CN101790564B - Saturated polyester resin composition and hot melt adhesive composition - Google Patents
Saturated polyester resin composition and hot melt adhesive composition Download PDFInfo
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- CN101790564B CN101790564B CN2008801045873A CN200880104587A CN101790564B CN 101790564 B CN101790564 B CN 101790564B CN 2008801045873 A CN2008801045873 A CN 2008801045873A CN 200880104587 A CN200880104587 A CN 200880104587A CN 101790564 B CN101790564 B CN 101790564B
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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Abstract
The invention discloses a saturated polyester resin composition which is excellent in sealing properties and adhesive strength to metal materials such as copper and aluminum as well as resin materials such as polyethylene terephthalate. This saturated polyester resin composition is particularly improved in adhesive strength at low temperatures. Specifically, the saturated polyester resin composition contains a saturated polyester resin, a crystalline polyolefin resin and a thermoplastic soft acrylic resin. The saturated polyester resin composition may further contain an epoxy resin. The thermoplastic soft acrylic resin preferably has a Shore A hardness of less than 90 and a melt index at 190 DEG C under a load of 2.16 kg of not less than 10 g/10 minutes.
Description
Technical field
The present invention relates to contain the saturated polyester resin composition of saturated polyester resin, crystalline polyolefin resinoid and thermoplastic soft acrylics and the hot-melt adhesive composition that provides by said composition.
Background technology
The electrical specification of saturated polyester resin and thermal property are excellent; And because it is to plastic materials such as vibrin; The characteristic that the adaptation of metallic substance such as copper, aluminium is excellent, the polyethylene terephthalate resinoid that has been widely used as IC-card and IC chip are installed the hotmelt that layer share the suitable wirning harness in hotmelt and automobile, electric and electronic field etc. of sheet material.Above-mentioned IC-card and wirning harness are being popularized in recent years, on the other hand, are improving for the requirement of the bond strength of the hotmelt that uses.Particularly carried out maintenance in the bond strength of wide temperature range, in the winter time, summer etc. the applied temps scope the stripping strength of protective membrane of IC-card keep having become problem.
Therefore, so far, have been proposed in the saturated polyester resin hot-melt adhesive composition that adds, mixed various resinous principles.For example, proposed in saturated polyester resin, to add ldpe resin, high-density polyethylene resin, and added the saturated polyester class hot-melt adhesive composition (with reference to patent documentation 1) of epoxy resin.In addition, proposed in saturated polyester resin, to have added the saturated polyester class hot-melt adhesive composition (with reference to patent documentation 2) of resol.In addition, proposed to comprise the saturated polyester class hot-melt adhesive composition (with reference to patent documentation 3) of crystallinity polyester resin and amorphism polyester resin and epoxy resin.
Patent documentation 1: the spy opens the 2004-269654 communique
Patent documentation 2: the spy opens the 2003-327940 communique
Patent documentation 3: the spy opens the 2002-138269 communique
Summary of the invention
The problem that invention will solve
According to the method for record in patent documentation 1, patent documentation 2 and the patent documentation 3, improve because of saturated polyester resin monomer as staple with the stripping strength of tackiness agent.But, do not solve and peel off the poor reliability under the applied temps (10 ℃～80 ℃) in adhesive interface under the low temperature.
The objective of the invention is to formation, provide and can realize the compsn of improvement the bond strength of resin material under low temperature (10 ℃～10 ℃) such as metallic substance such as copper, aluminium and polyethylene terephthalates through the improvement saturated polyester resin composition.
Be used to solve the means of problem
In view of above-mentioned problem; Inventor's further investigation; The result finds through cooperation crystalline polyolefin resinoid and thermoplastic soft acrylics in saturated polyester resin, thereby improvement has been accomplished the present invention in the bond strength of wide temperature range (10 ℃～80 ℃).
The present invention is described below.
1. saturated polyester resin composition is characterized in that, contains (A) saturated polyester resin, (B) crystalline polyolefin resinoid and (C) thermoplastic soft acrylics.
2. above-mentioned 1 described saturated polyester resin composition, the Shore A hardness of wherein said thermoplastic soft acrylics (C) are less than 90, and the melt index values under 190 ℃ of temperature and the load 21.2N is more than 10g/10 minute.
3. above-mentioned 2 described saturated polyester resin compositions, the Shore A hardness of wherein said thermoplastic soft acrylics (C) is 10～80.
4. above-mentioned 2 described saturated polyester resin compositions, the melt index values of wherein said thermoplastic soft acrylics (C) under 190 ℃ of temperature and load 21.2N is 10～100g/10 minute.
5. above-mentioned 1 described saturated polyester resin composition, wherein said thermoplastic soft acrylics (C) is a segmented copolymer.
6. above-mentioned 5 described saturated polyester resin compositions, the Shore A hardness of wherein said thermoplastic soft acrylics (C) are less than 90, and the melt index values under 190 ℃ of temperature and the load 21.2N is more than 10g/10 minute.
7. above-mentioned 1 described saturated polyester resin composition; When wherein said saturated polyester resin (A), said crystalline polyolefin resinoid (B) and said thermoplastic soft acrylics (C) being added up to 100 quality %, the content of said thermoplastic soft acrylics (C) is 0.5～30 quality %.
8. above-mentioned 1 described saturated polyester resin composition wherein also contains (D) epoxy resin.
9. above-mentioned 8 described saturated polyester resin compositions; When wherein said saturated polyester resin (A), said crystalline polyolefin resinoid (B), said thermoplastic soft acrylics (C) and said epoxy resin (D) being added up to 100 quality %, the content of said epoxy resin (D) is 1～25 quality %.
