CN106661312B - Polyester resin, coating fluid and laminated body - Google Patents
Polyester resin, coating fluid and laminated body Download PDFInfo
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- CN106661312B CN106661312B CN201580036143.0A CN201580036143A CN106661312B CN 106661312 B CN106661312 B CN 106661312B CN 201580036143 A CN201580036143 A CN 201580036143A CN 106661312 B CN106661312 B CN 106661312B
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
A kind of polyester resin, it is characterized in that, glass transition temperature is -40~40 DEG C, by temperature-deflection curve according to the softening temperature test method measurement of the thermo-mechanical analysis of JIS K7196, the quantity of inflection point is 2~7, and the maximum value of the temperature of inflection point is 5~55 DEG C.
Description
Technical field
It is formed the present invention relates to polyester resin, the coating fluid containing the polyester resin and on substrate and contains the polyester
Laminated body made of the film of resin.
Background technique
The polyester resin such as polyethylene terephthalate, polybutylene terephthalate (PBT) are steady due to mechanical strength, heat
Qualitative, hydrophobicity and resistance to chemical reagents etc. are excellent, so the material as formed bodys such as fiber, film or sheet materials is extensive in every field
It uses.
Polyester resin by proper choice of dicarboxylic acid component and diol component as constituent combination and gather
It closes, various structures and characteristic can be obtained.Then, the film and the substrate for polyester resin being coated on various substrates and being formed
Excellent adhesion, in addition, the film is also excellent relative to the cementability of other substrates.In this way, the adaptation of the film formed
With it is excellent in adhesion, therefore polyester resin in bonding agent, coating agent, ink binder or coating etc. with being widely used on the way.
In recent years, whens processing electronic component etc. in a manner of roll-to-roll, continuously coating is viscous on the plastic foil rolled out from roller
Agent is connect, the film for being formed with the film of bonding agent is temporarily batched in roller, is on one side rolled out it again, on one side progress and electronic component
Etc. the bonding of various bonded objects.In this way, temporarily batching when roller by the film for being formed with the film of bonding agent, need to prevent institute
The bonding agent film of formation and the adhesion of film for contacting and winding on the film.In general, adhesion in order to prevent, bonding agent glues
Connecing property is suppressed.But in bonding with bonded object, bonding agent needs to fully improve cementability, for this contradiction
Project, carried out various effort in the past.
For example, patent document 1 discloses a kind of adhesive composite, it is -20 DEG C~30 containing glass transition temperature
DEG C crystalline polyester resin, glass transition temperature be 40~90 DEG C of amorphous polyester resin and organic solvent.This is viscous
It connects agent composition to have excellent adhesion polyester film, tin-coated copper and electrolytic copper foil, and preventing adhesiving effect is also excellent, such as soft
The adaptation of the requirements such as property flat cable and metal with can use well on the way.
But adhesive composite documented by patent document 1 to improve cementability and preventing adhesiving effect while raising
For the purpose of heat resistance, therefore the bond processing for being formed in the film on substrate and bonded object can not carry out at low temperature.That is, specially
Adhesive composite documented by sharp document 1 and the bond processing of bonded object are carried out at 130 DEG C, low at such as 70~100 DEG C
Temperature is lower carry out bond processing with not being available on the way.
In recent years, as bonded object, increased using the situation of the electronic component for lacking heat resistance etc., this bonded object
It needs to carry out bond processing in a low temperature of such as 70~100 DEG C.In addition, in order to cut down cost when bond processing, under low temperature
The expectation of the excellent polyester resin of bond processing also get higher.However, not yet proposing the bonding under preventing adhesiving effect and low temperature
The two polyester resin for haveing excellent performance of processability.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2009-84348 bulletin
Summary of the invention
The purpose of the present invention is to provide a kind of preventing adhesiving effect is excellent, and the bond processing under low temperature is also excellent
Polyester resin and coating fluid therefrom and laminated body.
The present inventor has made intensive studies, as a result, it has been found that, specific polyester resin is able to solve above-mentioned class
Topic, completes the present invention.
That is, the gist of the invention is as follows.
(1) a kind of polyester resin, which is characterized in that glass transition temperature is -40~40 DEG C, by according to JIS
In temperature-deflection curve of the softening temperature test method measurement of the thermo-mechanical analysis of K7196, the quantity of inflection point is 2~7,
The maximum value of the temperature of inflection point is 5~55 DEG C.
