent.
The flame retardant element of the present invention is preferably contained in the polyester fiber structure in an amount of 1000ppm to 50000ppm as an element from the viewpoint of flame retardancy. If the amount of the flame retardant element is less than this range, the flame retardancy is undesirably low. On the other hand, if the amount of the flame retardant element is more than this range, not only the flame retardancy is substantially balanced, but also the physical properties of the polyester fiber structure are deteriorated and the processability is deteriorated, which is not preferable. The upper limit of the amount of the flame-retardant element is more preferably 30000ppm or less, and still more preferably 10000ppm or less. The lower limit of the amount of the flame-retardant element is more preferably 1500ppm or more.
The amount of flame retardant elements can be quantitatively determined by elemental analysis. Specific examples thereof include fluorescence X-ray analysis, ICP emission analysis, and atomic absorption analysis.
The polyester-based resin of the present invention is preferably selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polylactic acid. The polylactic acid includes poly-L-lactic acid, and poly-D-lactic acid. These may be used alone, or 2 or more of them may be used in combination.
The fiber structure preferably contains polyester fibers as a main component, and more preferably contains 70% by weight or more of polyester fibers with respect to the fiber structure. However, the resin composition can be blended or mixed with other fibers within a range not deteriorating the dripping suppressing effect, flame retardancy, physical properties of the resin composition, processability, and the like.
The polyester fiber structure of the present invention may contain additives such as antioxidants such as hindered phenols, amines, phosphites, and thioesters, ultraviolet absorbers such as benzotriazoles, benzophenones, and cyanoacrylates, organic pigments such as infrared absorbers, cyanines, stilbenes, phthalocyanines, anthraquinones, oranges, and quinacridones, inorganic pigments, fluorescent whitening agents, particles such as calcium carbonate, silica, and titanium dioxide, antibacterial agents, and antistatic agents.
The polyester-based fiber structure of the present invention may be in the form of a filament or a staple. For example, as the filaments for clothing use, it is preferable to use multifilaments having a single-filament fineness in the range of 0.1dtex to tens of dtex, a total fineness of 50dtex to 300dtex, and a number of filaments of 10 to 100.
For example, as a filament for industrial use, a multifilament having a single yarn fineness in the range of ten-odd Dtex to several hundred Dtex, a total yarn fineness in the range of several hundred Dtex to several thousand Dtex, and a number of single yarns in the range of 10 to 100 is preferably used.
Further, the fiber structure may be in the form of a fabric such as a woven fabric, a knitted fabric, or a nonwoven fabric.
For example, in the case of clothing applications, the filaments may be woven into a woven fabric having a triple or modified structure as a single structure, or a weft double or warp double structure as a double structure. The mass of the fabric at this time is preferably 50g/m 2 ～500g/m 2 The range of (1).
Further, the filament for industrial use may be woven into a fabric as in clothing use. This time fiberThe mass of the dimensional structure is 300g/m 2 ～1500g/m 2 The range of (1).
In addition, various post-processes may be performed in order to prevent the polyester-based fiber structure of the present invention from being affected by the post-process. For example, the functions such as hydrophobicity, hydrophilicity, antistatic property, deodorizing property, antibacterial property, and deep color property can be imparted by in-bath processing, suction processing, coating processing, roll-dry (Pad-dry) processing, roll-steam (Pad-steam) processing, and the like.
The polyester fiber structure of the present invention is preferably used as a fiber product particularly requiring a dripping suppressing effect and flame retardancy, and is capable of suppressing dripping and exhibiting flame retardancy in, for example, vehicle interior materials such as a seat and a foot pad, interior materials such as a curtain, a carpet and a chair cover, and clothing materials.
The production method of the present invention will be described in detail below.
The polysiloxane compound can be prepared by general polycondensation. Using e.g. R 3 SiOCl (triorganosilane), R 2 SiOCl 2 (diorganodichlorosilane), RSiOCl 3 (Monoorganotrichlorosilane), siOCl 4 (tetrachlorosilane) as a monomer, and condensing under the action of an acid or alkali catalyst to synthesize the polysiloxane compound. The molar ratio of the target M, D, T, Q units can be adjusted to adjust the raw material R 3 SiOCl (corresponding to M unit), R 2 SiOCl 2 (corresponding to D cell), RSiOCl 3 (corresponding to T unit), siOCl 4 (corresponding to the Q unit).
The content of the organic group R contained in the polysiloxane compound is determined by the content of the organic group R in the monomer. Therefore, the content of the phenyl group contained in the polysiloxane compound can be adjusted by substituting only a desired amount of the phenyl group for R in the monomer.