10. hot-melt adhesive composition is characterized in that, contains above-mentioned 1 described saturated polyester resin composition.
11. hot-melt adhesive composition is characterized in that, contains above-mentioned 8 described saturated polyester resin compositions.
The effect of invention
Use the adhesive member of saturated polyester resin composition of the present invention, because the driving fit improved performance, therefore the bond strength of resin materials such as metallic substance such as copper, aluminium and polyethylene terephthalate is improved as hot-melt adhesive composition.Particularly improve by the bond strength and destruction form of low temperature to the pyritous wide temperature range.In addition, owing to improve tackiness agent and, therefore can obtain the excellent adhesive member of stopping property by the interface peel state of sticking material.
Embodiment
An embodiment of the invention are explained as follows, but the present invention is not defined in this.In this specification sheets, " (methyl) vinylformic acid " expression vinylformic acid and methylacrylic acid, " (methyl) propenoate " expression propenoate and methacrylic ester.
Saturated polyester resin composition of the present invention; It is characterized in that, comprise (A) saturated polyester resin (below be also referred to as " resinous principle (A) "), (B) crystalline polyolefin resinoid (below be also referred to as " resinous principle (B) ") and (C) thermoplastic soft acrylics (below be also referred to as " resinous principle (C) ").
Above-mentioned resinous principle (A) does not have special qualification, the saturated polyester resin that can use polycondensation through sour composition and polyhydroxy reactant etc. to obtain.
Monomeric sour composition and polyhydroxy reactant as forming above-mentioned resinous principle (A) do not have special qualification, can use following each composition.
As above-mentioned sour composition, can enumerate aromatic acid, aliphatic dibasic acid and alicyclic diprotic acid etc.
As the specific examples of aromatic acid, can enumerate terephthalic acid, m-phthalic acid, Tetra hydro Phthalic anhydride, α-naphthalic acid, β-naphthalic acid and their ester organizer etc.
As the specific examples of aliphatic dibasic acid, can enumerate succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecylenic acid, dodecanedioic acid and their ester organizer etc.
In addition, as the specific examples of alicyclic diprotic acid, can enumerate 1,4 cyclohexanedicarboxylic acid, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride etc.
Above-mentioned sour composition can only use a kind, also can be with also using more than 2 kinds.
In the above-mentioned sour composition, preferred terephthalic acid and ester organizer thereof aspect bond strength, containing of terephthalic acid is proportional, is preferably 30 moles more than the % with respect to all acid composition.If the terephthalic acid composition is 30 moles more than the %, obtain enough resin cohesive force and hardness, bond strength is improved, so preferably.
In addition; As sour composition; In the scope of not damaging gelation and the bond strength of this saturated polyester resin (A) when synthetic, can be with unsaturated acid such as toxilic acid, fumaric acid, dimeracids, polycarboxylic acids such as trimellitic acid, PMA etc. and usefulness; With respect to all acid composition, can use 5 moles of scopes below the %.
As above-mentioned polyhydroxy reactant, can enumerate divalent alcohol and polyvalent alcohols such as aliphatic dihydroxy alcohol, alicyclic divalent alcohol.
In the above-mentioned divalent alcohol, as the specific examples of aliphatic dihydroxy alcohol, can enumerate terepthaloyl moietie, 1,2-Ucar 35,1; Ammediol, 1,3 butylene glycol, 1,4-butyleneglycol, 1; 5-pentanediol, 1,6-pinakon, 1,8-ethohexadiol, 1; 9-nonanediol, NSC 6366,3-methyl pentanediol, 2,2,3-neopentyl glycol, glycol ether, triglycol, dipropylene glycol etc.
As the specific examples of alicyclic divalent alcohol, can enumerate 1,4 cyclohexane dimethanol, Hydrogenated Bisphenol A 99 etc.
Above-mentioned divalent alcohol can only use a kind, also can be with also using more than 2 kinds.
As above-mentioned divalent alcohol, preferably use 1, the 4-butyleneglycol, 1, the 4-butyleneglycol is preferably 30 moles more than the % with respect to the ratio of whole polyhydroxy reactants.If 1, the 4-butyleneglycol is 30 moles more than the %, owing to obtain enough cohesive force, bond strength is improved, so obtain high heat resistance.
In addition, as above-mentioned polyvalent alcohol, can enumerate glycerine, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane etc.They can only use a kind, also can be with also using more than 2 kinds.Above-mentioned polyvalent alcohol can use 5 moles of scopes below the % with respect to whole polyhydroxy reactants.
The fusing point of saturated polyester resin of the present invention (A) is that the above main endotherm peak temperature of 1J/g is represented with the fusion heat that adopts DSC (below be also referred to as DSC) to measure; The preferred fusing point that uses this melting heat peak temperature to represent is 50 ℃～200 ℃ a vibrin, more preferably 60 ℃～150 ℃ vibrin.If this fusing point is 50 ℃～200 ℃ scopes, because coating temperature and tack temperature become suitable temperature, be difficult to take place the thermal degradation when and the oxidation of adhesive substrate, therefore obtain excellent adhesion strength.
The melt viscosity of above-mentioned saturated polyester resin (A) is 10～500g/10 minute surveying periodic melt index values (below be also referred to as " MI value ") under the condition of 190 ℃ of temperature, load 21.2N preferably.This MI value more preferably 10～300g/10 minute further is preferably 10～100g/10 minute.If the MI value of this saturated polyester resin (A) is 10～500g/10 minute, then can easily mix with other resinous principles, obtain showing the more resin combination of excellent adhesion strength.
