CN105940052B - Polyester resin composition, the polyester system: compositions preparation method and used the products formed of the polyester resin composition - Google Patents
Polyester resin composition, the polyester system: compositions preparation method and used the products formed of the polyester resin composition Download PDFInfo
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- CN105940052B CN105940052B CN201580006220.8A CN201580006220A CN105940052B CN 105940052 B CN105940052 B CN 105940052B CN 201580006220 A CN201580006220 A CN 201580006220A CN 105940052 B CN105940052 B CN 105940052B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/201—Pre-melted polymers
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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Abstract
A kind of polyester resin composition, the polyester resin composition contains polyester based resin (A) and the carbodiimide compound (B) shown in formula (1), relative to the mass parts of total amount 100 of polyester based resin (A) and carbodiimide compound (B), the content of carbodiimide compound (B) is 0.1 8 mass parts.
Description
Technical field
The present invention relates to the polyester resin composition containing polyester based resin and carbodiimide compound, the Polyester
The preparation method of resin combination and the products formed for having used the polyester resin composition.
Background technology
Polyester resin is due to the good transparency, mechanical strength, melt stability, solvent resistance and recycling
Property, it is widely used in film, sheet material etc., and then, also it was used in recent years in casing of household appliances or OA machines etc..
However, because polyester resin has the property easily hydrolyzed compared with the past general resin, therefore with raising
When hydrolytic resistance is purpose, the method for adding carbodiimide compound wherein is studied.
By being engaged, being molded with polyester resin by carbodiimide compound, by the carboxyl in polyester resin or pass through
Carboxyl caused by the decomposition of ester group is captured with carbodiimide compound during high-temperature mixing, can suppress the initial performance of article shaped
Reduce.Further, since carbodiimide compound remains in article shaped, the durability of article shaped also improves.
A kind of For example, Patent Document 1 discloses stabilizer against hydrolysis of unsaturated polyester resin, it is characterised in that
As the stabilizer against hydrolysis of the unsaturated polyester resin, its main component is that specific aliphatic or aromatic series carbonization two are sub-
Amines.
Patent Document 2 discloses the carbodiimides that carbodiimides structure is bonded with non-aromatic carbon atom, as
Stabilizer for causing cracking due to the hydrolysis of Polyester plastics, has carbodiimides structure and further amino first
Acrylate structure, urea structures or both the above structure, and be solid at 25 DEG C.
In patent document 3, for the purpose of obtaining the good aliphatic polyester resin composition of wet and heat ageing resistant, disclose
A kind of aliphatic polyester resin composition containing aliphatic polyester resin, hydrolysis inhibitor and non-reacted silicones.Wherein,
Disclose and use carbodiimides based compound to be used as the technology of plasticizer using adipate ester etc. as hydrolysis inhibitor.
In patent document 4, with hydrolytic resistance and bendability and purpose is saved as, discloses a kind of polyester-poly- carbonization two
Imine copolymer and the adhesion agent composition containing the copolymer, the polyester-polycarbodiimide copolymer is by counting equal molecule
Measure the chemical constitution institute being attached for 5000-30000 polyester fragment and polycarbodiimide fragment with amino-formate bond
Form.
Prior art literature
Patent document
Patent document 1：Unexamined Patent 9-249801 publications
Patent document 2：JP 2000-256436 publications
Patent document 3：JP 2009-256405 publications
Patent document 4：JP 2013-75972 publications
The content of the invention
In the technology of patent document 1, although the hydrolysis of polyester resin can be suppressed, in melting mixing and processing and forming
When, due to the carboxyl in polyester resin and carbodiimide-based vigorous reaction, viscosity increase be present and gelation occur,
It is difficult to prepare stable article shaped.
In the technology of patent document 2, although the carbodiimides of solid-like can be obtained, by the way that the carbodiimides is added
It is added in Polyester plastics, the strength retention under low temperature can be improved, but it is low hydrolytic resistance to be present, under the conditions of hot and humid
The problem of strength retention difference after preservation.
In the technology of patent document 3, although mouldability can be improved by using plasticizer, phthalic acid ester is used
During etc. in general plasticizer, the problem of following be present, addition difference can cause formed body to ooze out, formed body it is physical
Matter reduces, and exudate causes environment, healthy obstacle etc..In addition, these plasticizer, due to without the reactivity with carboxyl, depositing
Reduce carbodiimide compound hydrolysis inhibition situation, it is therefore contemplated that being improved.
In the technology of patent document 4, although for the purpose of obtaining hydrolytic resistance and the good film of bendability, by
In using polyester-polycarbodiimide copolymer as main component, the purposes that can be applicable is restricted, and for productivity ratio and
Cost is also contemplated that further improvement.
It is an object of the invention to provide hydrolytic resistance and resistance to exudative excellent, will not cause melt viscosity and solution viscosity
The polyester resin composition that is substantially increased, the preparation method of the polyester resin composition and the polyester based resin group is used
The products formed of compound.
The present inventor, have made intensive studies to achieve these goals, as a result find to be directed to polyester based resin,
By coordinating with specific carbodiimide compound with specific ratio, above-mentioned technical problem is can solve the problem that, so as to complete
The present invention.