The content of silanol groups contained in the polysiloxane compound can be controlled by the reaction time. In addition, can be made byR as a blocking agent 3 SiOCl or R 3 SiOH reacts with silanol groups to control the content of silanol groups. The content of silanol groups can be determined as described above 29 Si-NMR measurement.
The weight average molecular weight of the polysiloxane compound can be controlled by the reaction time during production. The molecular weight can be calculated by Gel Permeation Chromatography (GPC) measurement using polystyrene calibration.
Examples of the method for imparting a polysiloxane compound, a compound having an imide structure, a compound containing a flame retardant element, and the like to a fiber structure include a method of adding the polysiloxane compound, the compound having an imide structure, the compound containing a flame retardant element, and the like to a base material resin during polymerization; a method in which a base resin and these compounds are mixed with a solvent and then dried; a method of melt-mixing a base resin and these compounds with a mixing roll such as a twin-screw extruder or a banbury mixer; a method of spinning to obtain a fiber structure and then imparting these compounds by post-processing, and the like. But are not limited to these.
In terms of the polysiloxane-based compound and the compound having an imide structure, a method of melt-mixing a base material resin and these compounds by a kneading machine such as a twin-screw extruder or a banbury mixer is preferable from the viewpoint of stably producing a resin composition in which these compounds are sufficiently dispersed.
Further, the flame retardant element-containing compound is preferably added by post-processing after obtaining a fiber structure, because the production cost can be reduced.
Next, a method for producing the fiber structure will be described.
Examples of the method for producing the fibrous structure include a method of producing the fibrous structure by using a melt spinning machine.
For example, the resin composition obtained by the above method may be cut into 3mm square pieces, and the pieces may be fed into a hopper of a melt spinning machine and melt-spun at a temperature equal to or higher than the melting temperature of the base material resin to obtain a fiber structure.
In addition, a method of imparting a flame retardant element-containing compound to a fiber structure in post-processing will be described.
For example, the flame retardant element-containing compound may be imparted to the fiber structure by in-bath processing, roll-bake method, roll-steam-bake method, or the like.
Specifically, a case where a fiber containing polyethylene terephthalate and a polysiloxane compound is prepared by melt spinning and the obtained fiber is woven to form a woven fabric is used as a base material will be described. First, dirt such as oil solution adhering to the woven fabric serving as the base material is washed by a soaping step. Subsequently, the intermediate setting is performed at 150 to 200 ℃ for 0.1 to 2 minutes using a pin tenter, and then the intermediate setting is performed by dipping the intermediate setting in a solution containing a compound containing a flame retardant element using a calender and rolling. Further drying the fiber structure at 100 to 130 ℃ for 1 to 5 minutes by using a pin tenter, and baking the fiber structure at 130 to 200 ℃ for 0.5 to 5 minutes by using a pin tenter, thereby giving the fiber structure a compound containing a flame retardant element.
As the solution of the compound containing a flame retardant element used in the above method, a solution prepared by dissolving the compound containing a flame retardant element in a solvent capable of dissolving the compound and adjusting the solution concentration to 1 to 90% can be preferably used.
The present invention will be described in more detail below with reference to examples.
Examples
First, the preparation of the polysiloxane compounds in examples and comparative examples was carried out as follows to obtain the polysiloxane compounds 1 to 14 shown in table 1.
< modulation of the ratio of M, D, T, Q units >
R is to be 3 SiOCl (corresponding to R) 3 SiO 0.5 )、R 2 SiOCl 2 (corresponding to R) 2 SiO 1.0 )、RSiOCl 3 (corresponding to RSiO) 1.5 )、SiOCl 4 (corresponding to SiO) 2.0 ) The components were mixed in a molar ratio of each structural unit shown in table 1, and then hydrolyzed with water, and the generated hydrochloric acid was removed with methanol. Then, potassium hydroxide is used as a catalyst to carry out condensation, thereby preparing R 3 SiO 0.5 、R 2 SiO 1.0 、RSiO 1.5 、 SiO 2.0 Polysiloxane compounds with different proportion of structural units.
< adjustment of the ratio of phenyl group to methyl group >
Using the raw materials in which the R moieties are substituted with phenyl and methyl, polysiloxane compounds having different proportions of phenyl and methyl in terms of the molar ratio of the two are prepared.