Above-mentioned saturated polyester resin (A) can adopt synthetic, the manufacturing of usual method.For example, charging feedstock and catalyzer are arranged, the melt phase polycondensation that under the temperature more than the fusing point of resultant, heats; At the following polymeric solid phase polymerization method of the fusing point of resultant, use the solution polymerization process of solvent etc., can adopt any method; Polyester for the appropriate polymerization degree that obtains following the object of the invention; And from the economy aspect, the preferred molten polymerization adopts ester-interchange method, direct esterification manufactured.
In the saturated polyester resin composition of the present invention; The content of above-mentioned saturated polyester resin (A), the total amount with respect to above-mentioned resinous principle (A), resinous principle (B) and resinous principle (C) is preferably 40～98.5 quality %; More preferably 50～95 quality % are preferably 60～90 quality % especially.Above-mentioned resinous principle (A) if ratio be the scope of 40～98.5 quality % owing to obtain enough peel adhesion strength, so preferably.
In addition, in the saturated polyester resin composition of the present invention, contain crystalline polyolefin resinoid (B).Above-mentioned resinous principle (B) plays and prevents in the concentrated effect of the peel stress at adhesive substrate interface.Above-mentioned resinous principle (B) is in the state that is dispersed in the binder compsn with microgranular.This dispersed particle surface and low as the wettability at saturated polyester resin (A) interface of principal constituent.In addition, owing to, can make the peel stress that puts on adhesive member be scattered in the interface of the dispersed particle of saturated polyester resin (A) and crystalline polyolefin resinoid (B) because of crystallization has the high modulus of saturated polyester resin (A) than principal constituent.Its result can prevent the concentrating of peel stress at tackiness agent and adhesive substrate interface, and peel adhesion strength improves.
The percent crystallinity of above-mentioned resinous principle (B) preferably uses DSC to survey periodic melting heat as more than the 50J/g, and perhaps heat of crystallization is more than the 50J/g.Especially, more preferably melting heat is more than the 80J/g, and perhaps heat of crystallization is 80J/g above (being generally below the 220J/g).That is, can make the melting heat of resinous principle (B) or heat of crystallization is 50～220J/g, also can be the 80J/g～220J/g of above-mentioned lower value.If melting heat or heat of crystallization are the scope of 50～220J/g, the difference of the modulus of resinous principle (A) and resinous principle (B) becomes big, and peel stress disperses.Its result can prevent the concentrating of peel stress at tackiness agent and adhesive substrate interface, and peel adhesion strength improves.
The composition that forms above-mentioned resinous principle (B) is to be selected from more than a kind or 2 kinds of vinyl monomer with unsaturated double-bond.For example, be the olefines vinyl monomer of ethene, propylene, carbon number 2～20.Above-mentioned resinous principle (B) is preferably with high-density polyethylene resin and the ldpe resin of ethene as principal constituent, more preferably density 0.910～0.925g/cm
3New LDPE (film grade).
The melt viscosity of above-mentioned resinous principle (B) is surveyed periodic MI value and is preferably 0.5～150g/10 minute, more preferably 1～120g/10 minute under the condition of 190 ℃ of temperature, load 21.2N.If 0.5～150g/10 minute scope of MI value, can with above-mentioned resinous principle (A) and (C) uniform mixing, obtain stable bond strength.In addition, because resin combination has the flexibility of appropriateness, so even also can obtain sufficient bond strength at low temperature.
In the resin combination of the present invention, the content of above-mentioned crystalline polyolefin resinoid (B), the total amount with respect to above-mentioned resinous principle (A), resinous principle (B) and resinous principle (C) is preferably 1～30 quality %, more preferably 3～25 quality %.Resinous principle (B) is if in the scope of 1～30 quality %, then as problem of the present invention from low temperature to pyritous wide region temperature under bond strength improve.
Above-mentioned thermoplastic soft acrylics (C) has adaptation, the particularly function of low temperature adhesion intensity of improvement to metal bases such as resin base materials such as polyethylene terephthalate and copper.As the means of improving the adaptation of adhesive substrate, improving tackiness agent is important to the wettability of adhesive substrate.In addition, utilize the flexibility of binder compsn to prevent that the concentrating of peel stress at tackiness agent and adhesive substrate interface from also being important.This thermoplastic soft acrylics (C) can prevent the stress concentration at tackiness agent and adhesive substrate interface because at room temperature flexibility is also high for peel stress.
Above-mentioned resinous principle (C) is characterised in that, is that high soft of flexibility is resin.Here, so-called soft system be meant JIS K6253 regulation Shore A hardness less than 90.The Shore A hardness of above-mentioned resinous principle (C) is preferably 10～80 less than 90, and more preferably 30～70.Shore A hardness is 90 when above, because stress concentration at the interface of tackiness agent and adhesive substrate, therefore produces the unfavorable situation of peel adhesion strength reduction.
In addition, the melt viscosity of above-mentioned resinous principle (C) preferably has the melt viscosity that approaches above-mentioned resinous principle (A).The MI value of above-mentioned resinous principle (C) was preferably more than 10g/10 minute, more preferably 15～100g/10 minute, further was preferably 20～70g/10 minute.The MI value is during less than 10g/10 minute, because big with the melt viscosity difference of resinous principle (A), it is bad to produce the dispersion that resinous principle (C) takes place, and even can not make the unfavorable situation of compsn.