That is, the present invention for following polyester resin compositions, the polyester system: compositions preparation method and used this
The products formed of polyester resin composition.
[1] a kind of polyester resin composition, the polyester resin composition contain polyester based resin (A) and following formulas
(1) carbodiimide compound (B) shown in, relative to the total amount of polyester based resin (A) and carbodiimide compound (B)
100 mass parts, the content of carbodiimide compound (B) is 0.1-8 mass parts.
[chemical formula 1]
In formula, R1Represent the residue with one with the compound of functional group of the isocyanates with reactivity；R2Represent tool
There are the aliphatic group of the divalence of at least one alicyclic structure, and-N=C=N- and R2Alicyclic structure Direct Bonding.R3For
The residue of the divalence of polyester-diol.X represents the group selected from following formulas (2)-(4).M represents 1-20 number, and n represents 1-20's
Number, p represent 1-5 number.Multiple R2, X it is each identical or different.
[chemical formula 2]
- N=C=N- (4)
[2] polyester resin composition according to above-mentioned [1], wherein, the number-average molecular weight of the polyester-diol is
1000-40000。
[3] polyester resin composition according to above-mentioned [1] or [2], wherein, the R2For 4,4 '-two isocyanic acids
The residue of the divalence of ester dicyclohexyl methyl hydride.
[4] polyester resin composition according to any one in above-mentioned [1]-[3], wherein, the carbonization two is sub-
The carbodiimides equivalent of amines (B) is 100-1000.
[5] polyester resin composition according to any one in above-mentioned [1]-[4], wherein, the Polyester tree
Fat (A) is selected from polyethylene terephthalate, polybutylene terephthalate (PBT), poly butylene succinate, PLA
One or more of with poly (hydroxy alkanoate).
[6] polyester resin composition according to any one in above-mentioned [1]-[5], wherein, it is described that there is one
The compound with isocyanates with the functional group of reactivity is monohydric alcohol, monohydric phenol, monoisocyanates or monoamine.
[7] preparation method of the polyester resin composition in above-mentioned [1]-[6] described in any one, this method is by described in
Polyester based resin (A) and the carbodiimide compound (B) melting mixing.
[8] preparation method of the polyester resin composition according to above-mentioned [7], wherein, the carbodiimides
Compound (B) is the compound through granulating.
[9] a kind of products formed, the products formed use the polyester resin composition described in any one in above-mentioned [1]-[6]
It is molded with.
In accordance with the invention it is possible to provide hydrolytic resistance and resistance to exudative excellent, melt viscosity and solution viscosity will not be caused
The polyester resin composition that is substantially increased, the preparation method of the polyester resin composition and the polyester based resin group is used
The products formed of compound.
Embodiment
[polyester resin composition]
The polyester resin composition of the present invention, it is characterised in that the polyester resin composition contains polyester based resin
(A) carbodiimide compound (B) and shown in following formulas (1), relative to polyester based resin (A) and carbodiimides chemical combination
The mass parts of total amount 100 of thing (B), the content of carbodiimide compound (B) is 0.1-8 mass parts.
[chemical formula 3]
In formula, R1Represent the residue with one with the compound of functional group of the isocyanates with reactivity；R2Represent tool
There is the aliphatic group of the divalence of at least one alicyclic structure.And-N=C=N- and R2Alicyclic structure Direct Bonding.R3For
The residue of the divalence of polyester-diol.X represents the group selected from following formulas (2)-(4).M represents 1-20 number, and n represents 1-20's
Number, p represent 1-5 number.Multiple R2, X it is each identical or different.
[chemical formula 4]
- N=C=N- (4)
The polyester resin composition of the present invention, hydrolytic resistance and it is resistance to it is exudative it is excellent, melt viscosity and molten will not be caused
The reasons why fluid viscosity is substantially increased is although indefinite, but may be considered as following reason.
The carbodiimide compound (B) shown in formula (1) contained in the polyester resin composition of the present invention, due to
There is polyester fragment between polycarbodiimide base, appropriately distance can be paid between polycarbodiimide base, thus,
Viscosity caused by cross-linking reaction when can suppress melting mixing drastically rises.
In addition, carbodiimide compound (B), by having polyester fragment between polycarbodiimide base, can make
The dissolubility and dispersiveness of carbodiimide compound (B) in polyester based resin (A) improve, and suppress melt viscosity and solution glues
While the rising of degree, hydrolytic resistance and resistance to exudative good article shaped can be obtained.
Further, as polycarbodiimide, by using the polycarbodiimide with specific alicyclic structure, i.e.,
Make for the carbodiimide-based concentration lower than conventional aliphatic polycarbodiimide, can also play good hydrolysis
Property.
＜ polyester based resins (A) ＞
As polyester based resin (A), have no particular limits, the resin with ester group can be used.