< adjustment of the content of silanol group >
The reaction time of the polysiloxane compound during condensation is respectively adjusted to obtain the polysiloxane compound. By passing 29 Si-NMR using CDCl 3 TMS (tetramethylsilane) is used as solventThe obtained polysiloxane compound was measured 256 times as a standard substance. SiO produced from a structure not containing silanol groups 2.0 、RSiO 1.5 、R 2 SiO 1.0 、R 3 SiO 0.5 The peak area (integrated value) of (A) and Si (OH) generated from a structure containing a silanol group 4 、SiO 0.5 (OH) 3 、SiO 1.0 (OH) 2 、 SiO 1.5 (OH)、RSi(OH) 3 、RSiO 0.5 (OH) 2 、RSiO 1.0 (OH)、R 2 Si(OH) 2 、 R 2 SiO 0.5 (OH)、R 3 The silanol group amount (wt%) was calculated from the ratio of the peak area (integrated value) of Si (OH).
< measurement of weight average molecular weight >
The reaction time for the condensation of the polysiloxane compound was adjusted, and the weight average molecular weight was calculated by measuring the concentration of the sample at 1wt% with an RI detector and calibrating the sample with polystyrene using chloroform as an eluent by Gel Permeation Chromatography (GPC) on the obtained polysiloxane compound.
TABLE 1
| Polysiloxanes Compound (I) | R 3 SiO 0.5 (％) | R 2 SiO 1.0 (％) | RSiO 1.5 (％) | SiO 2.0 (％) | Methyl radical (％) | Phenyl radical (％) | Silanol group (％) | Molecular weight (Mw) |
| 1 | - | - | 100 | - | 0 | 100 | 4.9 | 5308 |
| 2 | - | - | 100 | - | 30 | 70 | 5.1 | 5112 |
| 3 | 2 | - | 90 | 8 | 0 | 100 | 3.4 | 5902 |
| 4 | 2 | - | 90 | 8 | 30 | 70 | 3.9 | 5883 |
| 5 | - | 30 | 70 | - | 0 | 100 | 4.2 | 5434 |
| 6 | - | 30 | 70 | - | 30 | 70 | 3.8 | 5290 |
| 7 | 2 | 48 | 50 | - | 0 | 100 | 3.4 | 6112 |
| 8 | 2 | 48 | 50 | - | 30 | 70 | 3.1 | 6310 |
| 9 | - | - | 100 | - | 0 | 100 | 1.8 | 5362 |
| 10 | 2 | - | 90 | 8 | 0 | 100 | 1.1 | 6208 |
| 11 | - | 30 | 70 | - | 0 | 100 | 1.2 | 5542 |
| 12 | 2 | 48 | 50 | - | 0 | 100 | 1.1 | 5113 |
| 13 | - | 100 | - | - | 15 | 85 | 3.5 | 4983 |
| 14 | - | 100 | - | - | 100 | 0 | 3.2 | 4891 |
The combustion evaluation in each example was performed as follows.
< method for evaluating dripping Property of resin composition >
A flat plate with the length of 125mm +/-5 mm, the width of 13.0mm +/-0.5 mm and the thickness of 3mm is manufactured to be used as a test piece, the number of drips after 10 seconds of flame exposure was evaluated according to the 20mm vertical burn test (UL 94V) set by V124491251248012521\\124791250812512512512522125221252212574 (Underwriters Laboratories).
< method (1) for evaluating dripping Property of fiber Structure >
A fiber structure having a length of 100mm and a mass of 1g was prepared as a test piece, and evaluated by the JIS L1091D method to evaluate the number of dripping after flame contact.
< method (2) for evaluating dripping Properties of fiber Structure >
A fiber structure having a length of 300mm and a width of 70mm was prepared as a test piece, and evaluated by the method of JIS L1091A-4 to evaluate the number of dripping after flame contact.
< determination of oxygen index (LOI) >
In the evaluation of the resin composition, a flat plate having a length of 150mm, a width of 6.5 mm. + -. 0.5mm and a thickness of 3mm was prepared as a test piece. In the evaluation of the fiber structure, a fiber fabric having a length of 150mm and a width of 60mm was produced, and the oxygen index was determined in accordance with JIS K7201 (method for testing combustion of a polymer material by the oxygen index method).
< method for measuring amount of flame retardant element >
The content of P element was determined by fluorescent X-ray analysis.
Examples 1 to 8 and comparative examples 1 to 5
Polyethylene terephthalate having an Intrinsic Viscosity (IV) of 0.65 was used as the base resin. Using polysiloxane compounds 1 to 12 shown in Table 1, resin compositions containing polyethylene terephthalate and polysiloxane compounds were obtained at a mixing ratio of polyethylene terephthalate to polysiloxane compounds of 95wt% to 5wt% as shown in Table 2. Kneading was carried out using a twin-screw extruder under conditions of a kneading temperature of 275 ℃, an L/D of 30 and a screw revolution of 300 rpm.