The main monomer composition that forms above-mentioned resinous principle (C) is for being selected from (methyl) propenoate; For example, in the esterification set of monomers of the alkyl alcohol composition of carbon numbers 1～20 such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) Bing Xisuandingzhi and (methyl) acrylic component more than a kind or 2 kinds.Preferably, be principal constituent with TEB 3K, Bing Xisuandingzhi.
In addition; In the scope of not damaging the object of the invention; Can use olefin monomers such as ethene, propylene; The fragrant same clan such as vinylbenzene, alpha-methyl styrene vinyl monomer, Tetra hydro Phthalic anhydride, vinylformic acid etc. contains the monomer of carboxyl, and (methyl) glycidyl acrylate etc. contains the monomer of epoxy group(ing) etc.
Above-mentioned resinous principle (C) in the use temperature scope, intensity of resin (for example tensile strength etc.) and flexibility and to deposit be necessary.Therefore, the segmented copolymer that hard segment with outspoken nature and the soft chain segment with flexibility constitute of hoping to serve as reasons.The hard segment of segmented copolymer has the effect that in common use temperature scope, keeps mechanical strength of resin, and soft chain segment has the effect of the flexibility of giving.Above-mentioned resinous principle (C) is under the situation of random copolymers, the balanced differences of the intensity of resin and flexibility in the use temperature scope, and the intensity of tackiness agent self reduces, and even causes the reduction of peel adhesion strength.
Make the method for the segmented copolymer of above-mentioned resinous principle (C), can use polymerization method arbitrarily.Preferably, can use the spy to open that 2000-44631 communique, spy are opened the 2001-158805 communique, the spy opens the method for manufacture of putting down in writing in 2003-277574 communique and the Te Kai 2004-2844 communique.
In the saturated polyester resin composition of the present invention; The content of above-mentioned thermoplastic soft acrylics (C); Total amount with respect to above-mentioned resinous principle (A), resinous principle (B) and resinous principle (C); Be preferably 0.5～30 quality %, more preferably 1～25 quality % further is preferably 1～20 quality %.
Above-mentioned resinous principle (C) is during less than 0.5 quality %, can not realize as problem of the present invention from low temperature to pyritous wide region temperature the improvement of bond strength.On the other hand, when surpassing 30 quality %, the intensity of said composition self reduces, and bond strength also reduces.
Saturated polyester resin composition of the present invention can further contain (D) epoxy resin (below be also referred to as " resinous principle (D) ").
Above-mentioned epoxy resin (D) is adjusted the thermotolerance and the modulus of saturated polyester resin composition of the present invention as the adhesion imparting agent, is used to adjust the adaptation to adhesive substrate effectively.As above-mentioned resinous principle (D), for example, can use bisphenol-type epoxy resin, phenol aldehyde type epoxy resin, phenolic resin varnish type epoxy resin, cresols phenolic resin varnish type epoxy resin etc.Be preferably bisphenol-type epoxy resin.
The R&B softening temperature of preferred above-mentioned resinous principle (D) is 50 ℃～180 ℃.Wherein, the R&B softening temperature is the resin rerum natura by JIS K-6863-1994 regulation.
The content of the resinous principle in the saturated polyester resin composition of the present invention (D), the total amount with respect to above-mentioned resinous principle (A), resinous principle (B), resinous principle (C) and resinous principle (D) is preferably 1～25 quality %, more preferably 2～20 quality %.Above-mentioned resinous principle (D) if the scope of content 1～25 quality %, then obtain enough adaptations to adhesive substrate, bond strength is improved.
In addition, in the scope of not damaging the object of the invention, can use the 2nd adhesion imparting agent.Can use for example terpine resin type adhesion imparting agents such as terpine resin, terpene phenolic resin, aromatic series modified terpene resin, hydrogenated terpene resin; Modified rosin resin types such as rosin modified phenolic resin adhesion imparting agent, petroleum resin types such as aliphatic category petroleum resin, alicyclic ring same clan petroleum resin, fragrant same clan petroleum resin adhesion imparting agent etc.
In the saturated polyester resin composition of the present invention, can use weighting agent arbitrarily in the scope of not damaging the object of the invention.Weighting agent is used to adjust thermotolerance, modulus, anti-adhesive, productivity of saturated polyester resin composition of the present invention etc. effectively.
As above-mentioned weighting agent; Can use for example mineral compound type weighting agents such as talcum, organic surface treatment talcum, clay, water-ground limestone, light calcium carbonate, silicon-dioxide, fumed silica, zinc oxide, Marinco H, white lake, titanium oxide, spun glass, smectite type laminar silicic acid salt compound, organic process smectite type laminar silicic acid salt compound, organic cpds type weighting agents such as carbon black, man-made fiber etc.The usage quantity of weighting agent with respect to 100 quality % saturated polyester resin composition of the present invention, is generally below the 30 quality %, is preferably below the 20 quality %, more preferably below the 10 quality %.
In saturated polyester resin composition of the present invention, can use the arbitrary stable agent in the scope of not damaging the object of the invention.Stablizer is used for the material of the stabilization adjustment of bond properties effectively for suppressing the thermolysis and the hydrolysis of saturated polyester resin composition of the present invention.As stablizer, can use anti hydrolysis agents such as for example gathering carbodiimide, phenol antioxidant, phosphorous acid esters inhibitor, thioether class inhibitor etc.The usage quantity of stablizer with respect to 100 quality % saturated polyester resin composition of the present invention, is generally below the 10 quality %, is preferably below the 5 quality %.