(2) polyester resin according to (1), which is characterized in that as dicarboxylic acid component, containing selected from terephthaldehyde
Acid, M-phthalic acid, adipic acid, azelaic acid, at least three kinds of dicarboxylic acids in decanedioic acid, as diol component, containing being selected from second
Glycol, butanediol, neopentyl glycol, butyl ethyl propylene glycol, 2- methyl-1,3-propanediol, polyethylene glycol, polyoxyethylene bisphenol A
At least three kinds of glycol in ether, polytetramethylene glycol.
(3) polyester resin according to (1) or (2), which is characterized in that containing glass transition temperature be -10~40
DEG C polyester resin (A) and glass transition temperature be -40~-10 DEG C of polyester resin (B), the mass ratio of two kinds of resins
((A)/(B)) is 20/80~95/5.
(4) a kind of coating fluid, which is characterized in that any in (1)~(3) in organic solvent containing 5 mass % or more
Polyester resin described in forms.
(5) a kind of laminated body, which is characterized in that formed on substrate containing polyester tree described in any one of (1)~(3)
The film of rouge forms.
(6) laminated body according to (5), which is characterized in that other substrates are further laminated on film on base material
It forms.
The preventing adhesiving effect of polyester resin of the invention is excellent, and can carry out Nian Jie add with bonded object at low temperature
Work, and the adhesive strength after bonding is also excellent.Therefore, it can be used in lack electronic component of heat resistance etc. as bonded object
Purposes, and cost when can also reduce bond processing.
Detailed description of the invention
Fig. 1 is the temperature-deflection curve for indicating to measure by the softening temperature test method using thermo-mechanical analysis
Schematic diagram.
Specific embodiment
Hereinafter, explaining the present invention in detail.
The glass transition temperature of polyester resin of the invention is -40~40 DEG C, by according to the thermomechanical of JISK7196
In temperature-deflection curve of the softening temperature test method measurement of analysis, the quantity of inflection point is 2~7, and the temperature of inflection point is most
Big value is 5~55 DEG C.
The glass transition temperature (Tg) of polyester resin of the invention needs to be -40~40 DEG C, wherein preferably -35~
30 DEG C, further preferably -35~20 DEG C, most preferably -35~0 DEG C.
If the Tg of polyester resin is less than -40 DEG C, preventing adhesiving effect is deteriorated, on the other hand, can not if Tg is greater than 40 DEG C
Bond processing is carried out at low temperature, is deteriorated carrying out bond processing bonding force.
Polyester resin of the invention needs temperature-deflection curve when using thermo-mechanical analysis device measurement softening point
In, the quantity of inflection point is 2~7, and the maximum value of the temperature of inflection point is 5~55 DEG C.By meeting this characteristic value, can obtain such as
Lower effect, that is, preventing adhesiving effect is excellent, the bond processing being able to carry out under low temperature, and the adhesive strength after bonding is also excellent.
In the present invention, such as above-mentioned characteristic value is that using thermo-mechanical analysis device, (TAInstruments is public by polyester resin
Department's system, " TMA2940 "), in load 500mN, 5 DEG C/min of heating rate, front end probe diameter 1mm, 200 μm of sample thickness, length
It is found out under conditions of 0 DEG C of temperature of degree measurement by entering temperature-deflection curve when measurement is measured softening point by needle
Value.
It should be noted that inflection point is indicated in the form of peak in temperature-deflection curve differential map, and therefore, the number of inflection point
Amount, temperature are equal with the quantity at the peak in differential map, the temperature of summit, and differential map also can be used and find out.
It is illustrated using Fig. 1.Indicate that temperature-deflection curve is 1, inflection point is indicated by 3, temperature-shown in Fig. 1
There are 3 inflection points in deflection curve 1.Then, the respective temperature of inflection point 3 is shown in 5~7, and the maximum value of the temperature of inflection point is 5
Shown in temperature.Then, the minimum value of the temperature of inflection point is temperature shown in 7.Indicate temperature-deflection curve differential map
It is 2, indicate these peaks is 4.
Wherein, the quantity of above-mentioned inflection point is preferably 2~4, and further preferably 2~3.If the quantity of the inflection point of polyester resin
Less than 2, then can not play effect of the invention, any characteristic in the bond processing under preventing adhesiving effect, low temperature be deteriorated or
Two kinds of characteristics are deteriorated.On the other hand, if the quantity of the inflection point of polyester resin is greater than 7, adhesive strength is reduced.