Then, the obtained resin composition was molded under the conditions in the above-described evaluation method for the dripping property and the evaluation method for the oxygen index of the resin composition, and evaluation of the dripping property and measurement of the oxygen index (LOI value) as an index of flame retardancy were carried out.
In comparative example 1, since the polysiloxane compound was not contained, the mixture was directly molded without kneading, and the dropping property test and the oxygen index measurement were carried out.
As a result, as shown in Table 2, examples 1 to 8 did not drip, and a high drip-suppressing effect was exhibited as compared with comparative examples 1 to 5. Further, the results obtained in examples 1 to 8 also showed a high LOI value as the flame retardancy index LOI, and excellent dripping suppressing effect and flame retardancy as compared with comparative examples 1 to 5.
TABLE 2
| Use of Polysiloxanes Compound (I) | R 3 SiO 0.5 (％) | R 2 SiO 1.0 (％) | RSiO 1.5 (％) | SiO 2.0 (％) | Methyl radical (％) | Phenyl radical (％) | Silanol group (％) | Molecular weight (Mw) | Number of drips | Flame retardancy (LOI) | |
| Example 1 | 1 | - | - | 100 | - | 0 | 100 | 4.9 | 5308 | 0 | 30 |
| Example 2 | 2 | - | - | 100 | - | 30 | 70 | 5.1 | 5112 | 0 | 29 |
| Example 3 | 3 | 2 | - | 90 | 8 | 0 | 100 | 3.4 | 5902 | 0 | 29 |
| Example 4 | 4 | 2 | - | 90 | 8 | 30 | 70 | 3.9 | 5883 | 0 | 28 |
| Example 5 | 5 | - | 30 | 70 | - | 0 | 100 | 4.2 | 5434 | 0 | 28 |
| Example 6 | 6 | - | 30 | 70 | - | 30 | 70 | 3.8 | 5290 | 0 | 27 |
| Example 7 | 7 | 2 | 48 | 50 | - | 0 | 100 | 3.4 | 6112 | 0 | 27 |
| Example 8 | 8 | 2 | 48 | 50 | - | 30 | 70 | 3.1 | 6310 | 0 | 27 |
| Comparative example 1 | - | - | - | - | - | - | - | - | - | More than 10 times | 22 |
| Comparative example 2 | 9 | - | - | 100 | - | 0 | 100 | 1.8 | 5362 | 4 | 26 |
| Comparative example 3 | 10 | 2 | - | 90 | 8 | 0 | 100 | 1.1 | 6208 | 5 | 25 |
| Comparative example 4 | 11 | - | 30 | 70 | - | 0 | 100 | 1.2 | 5542 | 5 | 25 |
| Comparative example 5 | 12 | 2 | 48 | 50 | - | 0 | 100 | 1.1 | 5113 | 6 | 24 |
Examples 9 to 16 and comparative examples 6 to 10
The resin compositions of polyethylene terephthalate and silicone compound obtained in examples 1 to 8 and comparative examples 1 to 5 were cut into pieces of 3mm square. The obtained chips were dried at 150 ℃ for 12 hours under 2Torr in a vacuum dryer, and then spun at 290 ℃ at a spinning speed of 1500 m/min, a die diameter of 0.23mm to 24H (holes) and a discharge rate of 40 g/min to obtain an undrawn yarn having a composition ratio of polyethylene terephthalate to polysiloxane of 95wt% to 5 wt%. Subsequently, the undrawn yarn was drawn using a drawing machine. The drawn yarn was drawn at a draw ratio such that the fineness of the drawn yarn was 85dtex to 24 monofilaments at a processing speed of 400 m/min, a drawing temperature of 90 ℃ and a setting temperature of 130 ℃.
Then, the obtained drawn yarn was formed into a fiber structure of a knitted fabric by a circular knitting machine, a test piece was produced in accordance with the evaluation method of the dripping property of the fiber structure and the evaluation method of the oxygen index, and evaluation (1) of the dripping property of the fiber structure and measurement of the oxygen index (LOI value) were carried out.
In comparative example 6, since polyethylene terephthalate monomer was used, a fiber structure of a knitted fabric was produced by directly spinning, drawing and tubular knitting without kneading, and evaluated.
As a result, as shown in table 3, examples 9 to 16 showed no dripping, and showed higher dripping-suppressing effects than comparative examples 6 to 10. Further, the flame retardancy index LOI of examples 9 to 16 showed a higher LOI value than that of comparative examples 6 to 10, and the dripping suppressing effect and the excellent flame retardancy were obtained.