In the saturated polyester resin composition of the present invention,, can use coupling agent arbitrarily in the scope of not damaging the object of the invention.Coupling agent is the adhesive substrate surface that acts on saturated polyester resin composition of the present invention, is used for the material of the adjustment of moisture-proof thermostability effectively.As coupling agent, can use alkyl such as dimethyldimethoxysil,ne for example is that aluminium such as the silane coupling agents such as silane coupling agent that contain vinyl such as the silane coupling agent that contains amino silane coupling agent, 3-Racemic glycidol oxygen propyl trimethoxy silicane etc. and contain epoxy group(ing) such as silane coupling agent, 3-aminopropyltriethoxywerene werene, vinyltriacetoxy silane, acetyl alkoxyl group diisopropoxy aluminium are that titanic acid ester such as coupling agent, sec.-propyl three isostearoyl base titanic acid ester are coupling agent etc.These coupling agents further improve characteristic of the present invention sometimes, can suitably use.The usage quantity of coupling agent with respect to 100 quality % saturated polyester resin composition of the present invention, is generally below the 5 quality %, is preferably below the 3 quality %, more preferably below the 2 quality %.
In the saturated polyester resin composition of the present invention,, can use other additives arbitrarily in the scope of not damaging the object of the invention.For example, can use fire retardants such as bromide fire retardant, phosphorus flame retardant, UV light absorber, softening agent and crystallization nucleating agent etc.
Saturated polyester resin composition of the present invention obtains through adopting arbitrary method hybrid resin composition (A), resinous principle (B), resinous principle (C) etc.For example, through utilize single screw extrusion machine, engagement type cocurrent and parallel axle twin screw extruder, engagement type anisotropic parallel axle twin screw extruder, the incorgruous inclined shaft twin screw extruder of engagement type, non-engagement type twin screw extruder, not exclusively engagement type twin screw extruder, the forcing machine of kneading type altogether, planet-shaped forcing machine, transmit each raw material of mixing such as extrusion shaping machines such as mixing forcing machine, plunger-type extruder, roll-type forcing machine or kneader and obtain.In addition, also can before above-mentioned mixing, use Henschel mixer, rotary drum etc. with the raw material pre-mixing.
Each material composition of saturated polyester resin composition of the present invention can use pellet shape, powder shape, random shape or proterties such as liquid.
The form of saturated polyester resin composition of the present invention can be used any form.For example, can use pellet shape, Powdered, sheet or membranaceous, bar-shaped, as to be dissolved in solvent solution shape etc.
Saturated polyester resin composition of the present invention is to the bond strength of various metals and plastic material, and especially adaptation is excellent, can be used for various fields.For example, can be used for tackiness agent, sealing material, the packaged material of the parts in electronics, the machine field, in addition, in packaging field, can be used as the tackiness agent between laminate film, laminate film.Also can be used for the tackiness agent of the built-in material of automotive field, the sealing material of wirning harness etc.The method of use of saturated polyester resin composition of the present invention does not have special qualification, can fit to make the civilian described hot melt process in back etc.
Hot-melt adhesive composition of the present invention is characterized in that, contains the saturated polyester resin composition of the invention described above.
Hot-melt adhesive composition of the present invention can become and contains resinous principle (A), (B) and (C), contains the compsn of additive as required, and contains resinous principle (A), (B), (C) and (D), contains the compsn of additive as required.Under any situation, can be that 60 ℃～200 ℃ temperature becomes molten state all, with bonding between the sticking material of the quilt that is same to each other or different to each other through making hot-melt adhesive composition of the present invention.
Explain for using the bonding method of hot-melt adhesive composition of the present invention by sticking material.The shape of hot-melt adhesive composition of the present invention is under the membranaceous situation, can be present in each by between the sticking material through at room temperature making this film, and the limit adds flanging and is heated to 60 ℃～200 ℃ as required, thereby both are bonding.
Embodiment
Below enumerate embodiment, illustrate in greater detail the present invention, as long as but be no more than purport of the present invention, the present invention is not limited to said embodiment.
(manufacturing of saturated polyester resin)
In four-hole boiling flask with whipping appts, nitrogen ingress pipe, still tube, TM, 1 of 0.6mol DMT. Dimethyl p-benzenedicarboxylate, the 1.6mol that pack into, 1 of 4-butyleneglycol, 0.2mol, 6-pinakon and 0.2 * 10
-2Mol is as the tetra-n-butyl titanic acid ester of catalyzer; The limit imports the nitrogen limit and heats up, and after distillating methyl alcohol under 130 ℃～200 ℃, adds 0.15mol m-phthalic acid and 0.25mol sebacic acid; After distillating water under 200 ℃～240 ℃; Then slowly decompression the time, reacted 3 hours down, obtain saturated polyester resin (A-1) at 250 ℃, the decompression of 1mmHg.The rerum natura of saturated polyester resin (A-1), the fusing point that uses DSC under 10 ℃/minute intensification condition, to measure is 135 ℃, and second-order transition temperature is-18 ℃.According to JIS K 7210, the MI value is 80g/10 minute under 190 ℃, the condition of load 21.2N.In addition, analyzed the monomer of this vibrin formed by NMR and analyze, the result is with molar ratio computing, terephthalic acid/isophthalic acid/sebacic acid/1,4-butyleneglycol/1,6-pinakon=60/15/25/80/20.