Furthermore, wherein the maximum value of the temperature of inflection point is preferably 10~45 DEG C, further preferably 13~35 DEG C, optimal
It is selected as 17~30 DEG C.If the maximum value of the temperature of inflection point, less than 5 DEG C, the preventing adhesiving effect of polyester resin is deteriorated, on the other hand,
Bond processing is carried out if the maximum value of the temperature of inflection point is greater than 55 DEG C, under low temperature becomes difficult.
In turn, the minimum value of the temperature of inflection point is preferably -20~5 DEG C, wherein preferably -15~0 DEG C.If polyester resin
Inflection point temperature minimum value be less than -20 DEG C, then preventing adhesiving effect be easy be deteriorated, in addition, if the minimum value of the temperature of inflection point
Greater than 5 DEG C, then bond processing is carried out under low temperature and is easy to become difficult.
In polyester resin of the invention, as dicarboxylic acid component, preferably comprise selected from terephthalic acid (TPA), M-phthalic acid,
Adipic acid, azelaic acid, at least three kinds of dicarboxylic acids in decanedioic acid are preferably comprised as diol component selected from ethylene glycol, fourth two
Alcohol, neopentyl glycol, butyl ethyl propylene glycol, 2- methyl-1,3-propanediol, polyethylene glycol, polyoxyethylene bisphenol A ether, poly- four Asia
At least three kinds of glycol in methyl glycol.
In order to which the polyester resin of the invention having such as above-mentioned characteristic value, composition is made, it is preferably made containing following institutes
The polyester resin of 2 kinds of polyester resin (A) and polyester resin (B) showing.
Firstly, being illustrated to polyester resin (A).
Polyester resin (A) is preferably constituted using polybasic carboxylic acid ingredient and diol component as principal component.
As the polybasic carboxylic acid ingredient for constituting polyester resin (A), for example, terephthalic acid (TPA), M-phthalic acid, third can be enumerated
Diacid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid,
Tridecandioic acid, tetracosandioic acid, pentacosandioic acid, hexadecandioic acid (hexadecane diacid), heptadecane diacid, octadecane diacid, nonadecandioic acid,
Eicosane diacid, docosandioic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4 '-dicarboxylate biphenyls, M-phthalic acid 5- sulfonic acid
Sodium, 5- hydroxyl-M-phthalic acid, fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, pyromellitic acid, trimellitic acid, grass
Acid, 1,4 cyclohexanedicarboxylic acid, 1,3- cyclohexane cyclohexanedimethanodibasic, 1,2- cyclohexane cyclohexanedimethanodibasic, 2,5- norbornene dicarboxylic acids, dimerization
Acid, hydrogenated dimer acids etc. or its acid anhydride.They may be used singly or in combination of two or more.
Wherein, terephthalic acid (TPA), isophthalic diformazan are preferably comprised from viewpoints such as durabilities as polybasic carboxylic acid ingredient
Acid.
In addition, the carbon atom number for preferably comprising main chain is 4~18 aliphatic in order to improve the bond processing under low temperature
Dicarboxylic acids, wherein preferably comprise adipic acid (carbon atom number 6), azelaic acid (carbon atom number 9), decanedioic acid (carbon atom number 10), ten
Two docosandioic acids (carbon atom number 12).It is excellent in whole sour components of composition polyester resin (A) when using above-mentioned aliphatic dicarboxylic acid
Select the rouge of the aliphatic dicarboxylic acid of the carbon atom number 4~6 containing 25~50mol%, the carbon atom number 7~10 of 20~45mol%
The aliphatic dicarboxylic acid of the carbon atom number 11~18 of fat race dicarboxylic acids, 10~40mol%.
As the diol component of polyester resin (A) is constituted, for example, ethylene glycol can be enumerated, diethylene glycol, triethylene glycol, gathered
Ethylene glycol, polytetramethylene glycol, 1,4- butanediol, 1,5- pentanediol, 1,6-HD, 1,7- heptandiol, 1,8- ethohexadiol,
1,9- nonanediol, 1,10- decanediol, 1,12- dodecanediol, 1,4 cyclohexane dimethanol, 1,3- cyclohexanedimethanol, tricyclic
Decane dimethanol, the spiroglycol, dimer diol, neopentyl glycol, 2,2- butyl ethyl propylene glycol, 2- methyl-1,3-propanediol, 1,
2- propylene glycol, polyoxyethylene bisphenol A ether etc..They may be used singly or in combination of two or more.