As such polyester based resin (A), for example, can use selected from polyethylene terephthalate (below
Referred to as " PET "), poly butylene succinate (hereinafter also referred to " PBS "), poly butylene succinate-polybutyleneadipate
Ester copolymer (hereinafter also referred to " PBSA "), poly adipate succinic acid ester-polybutylene terephthalate (PBT) copolymer are (below
Referred to as " PBAT "), polybutylene terephthalate (PBT) (hereinafter also referred to " PBT "), PEN, polyacrylic acid
Ester, ethylene glycol terephthalate-isophthalic acid glycol ester copolymer, PLA (hereinafter also referred to " PLA ") and poly- butyric acid
Deng one or more of poly (hydroxy alkanoate) (hereinafter also referred to " PHA ").
In them, consider from the viewpoint of economy and processability, be preferably selected from polyethylene terephthalate, gather
One or more of mutual-phenenyl two acid bromide two alcohol ester, poly butylene succinate, PLA and poly (hydroxy alkanoate), more preferably
Polyethylene terephthalate.
Consider from the viewpoint of the hydrolytic resistance of polyester resin composition, melt viscosity and solution viscosity, it is of the invention
The content of polyester based resin (A) in polyester resin composition is preferably 80-99.9 mass %, more preferably 85-99.8 matter
%, more preferably 90-99.7 mass % are measured, is still more preferably 95-99.5 mass %.
＜ carbodiimide compounds (B) ＞
The carbodiimide compound (B) that the present invention uses is represented by following formulas (1).
[chemical formula 5]
In formula, R1Represent the residue with one with the compound of functional group of the isocyanates with reactivity；R2Represent tool
There is the aliphatic group of the divalence of at least one alicyclic structure.And-N=C=N- and R2Alicyclic structure Direct Bonding.R3For
The residue of the divalence of polyester-diol.X represents the group selected from following formulas (2)-(4).M represents 1-20 number, and n represents 1-20's
Number, p represent 1-5 number.Multiple R2, X it is each identical or different.
[chemical formula 6]
- N=C=N- (4)
In formula (1), R1Represent (following to be also referred to as with the compound of functional group of the isocyanates with reactivity with one
For " end-capping reagent (a) " or " (a) composition ") residue.
The carbodiimide compound (B) that the present invention uses, by the way that the terminal isocyanate of remaining is used as into end-capping reagent
(a) composition blocked, it is possible to increase the intermiscibility and polyester of carbodiimide compound (B) and polyester based resin (A)
The storage stability of based resin composition, improve quality.
(end-capping reagent；(a) composition)
As (a) composition, monohydric alcohol, monohydric phenol, monoisocyanates, monoamine etc. can be enumerated.
As the monohydric alcohol, methanol, ethanol, cyclohexanol, poly glycol monomethyl ether, polypropylene glycol monomethyl ether can be enumerated
Deng.
As the monohydric phenol, phenol, methylphenol, xylenol, naphthols etc. can be enumerated.
As the monoisocyanates, methyl isocyanate, ethyl isocyanate, propylisocyanate, positive fourth can be enumerated
The low alkyl group monoisocyanates of based isocyanate, sec-butyl isocyanates or t-butylisocyanate etc.；Cyclohexyl isocyanic acid
The ester ring type aliphatic mono-isocyanate of ester etc.；Phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate,
Aromatic monoisocyanate of 2,6- diisopropyl benzene based isocyanates etc. etc..
As the monoamine, the one-level amine of butylamine, cyclohexylamine etc. can be enumerated；Diethylamine, dibutyl amine, dicyclohexyl amine etc.
Secondary amine.
In them, from the intermiscibility and polyester based resin for improving carbodiimide compound (B) and polyester based resin (A)
The viewpoint of the storage stability of composition considers, preferably monohydric alcohol or monoisocyanates, more preferably monohydric alcohol, further
Preferably poly glycol monomethyl ether or polypropylene glycol monomethyl ether, it is still more preferably poly glycol monomethyl ether.
In formula (1), R2Represent the aliphatic group of the divalence with least one alicyclic structure, and-N=C=N-
With R2 alicyclic structure Direct Bonding.
The carbodiimide compound (B) that the present invention uses, passes through carbodiimide-based (- N=C=N-) and alicyclic structure
Direct Bonding, the reactivity raising of carbodiimide-based can be made, even if to be lower than conventional aliphatic polycarbodiimide
Carbodiimide-based concentration, can also play good hydrolytic resistance.
As the aliphatic group of the divalence with least one alicyclic structure, can enumerate with least one alicyclic structure
Diisocyanate (hereinafter also referred to " diisocyanate (b) " or " (b) composition ") residue of divalent.
(diisocyanate；(b) composition)
As (b) composition, for example, Isosorbide-5-Nitrae-diisocyanate cyclohexane, 4 can be enumerated, the hexamethylene of 4 '-diisocyanate two
Methylmethane, methylcyclohexane diisocyanate etc..Wherein, from the hydrolytic resistance of polyester resin composition, melt viscosity and molten
The viewpoint of fluid viscosity considers, in them, preferably 4, and 4 '-hexylmethane.
In formula (1), R3Represent the divalence of polyester-diol (hereinafter also referred to " polyester-diol (c) " or " (c) composition ")
Residue.