TABLE 3
| Use of Polysiloxanes Compound (I) | R 3 SiO 0.5 (％) | R 2 SiO 1.0 (％) | RSiO 1.5 (％) | SiO 2.0 (％) | Methyl radical (％) | Phenyl radical (％) | Silanol group (％) | Molecular weight (Mw) | Number of drips | Flame retardancy (LOI) | |
| Example 9 | 1 | - | - | 100 | - | 0 | 100 | 4.9 | 5308 | 0 | 29 |
| Example 10 | 2 | - | - | 100 | - | 30 | 70 | 5.1 | 5112 | 0 | 28 |
| Example 11 | 3 | 2 | - | 90 | 8 | 0 | 100 | 3.4 | 5902 | 0 | 28 |
| Example 12 | 4 | 2 | - | 90 | 8 | 30 | 70 | 3.9 | 5883 | 0 | 27 |
| Example 13 | 5 | - | 30 | 70 | - | 0 | 100 | 4.2 | 5434 | 0 | 27 |
| Example 14 | 6 | - | 30 | 70 | - | 30 | 70 | 3.8 | 5290 | 0 | 26 |
| Example 15 | 7 | 2 | 48 | 50 | - | 0 | 100 | 3.4 | 6112 | 0 | 26 |
| Example 16 | 8 | 2 | 48 | 50 | - | 30 | 70 | 3.1 | 6310 | 0 | 26 |
| Comparative example 6 | - | - | - | - | - | - | - | - | - | More than 10 times | 21 |
| Comparative example 7 | 9 | - | - | 100 | - | 0 | 100 | 1.8 | 5362 | 4 | 25 |
| Comparative example 8 | 10 | 2 | - | 90 | 8 | 0 | 100 | 1.1 | 6208 | 5 | 24 |
| Comparative example 9 | 11 | - | 30 | 70 | - | 0 | 100 | 1.2 | 5542 | 5 | 24 |
| ComparisonExample 10 | 12 | 2 | 48 | 50 | - | 0 | 100 | 1.1 | 5113 | 6 | 23 |
Examples 17 to 24 and comparative examples 11 to 13
Polyethylene terephthalate having an Intrinsic Viscosity (IV) of 0.65 was used as the base resin, and polyetherimide (product name ULTEM (registered trademark)) 1010 manufactured by GE Plastics having a glass transition temperature (Tg) of 210 ℃ was used as the compound having an imide structure. The resin compositions containing polyethylene terephthalate, polyetherimide and polysiloxane compound shown in Table 4 were obtained by using polysiloxane compounds 1 to 8, 13 and 14 shown in Table 1 at a mixing ratio of 75wt% (polyethylene terephthalate), 20wt% (polyetherimide) and 5wt% (polysiloxane compound). At the mixing temperature: 290 ℃ and L/D: 30. screw revolution: kneading was carried out at 300rpm using a twin-screw extruder.
Then, the obtained resin composition was molded in accordance with the conditions in the above-described evaluation method of the dripping property and the evaluation method of the oxygen index of the resin composition, and evaluation of the dripping property of the resin composition and measurement of the oxygen index (LOI value) as an index of flame retardancy were carried out.
In comparative example 11, polyethylene terephthalate and polyether imide were used in such a ratio that the mixing ratio was 75wt% (polyethylene terephthalate) to 25wt% (polyether imide) without containing a polysiloxane compound.
As a result, as shown in Table 4, examples 17 to 24 showed no dripping, and showed high dripping-suppressing effects as compared with comparative examples 11 to 13. In examples 17 to 24, the flame retardancy index LOI showed a higher LOI value than in comparative examples 11 to 13, and the results of the excellent dripping suppressing effect and flame retardancy were obtained.