Wherein, from viewpoints such as dissolubilities, as diol component, ethylene glycol, neopentyl glycol, 1,2- the third two is preferably comprised
Alcohol.
In addition, from it can be expected that effect same as aliphatic dicarboxylic acid and the bond processing under low temperature can be improved,
Preferably comprise the ployalkylene glycols such as 0.5~5mol%, polyethylene glycol, polytetramethylene glycol, polyoxyethylene bisphenol A ether.
As polyester resin (A), the polyester resin of following composition is preferably used.
Terephthalic acid (TPA) (20~60mol%)/M-phthalic acid (20~55mol%)/decanedioic acid or azelaic acid (20~
45mol%)/ethylene glycol (40~70mol%)/neopentyl glycol (30~60mol%)
Terephthalic acid (TPA) (20~55mol%)/M-phthalic acid (20~55mol%)/adipic acid (20~
50mol%)/ethylene glycol (40~70mol%)/neopentyl glycol (30~60mol%)
Polyester resin (A) can be within the scope of the effect of the invention as needed containing except above-mentioned polynary carboxylic
Other than sour component and diol component, other monomer components such as hydroxycarboxylic acid, aliphatic lactones, monocarboxylic acid, monohydric alcohol.
In addition, the copolymerization ratios of other monomer components in polyester resin (A) are preferably with respect to whole monomers contained by polyester resin (A)
Ingredient is less than 50mol%.
As hydroxycarboxylic acid, lactic acid, hydroxyacetic acid, 2- hydroxybutyric acid, 3-hydroxybutyrate, 4 hydroxybutyric acid, 2- can be enumerated
Hydroxy-iso-butyric acid, 2- hydroxy-2-methyl butyric acid, 2- hydroxypentanoic acid, 3- hydroxypentanoic acid, 4- hydroxypentanoic acid, 5- hydroxypentanoic acid, 6- hydroxyl
Base caproic acid, 10 hydroxy stearic acid, 4- hydroxy phenyl stearic acid, 4- (beta-hydroxy) ethoxybenzoic acid etc..
As aliphatic lactones, beta-propiolactone, beta-butyrolactone, gamma-butyrolacton, δ-valerolactone, 6-caprolactone etc. can be enumerated.
As monocarboxylic acid, can enumerate lauric acid, myristic acid, palmitinic acid, stearic acid, oleic acid, linoleic acid, linolenic acid,
Benzoic acid, p-tert-butyl benzoic acid, cyclohexane acid etc..
As monohydric alcohol, octanol, decyl alcohol, laruyl alcohol, myristyl alcohol, cetanol, stearyl alcohol, 2- Phenoxyethanol can be enumerated
Deng.
The glass transition temperature of polyester resin (A) is preferably -10~40 DEG C, wherein and more preferably -5~30 DEG C, into one
Preferably 0~20 DEG C of step.If the glass transition temperature of polyester resin (A) is greater than 40 DEG C, by polyester resin (A) and polyester tree
The polyester resin that rouge (B) is constituted is easy to be difficult to carry out the bond processing under low temperature.On the other hand, if the glass of polyester resin (A)
Change transition temperature and be less than -10 DEG C, then the preventing adhesiving effect for the polyester resin being made of polyester resin (A) and polyester resin (B) holds
Easily it is deteriorated.
In addition, the watery fusion heat of polyester resin (A) is preferably smaller than 1J/g.That is, polyester resin (A) is preferably amorphism.
If the watery fusion heat of polyester resin (A) is 1J/g or more, due to crystallinity, by polyester resin (A) and polyester resin
(B) polyester resin constituted is difficult to carry out the bond processing under low temperature, in addition, even if being able to carry out bond processing adhesive strength
It is easy to be deteriorated.
Next, being illustrated to polyester resin (B).
In polyester resin of the invention, the polyester resin (B) contained together with polyester resin (A) is it is also preferred that by polybasic carboxylic acid
Ingredient and diol component are constituted as principal component.