The carbodiimide compound (B) that the present invention uses, by with being used as R3Polyester fragment, with polyester based resin
(A) compatibility is good, can improve the dissolubility of carbodiimide compound (B) and dispersiveness in polyester based resin (A),
Thus suppress the rising of melt viscosity and solution viscosity, and improve hydrolytic resistance and resistance to exudative.
(polyester-diol；(c) composition)
As (c) composition, have no particular limits, there is the glycol of ester group, pass through multivalence for example, can enumerate
The material that the chemical constitution that the polycondensation of carboxylic acid and multivalence alcohol obtains is formed.
As polyvalent carboxylic acid, preferably using selected from butanedioic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, ten
The aliphatic dibasic acid of three docosandioic acids, dimeric dibasic acid and its hydride etc., 1,2- cyclohexyl dicarboxylic acid, 1,3- cyclohexyl dicarboxylic acids, Isosorbide-5-Nitrae-
The fragrance of the aliphatic dibasic acid of cyclohexyl dicarboxylic acid etc., terephthalic acid (TPA), M-phthalic acid, phthalic acid, naphthalene dicarboxylic acids etc.
One or more of binary acid of race's binary acid etc..
In addition, as multivalence alcohol, preferably using selected from ethylene glycol, propane diols, butanediol, neopentyl glycol, methyl pentanediol,
The aliphatic diol of pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol, decanediol, dodecane dihydric alcohol, two polyalcohols etc.,
Cyclohexanediol, hydrogenation xylyleneglycol etc. ester ring type glycol, xylyleneglycol etc. containing aromatic rings
One or more of glycol of glycol etc..
As the number-average molecular weight of (c) composition, glued from the hydrolytic resistance of polyester resin composition, melt viscosity and solution
The viewpoint of degree considers, preferably 1000-40000, more preferably 1500-35000, more preferably 2000-30000.And
And number-average molecular weight is by exclusion chromatography, is determined using polystyrene as standard substance.
Consider from the viewpoint of the hydrolytic resistance of polyester resin composition, melt viscosity and solution viscosity, formula (1)
In, m represents 1-20 number, more preferably preferably 2-18, more preferably 4-16,6-15.
Consider from same viewpoint, in formula (1), n represents 1-20 number, preferably 2-18, more preferably 4-16, enters
One step is preferably 6-15.
Consider from same viewpoint, in formula (1), p represents 1-5 number, more preferably preferably 1-4,1-3.
(carbodiimides equivalent)
Consider from the viewpoint of the hydrolytic resistance of polyester resin composition, melt viscosity and solution viscosity, carbonization two is sub-
Amines (B) carbodiimides equivalent is preferably 100-1000 (per the formula weight of 1mol carbodiimide-baseds), more preferably
For 150-850, more preferably 200-600.
(content of carbodiimide compound (B))
Consider from the viewpoint of the hydrolytic resistance of polyester resin composition, melt viscosity and solution viscosity, relative to poly-
The mass parts of total amount 100 of ester system resin (A) and carbodiimides (B), the content of the carbodiimide compound (B) is 0.1-
8 mass parts, preferably 0.2-7 mass parts, more preferably 0.3-6 mass parts, more preferably 0.5-5 mass parts.
The preparation method ＞ of ＜ carbodiimide compounds (B)
The carbodiimide compound (B) that the present invention uses can be prepared by known method.
Can enumerate for example,
(i) in the presence of a catalyst, diisocyanate (b) is carried out carbodiimides and obtain polycarbodiimide
(hereinafter also referred to " (d) composition "), next, adding end-capping reagent (a) and polyester-diol (c) in (d) composition, be copolymerized instead
Should be with the method for end capping reaction；
(ii) in the presence of a catalyst, diisocyanate (b), polyester-diol (c) and end-capping reagent (a) is made to carry out carbonization two
The method of imidization, copolyreaction and end capping reaction；
(iii) diisocyanate (b) and polyester-diol (c) is carried out copolyreaction, then, add end-capping reagent (a) and urge
Agent, the method for carrying out carbodiimides reaction and end capping reaction.
Wherein, from the perspective of productivity ratio, preferably prepared by the method for (i).
(preparation of polycarbodiimide (d))
The polycarbodiimide (d), diisocyanate (b), having as carbodiimides catalyst can be used
Machine phosphorus series compound or organo-metallic compound etc., solvent-free or in atent solvent, carry out carbodiimides reaction and
Synthesis.
As the concrete example of the carbodiimides, can enumerate 3- methyl isophthalic acids-phenyl -2- phosphorus -1- oxides, 3- methyl -
1- ethyl -2- phosphorus -1- oxides, 1,3- dimethyl -2- phosphorus -1- oxides, 1- phenyl -2- phosphorus -1- oxides, 1- ethyls -2-
Phosphorus -1- oxides, 1- methyl -2- phosphorus -1- oxides etc..3- methyl isophthalic acids-phenyl-the 2- being preferably industrially readily obtained in them
Phosphorus -1- oxides.Carbodiimides catalyst individually one kind or two or more can be applied in combination.
