CN104066789B - The manufacture method of thermoplastic resin composition and thermoplastic resin composition - Google Patents
The manufacture method of thermoplastic resin composition and thermoplastic resin composition Download PDFInfo
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- CN104066789B CN104066789B CN201380005043.2A CN201380005043A CN104066789B CN 104066789 B CN104066789 B CN 104066789B CN 201380005043 A CN201380005043 A CN 201380005043A CN 104066789 B CN104066789 B CN 104066789B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/60—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
The invention provides and there is excellent height circulation formability and the thermoplastic resin composition of the good products formed of appearance and the manufacture method of thermoplastic resin composition can be obtained.Thermoplastic resin composition of the present invention, contain: (A) polybutylene terephthalate resin, (B) pet resin, and (C) cross-linked resin, described (A) polybutylene terephthalate resin, the mixing ratio of described (B) pet resin and described (C) cross-linked resin is, relative to described (A) polybutylene terephthalate resin 100 mass parts, there is described (B) pet resin 10 ~ 70 mass parts, described (C) cross-linked resin 0.0001 ~ 10 mass parts.
Description
Technical field
The present invention relates to and be combined with the thermoplastic resin composition of polybutylene terephthalate resin, pet resin and cross-linked resin and the manufacture method of thermoplastic resin composition.
Background technology
The thermoplastic polyesters such as polybutylene terephthalate resin, pet resin, the excellences such as mechanical characteristics, electrical specification, resistance, thermotolerance, so widely used by as the vehicle inside and outside decorative elements such as various electric and electronic parts, automobile, train, electric car and general Industrial products manufacture material.And then, due to the mould transferability (moldtranscription) of these polybutylene terephthalate resins, pet resin excellent, so be also used to the parts of the such pursuit outward appearance of external decorating member, it utilizes scope also in continuous expansion.As the polyester and resin composition of the good appearance for external decorating member, disclose such as, be made up of polybutylene terephthalate resin, pet resin and barium sulfate, at the resin combination (for example, referring to patent documentation 1) that the weight loss on heating of 250 DEG C of thermal treatments after 30 minutes is below 0.5 quality %.In recent years, in this external decorating member purposes, for the object improving productivity raising, pursue the shortening in injection molding cycle, thus the thermoplastic resin composition of demand outward appearance and high circulation formability (high-cyclemoldability) excellence.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2002-332396 publication
Summary of the invention
The problem that invention will solve
The present invention's problem in view of the aforementioned technical background, its object is to provide and has excellent height circulation formability, can obtain the thermoplastic resin composition of the good products formed of appearance and the manufacture method of thermoplastic resin composition.
Solve the means of problem
In order to solve above-mentioned problem, realize object, thermoplastic resin composition of the present invention, contain: (A) polybutylene terephthalate resin, (B) pet resin, and (C) cross-linked resin, described (A) polybutylene terephthalate resin, the mixing ratio of described (B) pet resin and described (C) cross-linked resin is, relative to described (A) polybutylene terephthalate resin 100 mass parts, there is described (B) pet resin 10 ~ 70 mass parts, described (C) cross-linked resin 0.0001 ~ 10 mass parts.
In addition, thermoplastic resin composition of the present invention, in the present invention as stated above, described (C) cross-linked resin contains the resin with the crosslinking structure formed via (D) linking agent.
In addition, thermoplastic resin composition of the present invention, in the present invention as stated above, described (C) cross-linked resin is the cross-linked resin that the resin containing vibrin, acrylic resin and/or urethane resin has been cross-linked via (D) linking agent.
In addition, thermoplastic resin composition of the present invention, in the present invention as stated above, described (D) linking agent contains
azoles quinoline class linking agent and/or melamine class linking agent.
In addition, thermoplastic resin composition of the present invention, in the present invention as stated above, described (B) pet resin contains and experiences at least a kind of operation being selected from film molding procedure, melt-spinning operation and injection molding operation and the pet resin (B1) that obtains.
In addition, thermoplastic resin composition of the present invention, in the present invention as stated above, at least a kind of operation being selected from described film molding procedure, described melt-spinning operation and described injection molding operation is experienced and the melt flow rate (MFR) of pet resin (B1) that obtains is 10 ~ 100g/10 minute.
In addition, thermoplastic resin composition of the present invention, in the present invention as stated above, experience at least a kind of operation being selected from described film molding procedure, described melt-spinning operation and described injection molding operation and the intensification of the pet resin (B1) that obtains time crystallized temperature be 140 DEG C ~ 160 DEG C.
In addition, thermoplastic resin composition of the present invention, in the present invention as stated above, described (C) cross-linked resin is from stack membrane.
In addition, the manufacture method of thermoplastic resin composition of the present invention, by coordinating (A) polybutylene terephthalate resin, (B) pet resin and be formed with the stack membrane of the layer containing (C) cross-linked resin at least one side of the base material film formed by polybutylene terephthalate and/or polyethylene terephthalate, by they melting mixings, thus the thermoplastic resin composition described in any one of manufacturing claims 1 ~ 8.
In addition, the manufacture method of thermoplastic resin composition of the present invention, in the present invention as stated above, after by described stack membrane pulverizing and/or granulation, be coupled in described (A) polybutylene terephthalate resin and described (B) pet resin, and carry out melting mixing.
Invention effect
The present invention, can provide the thermoplastic resin composition having excellent height circulation formability, can obtain the good products formed of appearance.The thermoplastic resin composition of the application of the invention, can significantly shorten the injection molding cycle.
Embodiment
To be specifically described the present invention below.