TABLE 4
| Use of Polysiloxanes Compound (I) | R 3 SiO 0.5 (％) | R 2 SiO 1.0 (％) | RSiO 1.5 (％) | SiO 2.0 (％) | Methyl radical (％) | Phenyl radical (％) | Silanol group (％) | Molecular weight (Mw) | Number of drips | Flame retardancy (LOI) | |
| Example 17 | 1 | - | - | 100 | - | 0 | 100 | 4.9 | 5308 | 0 | 33 |
| Example 18 | 2 | - | - | 100 | - | 30 | 70 | 5.1 | 5112 | 0 | 32 |
| Example 19 | 3 | 2 | - | 90 | 8 | 0 | 100 | 3.4 | 5902 | 0 | 32 |
| Example 20 | 4 | 2 | - | 90 | 8 | 30 | 70 | 3.9 | 5883 | 0 | 30 |
| Example 21 | 5 | - | 30 | 70 | - | 0 | 100 | 4.2 | 5434 | 0 | 32 |
| Example 22 | 6 | - | 30 | 70 | - | 30 | 70 | 3.8 | 5290 | 0 | 32 |
| Example 23 | 7 | 2 | 48 | 50 | - | 0 | 100 | 3.4 | 6112 | 0 | 32 |
| Example 24 | 8 | 2 | 48 | 50 | - | 30 | 70 | 3.1 | 6310 | 0 | 31 |
| Comparative example 11 | - | - | - | - | - | - | - | - | - | More than 10 times | 21 |
| Comparative example 12 | 13 | - | 100 | - | - | 15 | 85 | 3.5 | 4983 | 4 | 24 |
| Comparative example 13 | 14 | - | 100 | - | - | 100 | 0 | 3.2 | 4891 | 5 | 24 |
Examples 25 to 32 and comparative examples 14 to 16
The resin compositions of polyethylene terephthalate, polyether imide and polysiloxane compound obtained in examples 17 to 24 and comparative examples 11 to 13 were cut into pieces of 3mm square. The obtained chips were dried in a vacuum dryer at 150 ℃ for 12 hours under 2Torr, and then spun at 290 ℃ in spinning temperature at 1500 m/min with a die diameter of 0.23mm to 24H (holes) and a discharge amount of 40 g/min to obtain undrawn yarn having a composition ratio of 75wt% (polyethylene terephthalate) to 20wt% (polyetherimide) to 5wt% (polysiloxane compound). Subsequently, the undrawn yarn was drawn using a drawing machine. The drawn yarn was drawn at a draw ratio such that the fineness of the drawn yarn was 85dtex to 24 monofilaments at a processing speed of 400 m/min, a drawing temperature of 90 ℃ and a setting temperature of 130 ℃ to obtain a drawn yarn.
Then, the obtained drawn yarn was formed into a fiber structure of a knitted fabric by a circular knitting machine, a test piece was produced according to the evaluation method (2) of the dripping property of the fiber structure and the evaluation method of the oxygen index, and the dripping property and the oxygen index (LOI value) were evaluated.
As a result, as shown in table 5, examples 25 to 32 showed no dripping, and showed higher dripping-suppressing effects than comparative examples 14 to 16. Further, the flame retardancy index LOI of examples 25 to 32 also showed a high LOI value as compared with comparative examples 14 to 16, and the results of excellent dripping suppressing effect and flame retardancy were obtained.
TABLE 5
| Use of Polysiloxanes Compound (I) | R 3 SiO 0.5 (％) | R 2 SiO 1.0 (％) | RSiO 1.5 (％) | SiO 2.0 (％) | Methyl radical (％) | Phenyl radical (％) | Silanol group (％) | Molecular weight (Mw) | Number of drips | Flame retardancy (LOI) | |
| Example 25 | 1 | - | - | 100 | - | 0 | 100 | 4.9 | 5308 | 0 | 32 |
| Example 26 | 2 | - | - | 100 | - | 30 | 70 | 5.1 | 5112 | 0 | 31 |
| Example 27 | 3 | 2 | - | 90 | 8 | 0 | 100 | 3.4 | 5902 | 0 | 31 |
| Example 28 | 4 | 2 | - | 90 | 8 | 30 | 70 | 3.9 | 5883 | 0 | 29 |
| Example 29 | 5 | - | 30 | 70 | - | 0 | 100 | 4.2 | 5434 | 0 | 31 |
| Example 30 | 6 | - | 30 | 70 | - | 30 | 70 | 3.8 | 5290 | 0 | 31 |
| Example 31 | 7 | 2 | 48 | 50 | - | 0 | 100 | 3.4 | 6112 | 0 | 31 |
| Example 32 | 8 | 2 | 48 | 50 | - | 30 | 70 | 3.1 | 6310 | 0 | 30 |
| Comparative example 14 | - | - | - | - | - | - | - | - | - | More than 10 times | 21 |
| Comparative example 15 | 13 | - | 100 | - | - | 15 | 85 | 3.5 | 4983 | 5 | 24 |
| Comparative example 16 | 14 | - | 100 | - | - | 100 | 0 | 3.2 | 4891 | 6 | 24 |
Examples 33 to 40 and comparative examples 17 to 21
The polyethylene terephthalate obtained in examples 9 to 16 and the silicone compound were drawn into a drawn yarn having a composition ratio of 95wt% to 5wt%, and the weight per unit area (weight per unit area) was 400g/m 2 The plain weave fiber structure of (1). The flame retardant element-containing compound was a cyclic phosphonate ester (product name K-19A) produced by Micheng chemical industry Co., ltd., having a P element content of 20%, prepared into a 20% aqueous solution, and the plain-woven fiber structure was impregnated with the aqueous solution by a roll-bake method to obtain the flame retardant element-containing fiber structure shown in Table 6.