(the formability evaluation of the method for manufacture of compsn 1, compsn)
With 1440g as the saturated polyester resin (A-1) of resinous principle (A), 280g Japanese polyolefine society system new LDPE (film grade), trade(brand)name " ジ エ イ レ Star Network ス LD JM910 " (density: 0.918g/cm as resinous principle (B)
3Melting heat: 112J/g; MI value under 190 ℃ of temperature and the load 21.2N: 20g/10 minute; Below be also referred to as " LDPE ") and 280g, drop in the Chi Beishe system 30mm twin screw extruder " PCM-30 ", in advance behind the uniform mixing as the Kuraray society of resinous principle (C) system trade(brand)name " LA-2140E " (below be also referred to as " C-1 ") 160 ℃ of following melting mixing.The molten resin cooling curing that in tank, will utilize forcing machine to extrude with line material shape cuts into pellet shape with tablets press, obtains 1000g compsn 1.This moment Visual Confirmation line material the state of extruding, extrusion capacity is stable, line material surface is also level and smooth, formability is judged as well.
Should explain that above-mentioned C-1 is the ternary block polymer of polymethylmethacrylate-butyl polyacrylate-polymethylmethacrylate.In addition, adopt the Shore A hardness of measuring C-1 according to the method for JIS K6253, the result is 32 (mensuration temperature: 23 ℃).
(making method of compsn/copper bond test sheet)
Hot pressing under 180 ℃ condition (0.1MPa, 30 seconds) compsn 1 is made the thick sheet material of about 100 μ m (80～120 μ m).The sheet cutting that obtains is become wide 25mm, long 50mm, make adhesive sheet.
The copper coin (material is C-1100P, and thick is 50 μ m) of adhesive substrate is cut into wide 25mm, long 75mm.
Adhesive sheet is clipped between 2 copper coins, makes the about 25mm of length residue between the stretching clamp, hot pressing is 30 seconds under 180 ℃, 0.1MPa, making compsn 1/ bronze medal test film.
(to the adhesion test of copper base material)
Embodiment 1
Use tensile testing machine (society of Shimadzu Seisakusho Ltd. system " オ one ト グ ラ Off DSS-500 "); Make compsn 1/ bronze medal test film become the T font and be fixed in the anchor clamps of tension test, the peel adhesion strength when under the draw speed condition of 5 ℃ of temperature, 200mm/ minute, measuring tension load is 113N/25mm.In addition, for the compsn of under same condition, making 1/ bronze medal test film, the peel adhesion strength when to make temperature condition be 23 ℃, 40 ℃ and 50 ℃ is respectively 108N/25mm, 76N/25mm and 50N/25mm.In addition, Visual Confirmation is peeled off form, and the result destroys form for cohesion under the temperature condition of 40 ℃ and 50 ℃.
Embodiment 2
Except the Kuraray society system trade(brand)name " LA-2250 " of using 280g (below be also referred to as " C-2 ") as the resinous principle (C), is used with compsn 1 same method and is made compsn 2.Good forming ability.In addition, under the condition same, make compsn 2/ bronze medal test film with making compsn 1/ bronze medal bond test sheet.And use with embodiment 1 same method and measure bond strength.When its result, test temperature were 5 ℃, 23 ℃, 40 ℃ and 50 ℃, stripping strength separately was 128N/25mm, 96N/25mm, 69N/25mm and 44N/25mm.In addition, Visual Confirmation is peeled off form, and the result destroys form for cohesion under the temperature condition of 40 ℃ and 50 ℃.
Comparative example 1
With 1720g saturated polyester resin (A-1) with as the 280g of resinous principle (B) above-mentioned " ジ エ イ レ Star Network ス LD JM910 " uniform mixing, adopt with compsn 1 same method and obtain compsn 3.And formability is good.In addition, under the condition same, make compsn 3/ bronze medal test film with making compsn 1/ bronze medal bond test sheet.And use with embodiment 1 same method and measure bond strength.When its result, test temperature were 5 ℃, 23 ℃, 40 ℃ and 50 ℃, stripping strength separately was 21N/25mm, 54N/25mm, 47N/25mm and 29N/25mm.In addition, Visual Confirmation is peeled off form, and the result destroys form for cohesion under 50 ℃ temperature condition.
Embodiment 1 compares with comparative example 1 with 2, finds high about 2～5 times degree of peel adhesion strength of 5 ℃～50 ℃ of TRs, in addition, destroys form and also is prone to produce to condense destroy.Can know that by this result through in saturated polyester resin, adding the thermoplastic soft acrylics, to the adaptation raising of copper base material, bond properties and sealing property improve.
(method of manufacture of compsn 4～9, formability evaluation)
According to the compsn proportioning of record in the table 1, prepare composition material, employing obtains compsn 4～9 with the same method of method of manufacture of compsn 1.In addition, the formability of all compsns is all good.Moreover the resinous principle in the table 1 uses resin as follows.
(1)LDPE
Used ldpe resin (Japanese polyolefine society system, trade(brand)name " ジ エ イ レ Star Network ス LD JM910 ").
(2)C-1
Used thermoplastic soft acrylics (Kuraray society system, trade(brand)name " LA-2140E ").
Shore A hardness (JIS K6253) under 23 ℃ of the temperature is 32, and 190 ℃ of temperature are 31g/10 minute with MI value under the load 21.2N.
(3)C-2
Used thermoplastic soft acrylics (Kuraray society system, trade(brand)name " LA-2250 ").This C-2 is the ternary block polymer of polymethylmethacrylate-butyl polyacrylate-polymethylmethacrylate.