(A) polybutylene terephthalate resin used in the present invention is by terephthalic acid and/or its ester formative derivative, the polymkeric substance that carries out polycondensation and obtain with BDO and/or its ester formative derivative.As the ester formative derivative of terephthalic acid, can list such as, the alkyl ester etc. of the terephthalic acids such as dimethyl terephthalate (DMT).As the ester formative derivative of BDO, can list such as, the alkyl ester etc. of the glycol of BDO ester etc.
(A) of the present invention polybutylene terephthalate resin, in the limit of not destruction characteristic, other dicarboxylic acid or its ester formative derivative can also be made together with terephthalic acid or its ester formative derivative, with BDO and/or its ester formative derivative to carry out copolymerization.In addition, other glycol or its ester formative derivative also can be made together with BDO or its ester formative derivative, with terephthalic acid and/or its ester formative derivative to carry out copolymerization.The dicarboxylic acid used as copolymer composition or its ester formative derivative, can list such as, m-phthalic acid, hexanodioic acid, oxalic acid, sebacic acid, decane dicarboxylic, naphthalic acid and their alkyl ester etc.They also can use two or more.In addition, the glycol used as copolymer composition or its ester formative derivative, can list such as, ethylene glycol, propylene glycol, neopentyl glycol, 1, the polyoxyethylene glycol of 5-pentanediol, 1,6-hexylene glycol, decamethylene-glycol, cyclohexanedimethanol, cyclohexane diol, molecular weight 400 ~ 6000 or poly-1, the long chain diol of ammediol, poly-BDO etc. and their fatty acid ester etc.They also can use two or more.These copolymer compositions preferably account for below 20 quality % in the raw material forming (A) polybutylene terephthalate resin.
As the preference of this multipolymer, poly-(terephthalic acid/isophthalic acid) butanediol ester, poly-(terephthalic acid/hexanodioic acid) butanediol ester, poly-(terephthalic acid/sebacic acid) butanediol ester, poly-(terephthalic acid/decane dicarboxylic) butanediol ester, poly-(terephthalic acid/naphthalic acid) butanediol ester, poly terephthalic acid (butyleneglycol/ethylene glycol) ester etc. can be listed.As (A) of the present invention polybutylene terephthalate resin, also can with the use of two or more in them.
(B) pet resin used in the present invention is by terephthalic acid and/or its ester formative derivative, the polymkeric substance that carries out polycondensation and obtain with ethylene glycol and/or its ester formative derivative.As the ester formative derivative of terephthalic acid, can list and to enumerate listed by the ester formative derivative as the terephthalic acid forming (A) polybutylene terephthalate resin.As the ester formative derivative of ethylene glycol, can list such as, as glycol fatty acid ester etc. fatty acid ester etc. listed by enumerate.
(B) of the present invention pet resin, can also, together with terephthalic acid or its ester formative derivative, other dicarboxylic acid or its ester formative derivative be made to carry out copolymerization with ethylene glycol and/or its ester formative derivative together in the limit of not destruction characteristic.In addition, other glycol or its ester formative derivative also can be made together with ethylene glycol or its ester formative derivative, with terephthalic acid or its ester formative derivative to carry out copolymerization.The dicarboxylic acid used as copolymer composition or its ester formative derivative, as glycol or its ester formative derivative, can to list as to enumerate listed by the copolymer composition forming (A) polybutylene terephthalate resin.They can use two or more.These copolymer compositions preferably account for below 20 quality % in the raw material forming (B) pet resin.
As the preference of this multipolymer, poly-(terephthalic acid/isophthalic acid) glycol ester, poly-(terephthalic acid/hexanodioic acid) glycol ester, poly-(terephthalic acid/sebacic acid) glycol ester, poly-(terephthalic acid/decane dicarboxylic) glycol ester, poly-(terephthalic acid/naphthalic acid) glycol ester etc. can be listed.(B) of the present invention pet resin can with the use of two or more.
The use level of (B) pet resin in thermoplastic resin composition of the present invention is 10 ~ 70 mass parts relative to (A) polybutylene terephthalate resin 100 mass parts.If (B) use level of composition is greater than 70 mass parts, then the curing speed of thermoplastic resin composition is significantly slack-off, and shaping cycle is elongated, namely, high circulation formability reduce.Be preferably below 65 mass parts.In addition, if the use level of (B) composition is lower than 10 mass parts, then curing speed accelerates, so mould transferability reduces, thus the appearance of products formed reduces.Be preferably more than 15 mass parts.
(A) polybutylene terephthalate resin used in the present invention and (B) pet resin can be manufactured by known condensation methods or ring-opening polymerization method etc.Any one in batchwise polymerization method and continuous polymerization can be used, but end carboxyl amount, mobility raising effect more broad aspect can reduced, preferred continuous polymerization.In addition, any one in transesterification reaction and direct polymerization reaction can be adopted, but in cost, preferred direct polymerization reaction.In order to enable esterification, transesterification reaction and/or polycondensation more effectively carry out, preferably add catalyzer when these react.As the concrete example of catalyzer, the methyl ester of metatitanic acid can be listed, four n-propyl esters, tetra-n-butyl ester, tetra isopropyl ester, four isobutyl, tetra-tert ester, cyclohexyl ester, phenylester, benzyl ester, tolyl ester, or the organic titanic compound of their mixed ester etc., Dibutyltin oxide, aminomethyl phenyl stannic oxide, tin tetraethyl, Hexaethyl tindioxide, ring six hexyl tindioxide, two (dodecyl) stannic oxide, triethylphosphine hydroxide, fentin hydroxide, triisobutyl tin acetic ester, dibutyltin bisacetate, phenylbenzene tin dilaurate tin, monobutyl-tin-trichloride, dibutyl tin dichloride, tributyltin chloride, dibutyltin sulfide and butylhydroxy stannic oxide, stannoacetic acid, ethyl stannonic acid, the tin compounds such as the alkyl tin acid of butyl stannonic acid etc., the zirconium compounds of four n-butoxy zirconiums etc., ANTIMONY TRIOXIDE SB 203 99.8 PCT, the antimony compounds etc. of antimony acetate etc.They can use two or more.Preferred organic titanic compound and tin compound, more preferably the tetra-n-butyl ester of metatitanic acid in these.The addition of catalyzer is generally 0.01 ~ 0.2 mass parts relative to (A) polybutylene terephthalate resin or (B) pet resin 100 mass parts.