In addition, a calender is used in the padding to contain the immersion in the treatment liquid. The mangle ratio after impregnation was about 80%, and drying was performed at 130 ℃ for 2 minutes using a pin tenter for drying. The baking was carried out at 190 ℃ for 2 minutes using a pin tenter.
The obtained fiber structure was prepared into a test piece according to the evaluation method (2) for the dripping property of the fiber structure and the evaluation method for the oxygen index, and the dripping property evaluation and the measurement of the oxygen index (LOI value) were performed.
In comparative examples 17 to 21, stretched yarns were obtained in the same manner as in examples 9 to 16, except that the silicone-based compound shown in Table 6 was used. From the drawn yarns obtained in the same manner as in examples 33 to 40, plain-woven fiber structures were produced, and the dripping property and the oxygen index were evaluated in the same manner as in examples 33 to 40. However, in comparative examples 17, 19 and 20, the flame retardant element was not impregnated by roll-bake-baking.
As a result, as shown in table 6, examples 33 to 40 showed no dripping, and showed a higher dripping suppressing effect than comparative examples 17 to 21. In examples 33 to 40, the flame retardancy index LOI showed the same or higher LOI value as that of comparative examples 17 to 21, and the dripping suppressing effect and the excellent flame retardancy were obtained.
TABLE 6
| Use of Polysiloxanes Compound (I) | R 3 SiO 0.5 (％) | R 2 SiO 1.0 (％) | RSiO 1.5 (％) | SiO 2.0 (％) | Methyl radical (％) | Phenyl radical (％) | Silanol group (％) | Molecular weight (Mw) | P element Content (c) of (ppm) | Number of drips | LOI | |
| Example 33 | 1 | - | - | 100 | - | 0 | 100 | 4.9 | 5308 | 28000 | 0 | 32 |
| Example 34 | 2 | - | - | 100 | - | 30 | 70 | 5.1 | 5112 | 25000 | 0 | 31 |
| Example 35 | 3 | 2 | 30 | 48 | 20 | 0 | 100 | 3.4 | 5902 | 26000 | 0 | 30 |
| Example 36 | 4 | 2 | 30 | 48 | 20 | 30 | 70 | 3.9 | 5883 | 25000 | 0 | 29 |
| Example 37 | 5 | 2 | 50 | 28 | 20 | 0 | 100 | 4.2 | 5434 | 22000 | 0 | 29 |
| Example 38 | 6 | 2 | 50 | 28 | 20 | 30 | 70 | 3.8 | 5290 | 24000 | 0 | 28 |
| Example 39 | 7 | 7 | 2 | 48 | 50 | - | 0 | 100 | 3.4 | 6112 | 0 | 28 |
| Example 40 | 8 | 8 | 2 | 48 | 50 | - | 30 | 70 | 3.1 | 6310 | 0 | 28 |
| Comparative example 17 | 1 | - | - | 100 | - | 0 | 100 | 4.9 | 5308 | 30 | 4 | 29 |
| Comparative example 18 | - | - | - | - | - | - | - | - | - | 30000 | More than 10 times | 27 |
| Comparative example 19 | 13 | - | 100 | - | - | 15 | 85 | 3.5 | 4983 | 30 | 6 | 23 |
| Comparative example 20 | 14 | - | 100 | - | - | 100 | 0 | 3.2 | 4891 | 27 | 7 | 22 |
| Comparative example 21 | 14 | - | 100 | - | - | 100 | 0 | 3.2 | 4891 | 30000 | More than 10 times | 28 |
Industrial applicability
The present invention provides a flame retardant material which is useful as a flame retardant resin material and a flame retardant fiber material, and more specifically, which is useful for industrial use, clothing use, non-clothing use, and the like, does not cause melt dripping, and can exhibit flame retardancy.
The fiber structure of the present invention is preferably used as a fiber product particularly requiring a dripping suppressing effect and flame retardancy, and is capable of suppressing dripping and exhibiting flame retardancy in, for example, vehicle interior materials such as a seat and a foot pad, interior materials such as a curtain, a carpet and a chair cover, and clothing materials.
In the description, claims and abstract of the present application, "above" and "below" include the present numbers.