As the polybasic carboxylic acid ingredient for constituting polyester resin (B), for example, terephthalic acid (TPA), M-phthalic acid, third can be enumerated
Diacid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid,
Tridecandioic acid, tetracosandioic acid, pentacosandioic acid, hexadecandioic acid (hexadecane diacid), heptadecane diacid, octadecane diacid, nonadecandioic acid,
Eicosane diacid, docosandioic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4 '-dicarboxylate biphenyls, M-phthalic acid 5- sulfonic acid
Sodium, 5- hydroxyl-M-phthalic acid, fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, pyromellitic acid, trimellitic acid, grass
Acid, 1,4 cyclohexanedicarboxylic acid, 1,3- cyclohexane cyclohexanedimethanodibasic, 1,2- cyclohexane cyclohexanedimethanodibasic, 2,5- norbornene dicarboxylic acids, dimerization
Acid, hydrogenated dimer acids etc. or its acid anhydride.They may be used singly or in combination of two or more.
Wherein, terephthalic acid (TPA), isophthalic diformazan are preferably comprised from viewpoints such as durabilities as polybasic carboxylic acid ingredient
Acid.
In addition, preferably comprising the aliphatic that the carbon atom number of main chain is 6~12 to improve the bond processing under low temperature
Dicarboxylic acids, wherein preferably comprise adipic acid (carbon atom number 6), azelaic acid (carbon atom number 9), decanedioic acid (carbon atom number 10), ten
Two docosandioic acids (carbon atom number 12).It is excellent in whole sour components of composition polyester resin (B) when using above-mentioned aliphatic dicarboxylic acid
Select the aliphatic dicarboxylic acid of the carbon atom number 6~12 containing 10~40mol%, the further preferably carbon of 20~40mol%
The aliphatic dicarboxylic acid of the aliphatic dicarboxylic acid of atomicity 6~8, the carbon atom number 9~12 of 10~30mol%.
As the diol component of polyester resin (B) is constituted, for example, ethylene glycol can be enumerated, diethylene glycol, triethylene glycol, gathered
Ethylene glycol, polytetramethylene glycol, 1,4- butanediol, 1,5- pentanediol, 1,6-HD, 1,7- heptandiol, 1,8- ethohexadiol,
1,9- nonanediol, 1,10- decanediol, 1,12- dodecanediol, 1,4 cyclohexane dimethanol, 1,3- cyclohexanedimethanol, tricyclic
Decane dimethanol, the spiroglycol, dimer diol, neopentyl glycol, 2,2- butyl ethyl propylene glycol, 2- methyl-1,3-propanediol, 1,
2- propylene glycol, polyoxyethylene bisphenol A ether etc..They may be used singly or in combination of two or more.
Wherein, from the viewpoint of crystallinity, as diol component, 1,4-butanediol is preferably comprised.Contain 1,4- fourth two
When alcohol, content is in the whole diol components for constituting polyester resin (B), preferably 50mol% or more, further preferably
70mol% or more.
In addition, preferably comprising 0.5~5mol%, polyethylene glycol, poly- four Asia to improve the bond processing under low temperature
The ployalkylene glycols such as methyl glycol, polyoxyethylene bisphenol A ether.
It, can it is preferable to use the polyester resin of following composition as polyester resin (B).
Terephthalic acid (TPA) (15~50mol%)/M-phthalic acid (20~50mol%)/decanedioic acid or azelaic acid (10~
30mol%)/1,4- butanediol (96mol% or more)
Terephthalic acid (TPA) (15~50mol%)/M-phthalic acid (20~50mol%)/adipic acid (20~
50mol%)/1,4- butanediol (96mol% or more)
Polyester resin (B) can be within the scope of the effect of the invention as needed containing except above-mentioned polynary carboxylic
Other than sour component and diol component, other monomer components such as hydroxycarboxylic acid, aliphatic lactones, monocarboxylic acid, monohydric alcohol.
In addition, the copolymerization ratios of other monomer components in polyester resin (B) are preferably with respect to whole monomers contained by polyester resin (B)
Ingredient is less than 50mol%.
As hydroxycarboxylic acid, lactic acid, hydroxyacetic acid, 2- hydroxybutyric acid, 3-hydroxybutyrate, 4 hydroxybutyric acid, 2- can be enumerated
Hydroxy-iso-butyric acid, 2- hydroxy-2-methyl butyric acid, 2- hydroxypentanoic acid, 3- hydroxypentanoic acid, 4- hydroxypentanoic acid, 5- hydroxypentanoic acid, 6- hydroxyl
Base caproic acid, 10 hydroxy stearic acid, 4- hydroxy phenyl stearic acid, 4- (beta-hydroxy) ethoxybenzoic acid etc..