Thermoplastic resin composition of the present invention, the pet resin (B1) that (B) pet resin preferably obtains containing a kind of operation through being selected from film molding procedure, melt-spinning operation and injection molding operation.Experience these operations and the pet resin (B1) obtained, compared with not passing through the original pet resin of these operations, receive more thermal history, so the mobility of the thermoplastic resin composition of gained improves.Pet resin (B1), also can experience for several times above-mentioned operation, also can experience operation of more than two kinds, operation number of times and operation kind more, then the mobility of the thermoplastic resin composition of gained is higher.Equally, (A) polybutylene terephthalate resin is also, due to can mobility be improved by experience film molding procedure, melt-spinning operation or injection molding operation, so the polybutylene terephthalate resin that can also use experience film molding procedure, melt-spinning operation or injection molding operation as thermoplastic resin composition of the present invention and obtain.
In thermoplastic resin composition of the present invention, the melt flow rate (MFR) (being denoted as MFR below) that preferably experiences at least a kind of operation be selected from described film molding procedure, melt-spinning operation and injection molding operation and the pet resin (B1) obtained or (B) pet resin containing pet resin (B1) is 10 ~ 100g/10 minute.If MFR is more than 10g/10 minute, then the mobility of the thermoplastic resin composition of gained becomes higher.Be more preferably more than 12g/10 minute.On the other hand, if MFR is less than 100g/10 minute, then the mechanical properties of the products formed formed by thermoplastic resin composition of the present invention improves.More preferably less than 90g/10 minute.Wherein, the MFR in the present invention uses in advance at the pellet of 130 DEG C of dryings after 4 hours, according to ISO1133, and the amount of polymers flowed out when measuring under the condition of test temperature 275 DEG C, load 325g.There is the pet resin (B1) of the MFR of this scope, as long as such as experience at least a kind of operation being selected from film molding procedure, melt-spinning operation and injection molding operation and obtain, but preferably use will at least a kind of operation being selected from film molding procedure, melt-spinning operation and injection molding operation of experience and the pet resin (B1) that obtains drop in pulverizer be ground into clastic.The pulverizing process number of times of pet resin (B1) is more, then have the MFR value of pet resin (B1) to become higher tendency.
The crystallized temperature during intensification of at least a kind of operation in thermoplastic resin composition of the present invention, through being selected from film molding procedure, melt-spinning operation and injection molding operation and the pet resin (B1) that obtains or (B) pet resin containing pet resin (B1) (below be denoted as Tcc) is preferably 140 ~ 160 DEG C.If Tcc is within the scope of this, then crystal growth rate can become the scope being more suitable for forming process, and formability becomes higher.Wherein, Tcc in the present invention, refer to and use compact hot press etc. to be heated to more than 270 DEG C, at once quenching in the heat-eliminating medium of liquid nitrogen etc. is put into, the value of endotherm(ic)peak when being used by the sample of gained differential scanning calorimeter (DSC) to be warmed up to 300 DEG C with 20 DEG C/minute of heat-up rates from 40 DEG C after melting.There is the pet resin (B1) of the Tcc of this scope; such as; as long as experience at least a kind of operation being selected from film molding procedure, melt-spinning operation and injection molding operation and obtain; but preferably use and will experience at least a kind of operation be selected from film molding procedure, melt-spinning operation and injection molding operation and the pet resin (B1) obtained and drop in pulverizer and be ground into fragmental; then to put in tablets press, use rotating roller to apply pressure compaction, spue.At pet resin (B1) if granulation time heating, then have the tendency that Tcc reduces, if cool, then have the tendency that Tcc improves.
Thermoplastic resin composition of the present invention, is characterised in that, and then also containing (C) cross-linked resin.By making thermoplastic resin composition of the present invention contain (C) cross-linked resin, in thermoplastic resin composition of the present invention, (C) cross-linked resin becomes the nuclei of crystallization, so curing speed is accelerated, high circulation formability improves.As (C) cross-linked resin, the thermosetting resin that the resins such as unsaturated polyester resin, urethane resin, epoxy resin, silica resin, urea resin, resol can be cross-linked separately can be listed, and thermoplastic polyester, acrylic resin etc. by so with crosslinker combination and the thermoplastic resin etc. that can be cross-linked.Can also by thermosetting resin and then and crosslinker combination, make its be cross-linked.
(C) cross-linked resin used in the present invention, preferably containing the resin with the crosslinking structure formed via (D) linking agent.As the resin with the crosslinking structure formed via (D) linking agent, can list such as, the resin that vibrin, acrylic resin, urethane resin, epoxy resin, silica resin, urea resin, resol etc. have been cross-linked via (D) linking agent.As (C) cross-linked resin used in the present invention, two or more in them can be used.