Claims (21)
1. A polyester resin composition comprising a polyester resin and a polysiloxane compound, wherein the polysiloxane compound contains at least RSiO 1.5 A polysiloxane compound of the structural unit, wherein R is an organic group, the silanol group content of the polysiloxane compound is 2to 10 percent by weight relative to the total polysiloxane compound, and the mixing ratio of the polysiloxane compound to the polyester resin is more than 100: 0.1 and less than 100: 10 by weight.
2. The polyester resin composition according to claim 1, wherein the polysiloxane compound contains a phenyl group as the organic group, and the content of the phenyl group is 85% or more in terms of a molar ratio to the total organic groups contained in the polysiloxane compound.
3. The polyester resin composition according to claim 1, wherein the weight average molecular weight of the polysiloxane compound is 500 to 100000.
4. The polyester resin composition according to claim 1, wherein the polysiloxane compound contains RSiO in a molar ratio of 90% or more based on the total polysiloxane compound 1.5 A structural unit.
5. The polyester-based resin composition according to claim 1, wherein the polyester-based resin is selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polylactic acid.
6. A resin molded article comprising the polyester resin composition according to claim 1.
7. A fiber structure comprising the polyester resin composition according to claim 1.
8. The fiber structure according to claim 7, wherein the fiber structure is in a form selected from the group consisting of a filament, a staple and a fabric.
9. A fibrous article comprising the fibrous structure according to claim 7.
10. A resin composition comprising: base resin containing at least RSiO 1.5 Polysiloxane compounds with structural units shown as the specification and compounds with imide structures, wherein R isAn organic group.
11. The resin composition according to claim 10, wherein the organic group contained in the polysiloxane compound contains a phenyl group, and the content of the phenyl group is 20% or more in terms of a molar ratio with respect to the total organic groups contained in the polysiloxane compound.
12. The resin composition according to claim 10, wherein the amount of the silanol group contained in the polysiloxane compound is 2to 10% by weight based on the total polysiloxane compound.
13. The resin composition according to claim 10, wherein the compound having an imide structure has a Tg of 130 to 300 ℃.
14. The resin composition according to claim 10, wherein the compound having an imide structure is a polyether imide.
15. A molded resin article comprising the resin composition according to claim 10.
16. A fiber structure comprising the resin composition according to claim 10.
17. A fibrous article comprising the fibrous structure of claim 16.
18. A polyester fiber structure comprising a polyester resin, a silicone compound containing at least RSiO, and a flame retardant element 1.5 The structural unit is shown, wherein R is an organic group, the content of the polysiloxane compound in the resin composition is 0.5-30% by weight, and the content of the flame retardant element in the resin composition is 1000-50000 ppm.
19. The polyester fiber structure according to claim 18, wherein the organic group contained in the polysiloxane compound contains a phenyl group, and the content of the phenyl group is 20% or more in terms of a molar ratio to the total organic groups in the polysiloxane compound.
20. The fiber structure according to claim 18, wherein the amount of the silanol group contained in the polysiloxane compound is 2to 10% by weight based on the total polysiloxane compound.
21. A fibrous article comprising the polyester-based fiber structure according to claim 18.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP020938/2005 | 2005-01-28 | ||
| JP2005020938 | 2005-01-28 | ||
| JP206674/2005 | 2005-07-15 |
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| Publication Number | Publication Date |
|---|---|
| CN101107316A true CN101107316A (en) | 2008-01-16 |
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| CNA2006800031272A Pending CN101107316A (en) | 2005-01-28 | 2006-01-26 | Resin composition and fiber structural product |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059305A (en) * | 2013-01-25 | 2013-04-24 | 杭州贝斯特化纤有限公司 | Preparation method of antibacterial hydrophobic complexing agent for polyester fibers |
| CN110331466A (en) * | 2019-07-30 | 2019-10-15 | 晋江市亿泰隆化纤制造有限公司 | Short fine filler of flame-resistant terylene and preparation method thereof |
-
2006
- 2006-01-26 CN CNA2006800031272A patent/CN101107316A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059305A (en) * | 2013-01-25 | 2013-04-24 | 杭州贝斯特化纤有限公司 | Preparation method of antibacterial hydrophobic complexing agent for polyester fibers |
| CN103059305B (en) * | 2013-01-25 | 2015-04-08 | 杭州贝斯特化纤有限公司 | Preparation method of antibacterial hydrophobic complexing agent for polyester fibers |
| CN110331466A (en) * | 2019-07-30 | 2019-10-15 | 晋江市亿泰隆化纤制造有限公司 | Short fine filler of flame-resistant terylene and preparation method thereof |
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