Shore A hardness (JIS K6253) under 23 ℃ of the temperature is 65, and 190 ℃ of temperature are 25g/10 minute with MI value under the load 21.2N.
(4)C-3
Used thermoplastic soft acrylics (Kuraray society system, trade(brand)name " LA-4285 ").This C-3 is the ternary block polymer of polymethylmethacrylate-butyl polyacrylate-polymethylmethacrylate.
Shore A hardness (JIS K6253) under 23 ℃ of the temperature is 95, and 190 ℃ of temperature are 1.5g/10 minute with MI value under the load 21.2N.
(5) soft acrylic rubber
Mitsubishi rayon society system, trade(brand)name " メ タ Block レ Application W-310 " have been used.
(6) epoxy resin
Used bisphenol A type epoxy resin as resinous principle (D).The R&B softening temperature is 138 ℃.
Embodiment 3～4 and comparative example 2
Use compsn 4～6, make compsn/copper test film, use the mensuration of having implemented bond strength with embodiment 1 same method.Its result is shown in the embodiment 3～4 and the comparative example 2 of table 2.Among the result of the destruction form in the table 2, " interface " is expressed as the interface peel of resin combination and adhesive substrate, and the cohesion of " cohesion " expression resin combination destroys.
Comparative example 2 is the instances that do not contain resinous principle (C) and used epoxy resin.
Comparative example 2 is compared with comparative example 1, and under 23 ℃～50 ℃ temperature condition, peel adhesion strength is high a lot.And there is not to find an improvement of the peel adhesion strength under 5 ℃ coldcondition.
On the other hand, embodiment 3 compares with comparative example 2 with comparative example 1 with 4,5 ℃～50 ℃ temperature; Find about the high several times of peel adhesion strength; And cohesion also takes place and destroys in destruction form more than 40 ℃ easily, and high to the adaptation of copper base material, bond properties and sealing property improve.
Embodiment 5～7
Use compsn 7～9, make compsn/copper test film, use the mensuration of having implemented peel adhesion strength with embodiment 1 same method.With the embodiment 5～7 of its result in table 2.
In embodiment 5 and embodiment 6,, in 5 ℃～50 ℃ wide temperature range, confirm peel adhesion strength and the improvement that destroys form although the usage quantity of resinous principle (C) is respectively 5 quality %, 3 quality %.
(manufacturing of compsn 10～11 and formability evaluation)
Use acrylic acid or the like thermoplastic resin C-3 as resinous principle (C), according to the composition shown in the table 1, use with the same operation of the method for manufacture of compsn 1 and make compsn 10, line material half blocks as a result, can not obtain stable line material, fails to make compsn.
Therefore, for the acrylics that Shore A hardness is high, the MI value is low excessively, we can say to obtain the compsn shown in the present invention.
In addition; Replace resinous principle (C) and the soft propylene acids rubber of use non-thermal plasticity, non-segmented copolymer; According to the composition shown in the table 1, use with the same operation of the method for manufacture of compsn 1 and make compsn 11, countless concavo-convex of online material surface Visual Confirmation.
Therefore, used under the situation of soft propylene acids rubber of non-thermal plasticity since in resinous principle (A) homodisperse not, when for example providing as sheet or membranaceous tackiness agent, the possibility that produces unfavorable situations such as flake, fragment is big.
(to the adhesion test of polyethylene terephthalate film)
Embodiment 8 and comparative example 3
Except the compsn shown in the use table 16 and compsn 4 and use the thick polyethylene terephthalate film of 100 μ m (below be also referred to as " PET film ") as the adhesive substrate; Use and the same method of copper test film situation; Make the bond test sheet, implement and the same tension test of method shown in the embodiment 1.Its result is shown in Table 3.Among the result of the destruction form in table 3, " interface " is expressed as the interface peel of resin combination and adhesive substrate, and the cohesion of " cohesion " expression resin combination destroys, in addition, and the destruction of " material damage " expression PET film.
According to table 3, to compare with having used the comparative example 3 that does not contain the thermoplastic soft acrylics and contain the compsn of epoxy resin, embodiment 8 peel adhesion strength in wide temperature range is strong, forms the material damage of PET film easily.By this results verification, the compsn that contains thermoplastic soft acrylics (C) contains epoxy resin with replacing the thermoplastic soft acrylics compsn is compared, to the adaptation and the stopping property excellence of polyethylene terephthalate.
Utilize possibility on the industry
Saturated polyester resin composition of the present invention and to have used the hot-melt adhesive composition of said composition be high to the bond strength of metallic substance and resin material, the material that adaptation is also excellent.Therefore, be suitable for sealing material and packaged material or foreign material (metal/resin) bonding of electric-electronics, automotive field.
Claims (8)
1. saturated polyester resin composition is characterized in that, contains (A) saturated polyester resin, (B) crystalline polyolefin resinoid and (C) thermoplastic soft acrylics; The percent crystallinity of said crystalline polyolefin resinoid (B) uses DSC to survey periodic melting heat as more than the 50J/g, and the melt index values under 190 ℃ of temperature and the load 21.2N is 0.5～150g/10 minute; The Shore A hardness of said thermoplastic soft acrylics (C) is less than 90, and the melt index values under 190 ℃ of temperature and the load 21.2N is more than 10g/10 minute; When said saturated polyester resin (A), said crystalline polyolefin resinoid (B) and said thermoplastic soft acrylics (C) were added up to 100 quality %, the content of said crystalline polyolefin resinoid (B) and said thermoplastic soft acrylics (C) was respectively 1～30 quality % and 0.5～30 quality %.