As aliphatic lactones, beta-propiolactone, beta-butyrolactone, gamma-butyrolacton, δ-valerolactone, 6-caprolactone etc. can be enumerated.
As monocarboxylic acid, can enumerate lauric acid, myristic acid, palmitinic acid, stearic acid, oleic acid, linoleic acid, linolenic acid,
Benzoic acid, p-tert-butyl benzoic acid, cyclohexane acid etc..
As monohydric alcohol, octanol, decyl alcohol, laruyl alcohol, myristyl alcohol, cetanol, stearyl alcohol, 2- Phenoxyethanol can be enumerated
Deng.
The glass transition temperature of polyester resin (B) is preferably -40~-10 DEG C, wherein and more preferably -35~-16 DEG C,
Further preferably -35~-22 DEG C.If the glass transition temperature of polyester resin (B) is greater than -10 DEG C, by polyester resin (A)
It is easy to be difficult to carry out the bond processing under low temperature with polyester resin (B) polyester resin constituted.On the other hand, if polyester resin
(B) glass transition temperature be less than -40 DEG C, then the polyester resin being made of polyester resin (A) and polyester resin (B) it is anti-sticking
Even effect is easy to be deteriorated.
In addition, the watery fusion heat of polyester resin (B) is preferably 1~10J/g.That is, polyester resin (B) preferably crystallizes
Property.If the watery fusion heat of polyester resin (B) is greater than 10J/g, since crystallinity is got higher, dissolubility in organic solvent becomes
It is low, or the cementability of polyester resin being made of polyester resin (A) and polyester resin (B) reduces.On the other hand, if polyester resin
(B) watery fusion heat is less than 1J/g, the then effect that prevents adhesion for the polyester resin being made of polyester resin (A) and polyester resin (B)
Fruit is easy to be deteriorated.
The fusing point of polyester resin (B) is preferably 25~68 DEG C, and more preferably 30~66 DEG C.If the fusing point of polyester resin (B)
Greater than 68 DEG C, then the cementability of the polyester resin being made of sometimes polyester resin (A) and polyester resin (B) at low temperature is poor.Separately
On the one hand, if the fusing point of polyester resin (B) is less than 25 DEG C, the polyester being made of sometimes polyester resin (A) and polyester resin (B)
The preventing adhesiving effect of resin is poor.
The number-average molecular weight of polyester resin (A) and polyester resin (B) is respectively preferably 2000~35000, more preferably
4000~30000, further preferably 6000~25000.If the number-average molecular weight of polyester resin (A) and (B) are greater than 35000,
Solution viscosity when being then dissolved in organic solvent is got higher, and becomes difficult to equably mix mixing each solution, is being incited somebody to action
In the coating fluid that the solution of polyester resin (A) and the solution of polyester resin (B) mix, the bond processing under low temperature sometimes
Property, preventing adhesiving effect are poor.On the other hand, if the number-average molecular weight of polyester resin (A) and (B) are less than 2000, sometimes by polyester
Cementability of the polyester resin that resin (A) and (B) are constituted when film is made is lower.
The mass ratio ((A)/(B)) of polyester resin (A) and polyester resin (B) are preferably 20/80~95/5, wherein preferably
It is 40/60~80/20, further preferably 40/60~60/40.If the quality ratio of polyester resin (A) is greater than 95%, have
When low temperature under bond processing it is poor.On the other hand, if the quality ratio of polyester resin (A) is less than 20%, preventing adhesiving effect
It is easy to be deteriorated.
The important feature of polyester resin of the invention is that bond processing at low temperature is excellent.In general, low in order to obtain
The excellent polyester resin of bond processing under temperature, uses the low polyester resin of glass transition temperature.However, glass is used only
Changing the low polyester resin of transition temperature can not obtain such as effect of the invention.That is, there is such as above-mentioned characteristic with specific quantity cooperation
Polyester resin (A) and polyester resin (B), the characteristic value of resulting polyester resin is set as present invention provide that range, thus
It can meet simultaneously for the first time opposite as the bond processing under preventing adhesiving effect and low temperature (70~100 DEG C) of the invention
Performance.