As (C) of the present invention cross-linked resin, in the situation of resin using vibrin or be cross-linked via linking agent by vibrin, as vibrin, can list such as, pet resin, polybutylene terephthalate resin, poly terephthalic acid 1,3-PD ester resin, PEN resin, PBN resin, Polyester Resin Water Soluble etc. containing carboxylate group or sulphonate-base.In addition, in the situation of the resin using acrylic resin to be cross-linked via linking agent as (C) cross-linked resin, as acrylic resin, can list such as, the polymkeric substance of alkyl methacrylate, the polymkeric substance etc. of alkyl acrylate.Urethane resin is the resultant of reaction of polyol compound and isocyanate compound.The situation of the resin be cross-linked via linking agent by urethane resin or urethane resin is being used as (C) cross-linked resin, as polyol compound, can list such as, polyoxyethylene glycol, polypropylene glycol, polyoxyethylene glycol/propylene glycol, poly-1, 4-butyleneglycol, 1, 6-hexylene glycol, 1, 4-butyleneglycol, 1, 5-pentanediol, Diethylene Glycol etc., as isocyanate compound, can list such as, tolylene diisocyanate, 1, hexamethylene-diisocyanate, phenylene diisocyanate, diphenylmethanediisocyanate etc., as urethane resin, the arbitrary resultant of reaction of above-mentioned polyol compound and isocyanate compound can be listed.
As (C) cross-linked resin, the situation of resin using epoxy resin or be cross-linked via linking agent by epoxy resin, as epoxy resin, can list such as, glycidyl ether type epoxy resin, bisphenol A type epoxy resin, dihydroxyphenyl propane D type epoxy resin, bisphenol-s epoxy resin, Resorcinol type epoxy resin, polyoxyethylene-type epoxy resin etc.In the situation of resin using silica resin as (C) cross-linked resin or be cross-linked via linking agent by silica resin, as silica resin, can list such as, dimethyl polysiloxane, methylphenyl siloxane, alkyl-modified polysiloxane, PE modified polysiloxane, polyoxyamylene modified polyorganosiloxane etc.In the situation of resin using urea resin as (C) cross-linked resin or be cross-linked via linking agent by urea resin, as urea resin, can list such as, MU resin, thiourea resin, ethylene-urea resin, dihydroxymethyl urea resin, methylolurea resin etc.In the situation of resin using resol as (C) cross-linked resin or be cross-linked via linking agent by resol, as resol, can list such as, line style varnish-type phenolic resin, resol type phenol resin etc.Also two or more in them can be used.
As (C) cross-linked resin used in the present invention, in them, the resin that the resin preferably containing vibrin, acrylic resin and/or urethane resin has been cross-linked via (D) linking agent.Vibrin, acrylic resin, urethane resin are high with the consistency of (A) polybutylene terephthalate resin and (B) pet resin.Therefore, it is possible to dispersed in the thermoplastic resin composition of gained, so the crystallinity of thermoplastic resin composition improves, shaping cycle shortens, and namely high circulation formability becomes higher.
As (D) linking agent used in the present invention, can list such as,
azoles quinoline class linking agent, melamine class linking agent, carbodiimide class linking agent, isocyanates linking agent, epoxies linking agent etc.(D) linking agent used in the present invention also can use two or more in them.
azoles quinoline class linking agent has
the compound of azoles quinoline base, is using as (D) linking agent
the situation of azoles quinoline class linking agent, can list such as, 2-vinyl-2-
azoles quinoline, 2-vinyl-4-methyl-2-
azoles quinoline, 2-vinyl-5-methyl-2-
azoles quinoline, 2-pseudoallyl-2-
azoles quinoline, 2-pseudoallyl-4-methyl-2-
azoles quinoline, 2-pseudoallyl-5-ethyl-2-
azoles quinoline etc.
Melamine class linking agent is the melamine compound with imido grpup, methylol and/or alkoxy methyl, the situation of melamine class linking agent is being used as (D) linking agent, can list such as, imines fundamental mode methylated melamine, methylol type trimeric cyanamide, methylol type methylated melamine, completely alkyl type methylated melamine etc.Carbodiimide class linking agent is the compound with carbodiimide or more than 1, cyanamide base, the situation of carbodiimide class linking agent is being used as (D) linking agent, can list such as, dicyclohexyl methyl hydride carbodiimide, dicyclohexylcarbodiimide, tetramethyl xylene carbodiimide, urea carbon modified diimine etc.Using the situation of isocyanates linking agent as (D) linking agent, can list such as, tolylene diisocyanate, ditan-4,4 '-vulcabond, m xylene diisocyanate, hexa-methylene-1,6-vulcabond etc.Using the situation of epoxies linking agent as (D) linking agent, can list such as, Sorbitol Powder poly epihydric alcohol base ether, Polyglycerine poly epihydric alcohol base ether, two glycerine poly epihydric alcohol base ethers, polyethylene glycol diglycidyl base ether etc.
In them, preferably
azoles quinoline class linking agent and/or melamine class linking agent.
azoles quinoline class linking agent and melamine class linking agent, excellent with the reactivity of aforesaid vibrin, acrylic resin, urethane resin, so easily crosslinking structure can be formed in these resins.
(C) cross-linked resin, in the situation of to be resin containing vibrin, acrylic resin and/or urethane resin the be resin be cross-linked via (D) linking agent, the total amount of vibrin, acrylic resin and urethane resin is preferably 98/2 ~ 52/48 with the proportioning (mass ratio) of (D) linking agent.By making, the proportioning of resin is less than 98, the proportioning of linking agent is more than 2, and the effect as the nuclei of crystallization of (C) cross-linked resin can be made to improve, and high circulation formability becomes higher.On the other hand, by making, the proportioning of resin is more than 52, the proportioning of linking agent is less than 48, moderately can suppress the viscosity of (C) cross-linked resin, so operability is excellent.The total amount of vibrin, acrylic resin and urethane resin and the proportioning of (D) linking agent are more preferably 85/15 ~ 65/35.