Consider from the viewpoint of productivity ratio, the reaction temperature of the carbodiimidesization reaction is preferably 70-250 DEG C, more
Preferably 100-230 DEG C, more preferably 150-200 DEG C.
Consider from identical viewpoint, the reaction time of the carbodiimidesization reaction is preferably 1-50 hours, more excellent
Elect 10-40 hours, more preferably 20-30 hours as.
The usage amount of catalyst, can suitably it be determined according to the species of the catalyst used, relative to diisocyanate (b)
100 mass parts, preferably 0.01-10 mass parts, more preferably 0.05-5 mass parts, more preferably 0.2-1 mass parts.
(copolyreaction)
The copolyreaction, can be by making polycarbodiimide (d), end-capping reagent (a) and polyester-diol obtained above
(c) react and carry out in a heated condition.The order of addition (d) composition, (a) composition and (c) composition has no particular limits, from
Operational viewpoint during synthesis considers, is preferably (d) composition, (a) composition and (c) composition add simultaneously, from suppress it is secondary instead
The viewpoint answered considers, preferably adds (d) composition and (a) composition, after the completion of the reaction for confirming (d) composition and (a) composition, adds
Add (c) composition.
The mixed proportion of polycarbodiimide (d) and polyester-diol (c), from the water-fast of obtained polyester resin composition
Xie Xing, melt viscosity and solution viscosity viewpoint considers, the molal quantity of the terminal isocyanate acidic group of polycarbodiimide (d) with it is poly-
The ratio [NCO (d)/OH (c)] of the molal quantity for the hydroxyl that esterdiol (c) has, preferably 1.20-2, more preferably 1.25-2, enters
One step is preferably 1.33-2.
Consider from the viewpoint of productivity ratio, the reaction temperature of the copolyreaction is preferably 40-250 DEG C, more preferably 90-
220 DEG C, more preferably 130-200 DEG C.
Consider from identical viewpoint, the reaction time of the copolyreaction is preferably -20 hours 5 minutes, more preferably
- 10 hours 30 minutes, more preferably -3 hours 1 hour.
Consider from the viewpoint of the productivity ratio of polyester based resin, obtained carbodiimide compound (B) preferably with polyester
It is resin (A) melting mixing and masterbatch, or only carbodiimide compound (B) ingredient granules, is more preferably only carbonized two
Group with imine moiety (B) ingredient granules.Granulating, grain shape can be machined to carry out by known granulation.
The other composition ＞ of ＜
In polyester resin composition, can be properly added as needed pigment, filler, levelling agent, surfactant, point
The additive of powder, ultra-violet absorber, antioxidant, fire retardant, colouring agent etc..
Total content ＞ of ＜ polyester based resins (A) and carbodiimide compound (B)
Consider from the viewpoint of the processability of polyester resin composition, hydrolytic resistance, melt viscosity and solution viscosity, this
Total content of polyester based resin (A) and carbodiimide compound (B) in the polyester resin composition of invention is preferably
90-100 mass %, more preferably 92-100 mass %, more preferably 95-100 mass %.
[preparation method of polyester resin composition]
The present invention polyester resin composition preparation method, for by the polyester based resin (A) and it is described be carbonized two
The method of group with imine moiety (B) melting mixing.
The preparation method of the present invention, by using the carbodiimide compound (B), can suppress the big of melt viscosity
Width rises, and improves workability during melting mixing, thus the productivity ratio of polyester resin composition is good.
Melting mixing, which can use, possesses the progress such as known kneading machine of heater meanses.In each material input kneading machine
Order has no particular limits, and after preferably the polyester based resin (A) as base-material first puts into melting, then puts into carbodiimides
Compound (B) and the other compositions added as needed.
The time of melting mixing can determine according to the shape of agitator, rotary speed etc. are appropriate, usually 1-30 minutes,
Preferably 1-10 minutes, more preferably 1-5 minutes.In addition, temperature during melting mixing is according to the polyester based resin as base-material
(A) species and different, usually 150-350 DEG C or so, preferably 200-320 DEG C or so, more preferably 240-300 DEG C
Left and right.
The carbodiimide compound (B) that the preparation method of the present invention uses, is preferably granulated.
Conventional polycarbodiimide additive, when being added because fusing point is low using extruder feeder etc., exist
At input port position, melting causes the difficult situation of input, on the other hand, by powdered polyester carbodiimides additive and
During the dry blended addition of polyester based resin particle, because shape is different, carbodiimides additive is segregated, and generation concentration be present
Uneven situation.Further, because the intermiscibility of polycarbodiimide additive and polyester based resin (A) is slightly worse, it is difficult to
It is dispersed in formed body at low concentrations.
On the other hand, the carbodiimide compound (B) that uses of the present invention, can through granulating and with polyester based resin (A)
It is dry-mixed to be processed as formed body.Especially, the big carbodiimide compound of molecular weight (B), due to high-melting-point, easily carrying out
Granulating.Because graininess is difficult to be segregated, and polyester fragment intramolecular exist, therefore with polyester based resin (A)
Intermiscibility is good, also can be dispersed in polyester based resin (A) formed body under low concentration.