2. the described saturated polyester resin composition of claim 1, the Shore A hardness of wherein said thermoplastic soft acrylics (C) is 10～80.
3. the described saturated polyester resin composition of claim 1, wherein said thermoplastic soft acrylics (C) is 10～100g/10 minute 190 ℃ of temperature with melt index values under the load 21.2N.
4. the described saturated polyester resin composition of claim 1, wherein said thermoplastic soft acrylics (C) is a segmented copolymer.
5. the described saturated polyester resin composition of claim 1 wherein also contains (D) epoxy resin.
6. the described saturated polyester resin composition of claim 5; When wherein said saturated polyester resin (A), said crystalline polyolefin resinoid (B), said thermoplastic soft acrylics (C) and said epoxy resin (D) being added up to 100 quality %, the content of said epoxy resin (D) is 1～25 quality %.
7. hot-melt adhesive composition is characterized in that, contains the described saturated polyester resin composition of claim 1.
8. hot-melt adhesive composition is characterized in that, contains the described saturated polyester resin composition of claim 5.
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| JP2007223279 | 2007-08-29 | ||
| JP2007-223279 | 2007-08-29 | ||
| PCT/JP2008/065140 WO2009028477A1 (en) | 2007-08-29 | 2008-08-26 | Saturated polyester resin composition and hot melt adhesive composition |
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| CN101790564B true CN101790564B (en) | 2012-07-18 |
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| FR2951187B1 (en) * | 2009-10-08 | 2012-10-19 | Arkema France | THERMOPLASTIC COMPOSITION BASED ON ACRYLIC BLOCK COPOLYMERS AND USE THEREOF IN ENCAPSULATION OF PHOTOVOLTAIC ELEMENTS |
| JP5581099B2 (en) * | 2010-04-05 | 2014-08-27 | リケンテクノス株式会社 | Composite molded body |
| CN102585747B (en) * | 2011-11-28 | 2013-12-04 | 芜湖群跃电子科技有限公司 | Halogen-free hot melting adhesive suitable for flexible flat cables (FFCs) and preparing method thereof |
| CN103897646B (en) * | 2012-12-28 | 2016-01-06 | 上海轻工业研究所有限公司 | Resistant to hydrolysis polyester hot-melt adhesive and preparation method thereof |
| JP6120589B2 (en) * | 2013-02-01 | 2017-04-26 | ユニチカ株式会社 | Aqueous dispersion, aqueous coating composition using the same, and film |
| JP6313952B2 (en) * | 2013-06-13 | 2018-04-18 | 日東電工株式会社 | Adhesive resin composition |
| JP6809175B2 (en) * | 2016-03-18 | 2021-01-06 | 東洋紡株式会社 | Resin composition for sealing wire harness |
| CN108611038B (en) * | 2018-05-08 | 2021-07-30 | 江苏锦厚新材料科技有限公司 | Metal bottle cap sealant and preparation method thereof |
| JP7272115B2 (en) * | 2019-05-30 | 2023-05-12 | 凸版印刷株式会社 | makeup sheet |
| CN113717676A (en) * | 2021-08-25 | 2021-11-30 | 深圳市睿晖新材料有限公司 | Flame-retardant hot melt adhesive, flame-retardant hot melt adhesive film and flexible wire rod |
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| US4771106A (en) * | 1983-11-26 | 1988-09-13 | Sumitomo Chemical Co., Ltd. | Adhesive resin composition |
| US20010051227A1 (en) * | 1996-05-17 | 2001-12-13 | The Valspar Corporation | Powder coating compositions and method |
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| JPS5986677A (en) * | 1982-11-09 | 1984-05-18 | Sumitomo Chem Co Ltd | Adhesive resin composition |
| JPS61281A (en) * | 1984-06-13 | 1986-01-06 | Sumitomo Chem Co Ltd | Bondable resin composition |
| JPS60115657A (en) * | 1983-11-26 | 1985-06-22 | Sumitomo Chem Co Ltd | Bondable resin composition |
| JPH01254788A (en) * | 1988-04-04 | 1989-10-11 | Toagosei Chem Ind Co Ltd | Resin composition for bonding precoated steel sheet |
| ZA973692B (en) * | 1996-05-17 | 1997-11-25 | Dexter Corp | Extrusion coating compositions and method. |
| JP4277174B2 (en) * | 2003-03-06 | 2009-06-10 | 東洋紡績株式会社 | Resin composition |
| CA2628551C (en) * | 2005-11-25 | 2013-11-19 | Kuraray Co., Ltd. | Polylactic acid composition |
| JP5301783B2 (en) * | 2007-03-26 | 2013-09-25 | 三菱樹脂株式会社 | Heat-shrinkable film, molded article using the heat-shrinkable film, heat-shrinkable label, and container using or fitted with the molded article |
| JP5202853B2 (en) * | 2007-02-14 | 2013-06-05 | 古河電気工業株式会社 | Conductor or optical fiber coating, insulated wire or cable, and optical fiber cord or optical cable |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4771106A (en) * | 1983-11-26 | 1988-09-13 | Sumitomo Chemical Co., Ltd. | Adhesive resin composition |
| US20010051227A1 (en) * | 1996-05-17 | 2001-12-13 | The Valspar Corporation | Powder coating compositions and method |
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| JP5158086B2 (en) | 2013-03-06 |
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| TW200927826A (en) | 2009-07-01 |
| CN101790564A (en) | 2010-07-28 |
| JPWO2009028477A1 (en) | 2010-12-02 |
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