In addition, (C) cross-linked resin used in the present invention, preferably be selected from least a kind of operation in film molding procedure, melt-spinning operation and injection molding operation from aforesaid experience and the pet resin (B1) obtained, more preferably from stack membrane, be namely the stack membrane being formed layer at least partially by (C) cross-linked resin.And then particularly preferably use polybutylene terephthalate and/or polyethylene terephthalate as the base material film of stack membrane, and form the stack membrane of the layer containing (C) cross-linked resin at least one side of this base material film.Because stack membrane is heated when shaping, be subject to more thermal history, so in the situation selecting this stack membrane as the material of (C) cross-linked resin, the mobility of the thermoplastic resin composition of gained improves, shaping cycle shortens, high circulation formability becomes higher.Stack membrane, at least one mask of base material polybutylene terephthalate film and/or polyethylene terephthalate film have for give binding property, solvent resistance the situation of various resin layers a lot, in the present invention preferably as give binding property, solvent resistance resin layer and there is the layer containing (C) cross-linked resin.In addition, also can be used in add (C) cross-linked resin shaping membrane in mould material material, maybe will to add or the resin material of coating (C) cross-linked resin carries out melt-spinning, injection molding material as (C) cross-linked resin.The resin material being added (C) cross-linked resin is preferably polybutylene terephthalate and/or polyethylene terephthalate.
And then, (C) cross-linked resin of using in the present invention, the stack membrane that preferably at least will be formed with the layer containing (C) cross-linked resin is pulverized and/or granulation and obtaining.By being pulverized and/or granulation by stack membrane, raw material during melting mixing drops into and becomes easy, and melting mixing improves.
Such as, moreover (C) cross-linked resin contained in thermoplastic resin composition, can be determined by infrared absorption analysis, Differential Scanning Calorimetry mensuration etc.
The use level of (C) cross-linked resin used in the present invention is 0.0001 ~ 10 mass parts relative to (A) polybutylene terephthalate resin 100 mass parts.(C) when the use level of cross-linked resin is greater than 10 mass parts, mobility reduces, so shaping cycle is elongated, high circulation formability reduces.Be preferably below 8 mass parts.In addition, when the use level of (C) cross-linked resin is lower than 0.0001 mass parts, curing speed reduces, so shaping cycle is elongated, high circulation formability reduces.Be preferably more than 0.0005 mass parts.
In thermoplastic resin composition of the present invention, in the limit not destroying object of the present invention, the known additive such as fiber strengthening material, antioxidant, UV light absorber, softening agent, antistatic agent of the non-halogen based flame retardant, glass fibre etc. of the halogen flame, phosphorus type flame retardant etc. of the resin, brominated flame retardant etc. beyond (A) polybutylene terephthalate resin, (B) pet resin, (C) cross-linked resin can also be coordinated.In addition, also can matching surface promoting agent in thermoplastic resin composition of the present invention.As tensio-active agent, can list such as, carboxylic acid type amphoterics, betaine type amphoteric surfac-tant, phosphate surfactant, glycine type tensio-active agent, nonionic surfactant etc.By matching surface promoting agent in thermoplastic resin composition of the present invention, consistency and the dispersiveness of (A) polybutylene terephthalate resin and (B) pet resin can be improved.Moreover these surfactant components coordinated in thermoplastic resin composition, can pass through such as, the infrared absorption analysis, means of differential scanning calorimetry mensuration etc. of thermoplastic resin composition are determined.
Thermoplastic resin composition of the present invention can be manufactured by generally well-known method.Such as, by by mixing for other components fuse of (A) polybutylene terephthalate resin, (B) pet resin, (C) cross-linked resin and necessity, thus preparation thermoplastic resin composition.The present invention, both (C) cross-linked resin former state directly can be coordinated, also by least one side that is added in polybutylene terephthalate film or polyethylene terephthalate film having the stack membrane of the layer containing (C) cross-linked resin, (C) cross-linked resin can be coordinated.In thermoplastic resin composition of the present invention, at least one side being preferably engaged in polybutylene terephthalate film or polyethylene terephthalate film has the stack membrane of the layer containing (C) cross-linked resin.If coordinate the stack membrane being subject to more thermal history, then the mobility of the thermoplastic resin composition of gained improves, so shaping cycle shortens, high circulation formability is higher.In this situation, preferably described stack membrane to be pulverized and/or after granulation, with (A) polybutylene terephthalate resin melting mixing together with (B) pet resin.The stack membrane formerly will with the layer containing (C) cross-linked resin is pulverized and/or granulation, the then situation of melting mixing, and raw material during melting mixing drops into and becomes easy, and melting mixing improves.Melting mixing can use such as there is " ユ ニ メ Le ト (registered trademark) " or Dole McGee (Dulmage) type screw rod the multiple screw extruder such as single axle extruding machine, two axle forcing machines, three axle forcing machines, kneading type mixing roll etc.
If desired, also a part of composition can be pre-mixed, and then coordinate other composition, carry out melting mixing.As the example be pre-mixed, can list be dry mixed method, use the mechanical mixing apparatus such as pivoted arm (tumbler), ribbon blender and Henschel mixer and the method etc. that mixes.In addition, be combined with the situation of fiber strengthening material, also side opening for feed can be set in the midway of the main charging oral area of multiple screw extruder and discharge portion and add.In addition, in the situation of fluid,matching body additives, following methods can be used: arrange at the main charging oral area of multiple screw extruder and the midway of discharge portion and add liquid nozzle, carried out the method for adding by ram pump, and, the method etc. supplied from main charging oral area etc. with pump of constant delivery type.