Further, because polyester based resin (A) directly dry-mixed can be added, it is not necessary to prepare each Polyester
The masterbatch of resin (A), it is possible to reduce while preparation work amount, inactivation (ester caused by thermal histories in masterbatch can be avoided
It is the reaction of resin and carbodiimides).
[products formed for having used polyester resin composition]
The products formed of the present invention is the products formed for having used the polyester resin composition shaping of the present invention.
When obtaining products formed from the polyester resin composition of the present invention, extrusion can be passed through in above-mentioned melting mixing
Shaping, injection molding, blow molding etc. are molded, and chemical conversion masterbatch etc. can also be pre-mixed, then, with other materials melting mixing
And it is molded.
The present invention polyester resin composition, no matter use any forming method, due to shaping when melt viscosity not
It can be substantially increased, therefore operability is good.In addition, the products formed being molded by the polyester resin composition of the present invention, due to
Hydrolytic resistance is good, therefore the multinomial performance such as intensity is excellent.
Embodiment
Hereinafter, embodiment and comparative example are enumerated, more specific description is carried out to the present invention, but the present invention is not limited by it
It is fixed.
[assessment item]
(1) solution viscosity
Polyester resin composition through melting mixing is dried 4 hours at 130 DEG C, dried resin 0.15g exists
Mixed solution (phenol/tetrachloroethanes=1/1 (weight the ratio)) dissolving of 30mL phenol and tetrachloroethanes, with Kan Nong-Fen Sike
Viscosimeter is in 30 DEG C of measure.Unit is (dl/g).
(2) melt flow rate (MFR) (MFR) (melt viscosity)
Polyester resin composition through melting mixing is dried 4 hours at 130 DEG C, the melt viscosity analyzer used is
Melt flow rate (MFR) tester (island makes made VR-4100 in Co., Ltd.), in 270 DEG C of test temperature, testing load
Under 2.16kgf, melt flow rate (MFR) (MFR) is determined.Unit is (g/10min).Obtained MFR (g/10min) is viscous as melting
The index of degree.MFR value is bigger, represents that melt viscosity is lower.
(3) strength retention (hydrolytic resistance experiment)
By the polyester resin composition through melting mixing, the temperature more than softening point carries out flat-plate compressed, thickness is made
About 300 μm of thin slice, the thin slice is made to the long 70mm of wide 10mm rectangular sheet.
Next, by cupping machine, the tensile strength of rectangular sheet made of measure.Next, by made of
Rectangular sheet is put into Highly Accelerated Life Test device (ESPEC societies HASTCHAMBER EHS-210M), 121 DEG C,
Under conditions of 100%RH, sample is being taken out after 24 hours and after 40 hours, it is rectangular by cupping machine, measure
The tensile strength of shape thin slice.Calculate experiment before, experiment after respective 5 rectangular sheets tensile strength average value, under
State formula and try to achieve evaluation index of the strength retention as hydrolytic resistance.
Strength retention (%)=[(average value of the tensile strength after experiment)/(tensile strength before experiment is averaged
Value)] × 100
(4) resistance to exudative evaluation
Polyester resin composition through melting mixing is pressed under conditions of described in above-mentioned (3) strength retention,
The presence or absence of to obtained thin slice, confirm to ooze out by visual observation.
Synthesis example 1 (carbodiimide compound P1 synthesis)
By the mass parts of 4,4 '-hexylmethane 100 and carbodiimides catalyst (3- methyl isophthalic acids-
Phenyl -2- phosphorus -1- oxides) 0.5 mass parts are added in the reaction vessel with return duct and mixer, under stream of nitrogen gas
Stirred 24 hours at 185 DEG C, obtain poly- 4, the 4'- dicyclohexyl methyl hydrides carbodiimides that end is isocyanates.
Wavelength 2150cm is confirmed by infrared absorption (IR) spectroscopic assay-1Absorbed caused by front and rear carbodiimide-based
Peak.The isocyanate group concentration (hereinafter also referred to " NCO% ") remained by titration determination, is as a result 3.78%, (- R2- N-C=
N- the units (hereinafter also referred to " degree of polymerization ") that the component unit shown in) repeats is 9.0.
Next, end obtained above is heated for poly- 4, the 4'- dicyclohexyl methyl hydrides carbodiimides of isocyanates
To 150 DEG C, (Co., Ltd. is spun by Japan for addition poly glycol monomethyl ether (molecular weight 208) 7.9 mass parts and polyester-diol wherein
System " VYLON 220 ", molecular weight 3000) 57.3 mass parts, it is heated to 180 DEG C of stirring reactions 2 hours.
Wavelength 2200-2300cm is confirmed by infrared absorption (IR) spectroscopic assay-1The absorption of front and rear isocyanate group disappears
Afterwards, reactant is taken out from reaction vessel, is cooled to room temperature, obtain the carbodiimide compound P1 of pale yellow transparent.
Synthesis example 2-4 (carbodiimide compound P2-P4 synthesis)
In synthesis example 1, except raw material composition and reaction condition be changed into table 1 record condition in addition to, using with synthesis example 1
Identical method, obtain carbodiimide compound P2-P4.