Thermoplastic resin composition of the present invention, can be shaping by any means such as generally well-known injection molding, extrusion moulding, blow molding, compression mouldings, can use after being processed into various products formed.Various products formed, can use in the various uses such as trolley part, electrical and electronic parts, building element, various container, daily necessities, life foreign material and sanitary product.
Embodiment
Come by the following examples more specifically to illustrate effect of the present invention.Wherein, " part " all represents " mass parts ".The measuring method of each characteristic is as follows.
(1) MFR measuring method
By (B) pet resin of using in each embodiment and comparative example in the hot air dryer of 130 DEG C dry 4 hours, then under the condition of test temperature 270 DEG C, load 325g, measure according to the method for ISO1133 the amount of resin flowed out.
(2) Tcc measuring method
By (B) pet resin drying more than 3 hours in the hot air dryer of 130 DEG C used in each embodiment and comparative example, being then placed on design temperature is on the compact hot press of 270 DEG C, pressurization, melting.Then the pellet of melting is dropped in liquid nitrogen, cooling at once.Chilled pellet is warmed up to 300 DEG C with heat-up rate 20 DEG C/minute from 40 DEG C by differential scanning calorimeter (DSC), measures endotherm(ic)peak now.
(3) evaluation of appearance
The pellet each embodiment and comparative example obtained is drying more than 3 hours in the hot air dryer of 130 DEG C, then uses toshiba machine IS55EPN injection moulding machine to be shaped to the square plate of 80mm × 80mm × thick 3mm at the condition hemostasis of mold temperature 265 DEG C, die temperature 80 DEG C.The outward appearance of the square plate after visual observation injection molding, evaluates appearance.
Zero: glossy, surface does not confirm concavo-convex.
△: matt, surface does not confirm concavo-convex.
×: matt, confirming surface has concavo-convex.
(4) evaluation of high circulation formability (high-cyclemoldability)
The pellet each embodiment and comparative example obtained is drying more than 3 hours in the hot air dryer of 130 DEG C, then uses toshiba machine IS55EPN injection moulding machine to be shaped to the square little case of vertical 30mm × horizontal 30mm × high 30mm × thick 1.5mm at the condition hemostasis of mold temperature 265 DEG C, die temperature 80 DEG C.Change inject time and cooling time, circulation number of seconds shortened to 22 seconds while carry out injection molding from 35 seconds 1 second by 1 second, the distortion of little case when the little case that visual judgement end is all filled is pushed out with or without.Measure shaping cycle number of seconds when little case deforms at first.
(5) evaluation of mobility
By the pellet drying more than 3 hours in the hot air dryer of 130 DEG C obtained in each embodiment and comparative example, then use toshiba machine IS55EPN injection moulding machine carry out under the condition of mold temperature 265 DEG C, die temperature 80 DEG C, injection pressure 20MPa thick 3mm, wide 10mm long strip type shaping, the length of mensuration products formed.
(6) evaluation of tension strain
The pellet each embodiment and comparative example obtained is drying more than 3 hours in the hot air dryer of 130 DEG C, then use toshiba machine IS55EPN injection moulding machine under the condition of mold temperature 265 DEG C, die temperature 80 DEG C, carry out the injection molding of the ISO dumbbell of thickness 4mm, measure tension strain according to ISO527-1,2.
In addition, dummy suffix notation and the content of the raw material used in embodiment, comparative example are as follows.
(A) polybutylene terephthalate resin
A-1: polybutylene terephthalate (eastern beautiful system " ト レ コ Application (registered trademark) " 1100M)
(B) pet resin (B-2 ~ B-11 contains type siloxane cross-linked resin (C-6, LTC-300B))
B-1: pet resin (eastern beautiful system " テ ト ロ Application (registered trademark) " T900E)
B-2: polyethylene terephthalate (adding solvent-borne type silica resin (East レ ダ ウ コ ー ニ Application グ シ リ コ ー Application LTC-300B in F20K100 mass parts) makes the ratio of silica resin be 1 mass parts, after shaping membrane, carry out 1 pulverizing, granulation (controlling temperature during granulation at 130 DEG C).)
B-3: (add LTC-300B in F20K100 mass parts makes the ratio of silica resin be 1 mass parts to polyethylene terephthalate, carries out 3 times and pulverize and granulation (controlling temperature during granulation at 160 DEG C) after shaping membrane.)
B-4: (add LTC-300B in F20K100 mass parts makes the ratio of silica resin be 1 mass parts to polyethylene terephthalate, carries out after shaping membrane, carries out 3 times and pulverizes and granulation (temperature during granulation 110 DEG C).)
B-5: (add LTC-300B in F20K100 mass parts, the ratio making silica resin is 1 mass parts to polyethylene terephthalate, after shaping membrane, carries out 20 times and pulverizes and granulation (controlling temperature during granulation at 130 DEG C).)
B-6: (add LTC-300B in F20K100 mass parts makes the ratio of silica resin be 1 mass parts to polyethylene terephthalate, after shaping membrane, carries out 20 times and pulverizes and granulation (controlling temperature during granulation at 130 DEG C).)
B-7: (add LTC-300B in F20K100 mass parts makes the ratio of silica resin be 1 mass parts to polyethylene terephthalate, after shaping membrane, carries out 20 times and pulverizes and granulation (controlling temperature during granulation at 110 DEG C).)
B-8: (add LTC-300B in F20K100 mass parts makes the ratio of silica resin be 1 mass parts to polyethylene terephthalate, after shaping membrane, carries out 2 times and pulverizes and granulation (controlling temperature during granulation at 130 DEG C).)
B-9: (add LTC-300B in F20K100 mass parts makes the ratio of silica resin be 1 mass parts to polyethylene terephthalate, after shaping membrane, carries out 3 pulverizing, granulation (controlling temperature during granulation at 130 DEG C).)
B-10: (add LTC-300B in F20K100 mass parts makes the ratio of silica resin be 1 mass parts to polyethylene terephthalate, after shaping membrane, carries out 18 times and pulverizes and granulation (controlling temperature during granulation at 130 DEG C).)
B-11: (add LTC-300B in F20K100 mass parts makes the ratio of silica resin be 1 mass parts to polyethylene terephthalate, after shaping membrane, carries out 10 times and pulverizes and granulation (controlling temperature during granulation at 130 DEG C).)
B-12: pet resin (original that be not added, MFR8g/10 minute, Tcc135 DEG C)
(C) cross-linked resin
C-1: using as terephthalic acid 30 mass parts of sour composition, trimellitic acid 20 mass parts and the known method polycondensation of ethylene glycol 50 mass parts as diol component, obtain pet resin.Here, add
azoles quinoline class linking agent (2-vinyl-2-
azoles quinoline) 15 mass parts, mixing 10 minutes at 270 DEG C, thus the cross-linked resin obtaining vibrin Jie You oxazoline class linking agent and be cross-linked.
C-2: add in acrylic resin (alkyl methacrylate) 100 mass parts
azoles quinoline class linking agent (2-vinyl-2-
azoles quinoline) 15 mass parts, mixing 10 minutes at 150 DEG C, thus obtain acrylic resin via
azoles quinoline class linking agent and the cross-linked resin be cross-linked.
C-3: add in urethane resin 100 mass parts
azoles quinoline class linking agent (2-vinyl-2-
azoles quinoline) 15 mass parts, mixing 10 minutes at 220 DEG C, thus obtain urethane resin via
azoles quinoline class linking agent and the cross-linked resin be cross-linked.
C-4: polybutylene terephthalate resin and the known method of pet resin are melt extruded (extrusion temperature 270 DEG C), forms stack membrane.The stack membrane obtained is coated with above-mentioned C-1 (vibrin via
azoles quinoline class linking agent and the cross-linked resin be cross-linked) the 50 quality % aqueous solution, and dry.The stack membrane pulverizer obtained is ground into shred, and then compresses granulation with tablets press.
C-5: using as terephthalic acid 30 mass parts of sour composition, trimellitic acid 20 mass parts and the known method polycondensation of ethylene glycol 50 mass parts as diol component, thus obtain pet resin.Here, add melamine class linking agent (methylolated melamine) 15 mass parts, mixing 10 minutes at 270 DEG C, thus obtain the cross-linked resin that vibrin has been cross-linked via melamine class linking agent.
(D) barium sulfate
D-1: barium sulfate (median particle diameter 0.8 μm)
[embodiment 1 ~ 24, comparative example 1 ~ 7]
By each composition of the mass parts shown in table 1 ~ 5 in the screw rod footpath of barrel temperatures set at 260 DEG C
two axle forcing machines in carry out melting mixing.By spuing from die head, the strand come cools in cooling bath, then cuts machine pellet with rope.
The composition of each embodiment, comparative example and evaluation result are as shown in table 1 ~ 5.
Table 1
Table 2
As shown in table 1, the embodiment 2 ~ 5 identical according to the use level of (B) pet resin, (C) embodiment 3 and 4 of the use level of cross-linked resin in the scope of 0.0005 ~ 8 mass parts, shaping cycle is short, and high circulation formability is higher.
In addition, embodiment 1,3,6, situation that the kind of 7 such (C) cross-linked resins is identical with use level, (B) embodiment 3 and 6 of the use level of pet resin in the scope of 15 ~ 65 mass parts, the appearance of products formed is excellent, and shaping cycle is short, high circulation formability is higher.
And then it is known, in the situation that the use level of embodiment 3,8 ~ 11 such (A) polybutylene terephthalate resins, (B) pet resin, (C) cross-linked resin is identical, (C) cross-linked resin is from the embodiment 10 of stack membrane, mobility improves, and shaping cycle shortens thus, high circulation formability is higher.
As shown in Tables 1 and 2, the embodiment 1,3,6 that comparative example 1 is identical with use level with the kind of (C) cross-linked resin with (A) polybutylene terephthalate resin is compared with 7, (B) pet resin amount is few, so the appearance of products formed is poor.
In addition, comparative example 2, the embodiment 1,3,6 identical with use level with the kind of (C) cross-linked resin with (A) polybutylene terephthalate resin is compared with 7, (B) amount of pet resin is many, so shaping cycle is long, high circulation insufficient formability.
Comparative example 3,4, due to not containing (C) cross-linked resin, so shaping cycle is long, high circulation insufficient formability.
Table 3
Table 4
Table 5
※ represents the mass parts of the cross-linked resin composition conversion be coupled in granules
As shown in table 4, the embodiment 18 ~ 21 identical according to the Tcc of (B) pet resin, (B) MFR of pet resin was 10 ~ 100g/10 minute, embodiment 19,21 in the scope of more preferably dividing more than 12g/10 minute and lower than 90g/10, the mechanical properties of mobility and products formed is excellent, so can shorten shaping cycle, high circulation formability is higher.
As shown in Tables 3 and 4, compared with embodiment 12 ~ 17, embodiment 18 ~ 24 mobility of MFR and Tcc in preferable range of (B) pet resin is excellent, so short, the high circulation formability of shaping cycle is higher.
In addition, according to embodiment 22 ~ 24, (B) amount of pet resin is relative to the embodiment 23 of (A) polybutylene terephthalate resin 100 mass parts more than 15 mass parts below 65 mass parts, and the appearance of high circulation formability and products formed is higher.
As shown in table 5, comparative example 5 due to the amount of (B) pet resin few, so the appearance of products formed is poor.