Synthesis example 5 (carbodiimide compound P5 synthesis)
In synthesis example 1, except the species of reaction condition and end-capping reagent is changed into the condition of the record of table 1, polyester two is added without
Beyond alcohol (Japan spin Co. Ltd. system " VYLON 220 ", molecular weight 3000), using with the identical method of synthesis example 1, obtain carbon
Change diimine compounds P5.
Synthesis example 6 (granular carbonization diimine compounds P6 synthesis)
By the mass parts of 4,4 '-hexylmethane 100 and carbodiimides catalyst (3- methyl isophthalic acids-
Phenyl -2- phosphorus -1- oxides) 0.5 mass parts are added in the reaction vessel with return duct and mixer, under stream of nitrogen gas
Stirred 28 hours at 185 DEG C, obtain poly- 4, the 4'- dicyclohexyl methyl hydrides carbodiimides that end is isocyanates.By infrared
Absorb (IR) spectroscopic assay wavelength 2150cm-1Absworption peak caused by front and rear carbodiimide-based.NCO% measurement result is
2.92% (degree of polymerization=12.0).
Next, end obtained above is heated for poly- 4, the 4'- dicyclohexyl methyl hydrides carbodiimides of isocyanates
To 150 DEG C, poly glycol monomethyl ether (molecular weight 208) 6.1 mass parts are added wherein, are heated to 180 DEG C of stirring reactions 1 hour
Afterwards, reactant is taken out from reaction vessel, is cooled to room temperature, obtain the 4,4'- of the isocyanates list end of pale yellow transparent
Dicyclohexyl methyl hydride carbodiimides.
Next, by the mass parts of 4,4'- dicyclohexyl methyl hydrides carbodiimides 90.6 of above-mentioned isocyanates list end and
Polyester-diol (Japan spin Co. Ltd. system " VYLON 220 ", molecular weight 3000) 44.0 mass parts are supplied to double screw extruder
(Toyo Co., Ltd. is refined to make made, Labo Plastomill) carries out melting mixing at 180 DEG C, will obtain extrudate and exists
Grain shape is processed into comminutor, obtains granular carbodiimide compound P6.
Obtained granular carbonization diimine compounds P6 confirms wavelength 2200- by infrared absorption (IR) spectroscopic assay
2300cm-1Front and rear isocyanate group, which absorbs, to disappear.
Synthesis example 7 (granular carbonization diimine compounds P7 synthesis)
In synthesis example 6, except raw material composition and reaction condition be changed into table 1 record condition in addition to, using with synthesis example 6
Identical method, obtain carbodiimide compound P7.
Table 1
*1：HMDI, 4,4 '-hexylmethane
*2：TMXDI, tetramethyl xylylene diisocyanate
*3：3- methyl isophthalic acids-phenyl -2- phosphorus -1- oxides
*4：PG1, poly glycol monomethyl ether, molecular weight 208
*5：PG2, poly glycol monomethyl ether, mean molecule quantity 400
*6：Co. Ltd. system " VYLON 220 ", mean molecule quantity 3000 spin in PE1, polyester-diol, Japan
*7：PC, PCDL, Asahi Chemical Corp's system " DURANOL T-5650E ", mean molecule quantity
500
*8：PE2, polyester-diol, Unitika Co. Ltd. systems " XP-1233 ", mean molecule quantity 3900
*9：Per the formula weight of 1mol carbodiimide-baseds
Embodiment 1
The mass parts of PET resin (Sinopec system) 99.00 are melted under conditions of 270 DEG C by laboratory mixer
Afterwards, the obtained mass parts of carbodiimide compound P1 1.00 are added in synthesis example 1, mixes 3 minutes, obtains polyester based resin
Composition.The viscosity characteristics of obtained polyester resin composition are as shown in table 2.
Embodiment 2-5, comparative example 1-4
In embodiment 1, in addition to proportioning composition is changed into proportioning composition as shown in table 2, using same as Example 1
Method, obtain polyester resin composition.The viscosity characteristics of obtained polyester resin composition are as shown in table 2.
Table 2
*1：Pet resin (PET resin), Sinopec system
*2：Carbodiimides concentration (quality %)：Carbodiimide-based (- N=C=N-) contains in polyester resin composition
Amount=[theoretical carbodiimide-based concentration (quality %) × addition (mass parts)/polyester in carbodiimide compound (B)
Based resin composition (mass parts)] × 100
Embodiment 6-8, comparative example 5-8
Confirm the hydrolytic resistance for the polyester resin composition that each embodiment and comparative example obtain and the presence or absence of ooze out.As a result
As shown in table 3.
Table 3
*1：By the mass parts of PET resin (Sinopec system) 100 by laboratory mixer under conditions of 270 DEG C melt
Melt obtained material
From table 2-3, polyester resin composition of the invention, although being the carbodiimide-based equal with comparative example
Concentration, but no melt viscosity and solution viscosity are substantially increased, hydrolytic resistance and resistance to exudative good.
On the other hand, the carbodiimides chemical combination containing the residue in carbodiimide compound with PCDL
The melt viscosity of the polyester resin composition of thing P4 comparative example 1 rises notable.
In addition, the carbodiimide compound P5 containing the residue for not having diol compound in carbodiimide compound
Comparative example 2-3, and contain use as diisocyanate without alicyclic structure aliphatic diisocyanate carbonization
The thin slice (comparative example 6-8) that diimine compounds P3 comparative example 4 obtains, the thin slice (embodiment obtained than embodiment 1-2 and 4
Hydrolytic resistance 6-8) is poor.
Claims (9)
1. a kind of polyester resin composition, the polyester resin composition contains polyester based resin (A) and following formulas (1) institute
The carbodiimide compound (B) shown, relative to the mass of total amount 100 of polyester based resin (A) and carbodiimide compound (B)
Part, the content of carbodiimide compound (B) is 0.1-8 mass parts；
[chemical formula 1]
In formula, R1Represent the residue with one with the compound of functional group of the isocyanates with reactivity；R2Represent have extremely
The aliphatic group of the divalence of a few alicyclic structure, and-N=C=N- and R2Alicyclic structure Direct Bonding；R3For polyester
The residue of the divalence of glycol；X represents the group selected from following formulas (2)-(4), and m represents 1-20 number, and n represents 1-20 number, p
Represent 1-5 number；Multiple R2, X it is each identical or different；
[chemical formula 2]
- N=C=N- (4).
2. polyester resin composition according to claim 1, wherein, the number-average molecular weight of the polyester-diol is
1000-40000。
3. polyester resin composition according to claim 1 or 2, wherein, the R2For the ring of 4,4 '-diisocyanate two
The residue of the divalence of hexyl methane.
4. polyester resin composition according to claim 1 or 2, wherein, the carbon of the carbodiimide compound (B)
It is 100-1000 to change diimine equivalent.
5. polyester resin composition according to claim 1 or 2, wherein, the polyester based resin (A) is selected from poly- pair
In PET, polybutylene terephthalate (PBT), poly butylene succinate, PLA and poly (hydroxy alkanoate)
More than one.
6. polyester resin composition according to claim 1 or 2, wherein, it is described with one with isocyanates with
The compound of the functional group of reactivity is monohydric alcohol, monohydric phenol, monoisocyanates or monoamine.
7. the preparation method of the polyester resin composition in claim 1-6 described in any one, this method is by the polyester
It is resin (A) and the carbodiimide compound (B) melting mixing.
8. the preparation method of polyester resin composition according to claim 7, wherein, the carbodiimide compound
(B) it is the compound through granulating.
9. a kind of products formed, the products formed usage right requires the polyester resin composition shaping described in any one in 1-6
Form.
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| JP2014020609A JP5793586B2 (en) | 2014-02-05 | 2014-02-05 | POLYESTER RESIN COMPOSITION, PROCESS FOR PRODUCING THE POLYESTER RESIN COMPOSITION, AND MOLDED ARTICLE USING THE POLYESTER RESIN COMPOSITION |
| JP2014-020609 | 2014-02-05 | ||
| PCT/JP2015/053219 WO2015119191A1 (en) | 2014-02-05 | 2015-02-05 | Polyester-based resin composition, production method for said polyester-based resin composition, and molded article using said polyester-based resin composition |
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| JP6984838B2 (en) * | 2016-12-27 | 2021-12-22 | 日清紡ケミカル株式会社 | A method for producing a carboxyl group-containing aqueous resin composition, a molded product, and a polycarbodiimide compound. |
| JP7017460B2 (en) * | 2017-06-30 | 2022-02-08 | 三井化学株式会社 | Method for producing polycarbodiimide composition, polycarbodiimide composition, aqueous dispersion composition, solution composition, resin composition and cured resin |
| JP6947468B2 (en) * | 2017-08-28 | 2021-10-13 | 日清紡ケミカル株式会社 | Polycarbodiimide compound and thermosetting resin composition |
| CN108084056A (en) * | 2017-12-29 | 2018-05-29 | 上海朗亿功能材料有限公司 | A kind of block copolymerization type carbodiimides and preparation method thereof |
| JP2020070363A (en) * | 2018-10-31 | 2020-05-07 | 日清紡ケミカル株式会社 | Polyester resin modifier and method for producing the same and polyester resin composition |
| EP3875448A4 (en) * | 2018-10-31 | 2022-07-20 | Nisshinbo Chemical Inc. | Polycarbodiimide compound, and polyester resin composition and polyester resin modifier in which same is used |
| JP6799720B1 (en) * | 2019-03-22 | 2020-12-16 | 日清紡ケミカル株式会社 | Powdered polycarbodiimide compound and ester resin composition |
| JP7312005B2 (en) * | 2019-04-15 | 2023-07-20 | 日清紡ケミカル株式会社 | Polyester resin composition |
| JP7249197B2 (en) * | 2019-04-15 | 2023-03-30 | 日清紡ケミカル株式会社 | Polyester resin composition |
| JP2021066845A (en) * | 2019-10-28 | 2021-04-30 | 日清紡ケミカル株式会社 | Compatibilizer and polyester resin composition |
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