In addition, comparative example 6 due to the amount of (B) pet resin many, so shaping cycle is long, insufficient formability.
Comparative example 7 is not containing (C) cross-linked resin, so shaping cycle is long, high circulation insufficient formability.
Industry utilizability
The manufacture method of thermoplastic resin composition of the present invention and thermoplastic resin composition, due to the products formed that high circulation formability is excellent, appearance is good can be obtained, so the parts class used in various electrical and electronic parts class, trolley part class, especially particularly extraneous adornment can be performed well in.In addition, the manufacture method of thermoplastic resin composition of the present invention and thermoplastic resin composition, high circulation formability is excellent, can save energy, reduces the burden to environment.
Claims (10)
1. a thermoplastic resin composition, contain:
(A) polybutylene terephthalate resin,
(B) pet resin and
(C) cross-linked resin,
The mixing ratio of described (A) polybutylene terephthalate resin, described (B) pet resin and described (C) cross-linked resin is, relative to described (A) polybutylene terephthalate resin 100 mass parts, there are described (B) pet resin 10 ~ 70 mass parts, described (C) cross-linked resin 0.0001 ~ 10 mass parts
At least one side of the next comfortable base material film formed by polybutylene terephthalate and/or polyethylene terephthalate of described (C) cross-linked resin is formed with the stack membrane of the layer containing cross-linked resin.
2. thermoplastic resin composition as claimed in claim 1, described (C) cross-linked resin contains the resin with the crosslinking structure formed via (D) linking agent.
3. thermoplastic resin composition as claimed in claim 2, described (C) cross-linked resin is the cross-linked resin that the resin containing vibrin, acrylic resin and/or urethane resin has been cross-linked via (D) linking agent.
4. thermoplastic resin composition as claimed in claim 2 or claim 3, described (D) linking agent contains
azoles quinoline class linking agent and/or melamine class linking agent.
5. the thermoplastic resin composition as described in any one of claims 1 to 3, described (B) pet resin contains and experiences at least a kind of operation being selected from film molding procedure, melt-spinning operation and injection molding operation and the pet resin (B1) that obtains.
6. thermoplastic resin composition as claimed in claim 5, experience at least a kind of operation being selected from described film molding procedure, described melt-spinning operation and described injection molding operation and the melt flow rate (MFR) of pet resin (B1) that obtains is 10 ~ 100g/10 minute
Described melt flow rate (MFR) after dry 4 hours, is determined under the condition of test temperature 270 DEG C, load 325g according to the method for ISO1133 in the hot air dryer of 130 DEG C by described pet resin (B1).
7. thermoplastic resin composition as claimed in claim 5, when experiencing the intensification of at least a kind of operation be selected from described film molding procedure, described melt-spinning operation and described injection molding operation and the pet resin (B1) obtained, crystallized temperature is 140 DEG C ~ 160 DEG C.
8. thermoplastic resin composition as claimed in claim 6, when experiencing the intensification of at least a kind of operation be selected from described film molding procedure, described melt-spinning operation and described injection molding operation and the pet resin (B1) obtained, crystallized temperature is 140 DEG C ~ 160 DEG C.
9. a thermoplastic resin composition's manufacture method, by coordinating
(A) polybutylene terephthalate resin,
(B) pet resin and
At least one side of the base material film formed by polybutylene terephthalate and/or polyethylene terephthalate is formed the stack membrane of the layer containing (C) cross-linked resin,
By they melting mixings, thus the thermoplastic resin composition described in any one of manufacturing claims 1 ~ 8.
10. the manufacture method of thermoplastic resin composition as claimed in claim 9, after by described stack membrane pulverizing and/or granulation, be coupled in described (A) polybutylene terephthalate resin and described (B) pet resin, and carry out melting mixing.
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| JP2012-005915 | 2012-01-16 | ||
| PCT/JP2013/050587 WO2013108758A1 (en) | 2012-01-16 | 2013-01-15 | Thermoplastic resin composition and method for producing thermoplastic resin composition |
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| KR102173834B1 (en) | 2018-02-28 | 2020-11-04 | 롯데첨단소재(주) | Thermoplastic resin composition and article produced therefrom |
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| JPH03275727A (en) * | 1990-03-23 | 1991-12-06 | Diafoil Co Ltd | Production of regenerated pellet |
| JPH0459828A (en) * | 1990-06-29 | 1992-02-26 | Diafoil Co Ltd | Production of regenerated pellet |
| JPH09169858A (en) * | 1995-12-19 | 1997-06-30 | Diafoil Co Ltd | Polyester film |
| JPH11116742A (en) * | 1997-10-14 | 1999-04-27 | Shiseido Co Ltd | Molded article made of recycled resin |
| JP2000345016A (en) * | 1999-06-02 | 2000-12-12 | Teijin Ltd | Resin composition, molded article and preparation thereof |
| JP3933838B2 (en) * | 2000-02-21 | 2007-06-20 | ポリプラスチックス株式会社 | Insert molded product |
| JP2002036234A (en) * | 2000-07-31 | 2002-02-05 | Aisin Seiki Co Ltd | Method for manufacturing regenerated polyethylene terephthalate resin molding and regenerated polyethylene terephthalate resin molding |
| JP2002331629A (en) * | 2001-05-10 | 2002-11-19 | Toyobo Co Ltd | Polyester film for laminating metal sheet, film laminated metal sheet and metal container |
| JP2008207442A (en) * | 2007-02-26 | 2008-09-11 | Mitsubishi Plastics Ind Ltd | Polyester film for paperless thermosensitive stencil printing base paper |
| JP2009215510A (en) * | 2008-03-13 | 2009-09-24 | Mitsubishi Plastics Inc | Method for producing polyester film |
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