Such as above-mentioned polyester resin (A), ester resin (B) in order to obtain, for example, being able to use such as the following method.That is, will
After the starting monomers such as polybasic carboxylic acid, glycol put into reactor tank, esterification is carried out.Next, by carrying out in a known manner
Polycondensation can manufacture polyester resin up to reaching required molecular weight.
Esterification for example 180 DEG C or more at a temperature of carry out 4 hours or more.
In general, polycondensation reaction is carried out at 220~280 DEG C using polymerization catalyst under 130Pa decompression below.Make
For polymerization catalyst, the metal acetates such as the titanium compounds such as butyl titanate, zinc acetate, magnesium acetate, zinc acetate, three oxygen can be enumerated
Change organo-tin compounds such as two antimony, hydroxyl butyl tin oxide, tin octoate etc..In addition, having if the usage amount of polymerization catalyst is very few
When polymerization reaction it is slack-off, on the other hand, if excessively, sometimes resulting polyester resin tone reduce.Therefore, polymerization catalyst
Usage amount relative to 1 mole of sour component, preferably 0.1~20 × 10-4Mole.
Then, in order to adjust the acid value of polyester resin, polybasic carboxylic acid can be further added after above-mentioned polycondensation reaction,
Depolymerization reaction is carried out under inert atmosphere.
Polyester resin of the invention can also contain curing agent within the scope of the effect of the invention, solidification helps
Agent, fire retardant, heat stabilizer, antioxidant, lubricant, pigment, filler, bonding imparting agent, other resins, acid anhydrides, prevent it is quiet
The additives such as electric agent, foaming agent.
As curing agent, epoxy resin, acid anhydrides, hexamethylene diisocyanate, toluene di-isocyanate(TDI), hexichol can be enumerated
Dicyclohexylmethane diisocyanate, isophorone diisocyanate, xylene diisocyanate, dicyclohexyl methyl hydride diisocyanate etc.
Isocyanates and its blocked isocyanate, urea diones, beta-hydroxyalkylamides etc..As curing catalysts, can enumerate pungent
Ji Xi, triethylenediamine, triethylamine etc..
As heat stabilizer, phosphoric acid, phosphate etc. can be enumerated.As antioxidant, hindered phenol compound can be enumerated, be obstructed
Amine compounds, sulfide compound etc..
As lubricant, talcum, silica, polyethylene wax, paraffin etc. can be enumerated.As pigment, titanium dioxide can be enumerated
Titanium, calcium carbonate, zinc oxide etc..As bonding imparting agent, tackifier etc. can be enumerated.
As fire retardant, can enumerate decabrominated dipheny base ether, bis- (penta-bromophenyl) ethane, tetrabromobisphenol, hexabromocyclododecane,
The halide such as hexabromobenzene, triphenyl, tricresyl phosphate, 1,3- phenylene bis- (diphenyl phosphoesters), polyphosphoric acid
The phosphorus containing halogen such as the phosphorus compounds such as ammonium, polyphosphoric acid amide, phosphoguanidine, three (chloroethyl) phosphates, three (two chloropropyls) phosphates
Nitrogenated flame retardants, stannic oxide, five oxygen such as acid esters, red phosphorus, triazine, melamine-isocyanurate, ethylene two (melamine)
Change the inorganic fire-retarded auxiliary agent such as two antimony, antimony trioxide, aluminium hydroxide, magnesium hydroxide, organosilicon powder etc..
Coating fluid of the invention is the coating of the polyester resin of the invention in organic solvent containing 5 mass % or more
Liquid.
As organic solvent, the aromatic systems such as toluene, dimethylbenzene, solvent naphtha, solvesso solvent, first can be enumerated
The alcohol series solvents such as the ketone series solvents such as base ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, methanol, ethyl alcohol, isopropanol, isobutanol, acetic acid
Acetic acid ester series solvents such as the ester series solvents such as ethyl ester, n-butyl acetate, cellosolve acetate, methoxyacetic acid ester etc..They can be single
It solely uses, two or more can also be applied in combination.
The content of polyester resin in coating fluid preferably carries out appropriate adjustment depending on the application, wherein preferably 20 mass %
More than, further preferably 30 mass % or more.
Laminated body of the invention is layer made of the film of the polyester resin containing aforementioned present invention is formed on substrate
Stack.In order to form film in substrate surface, it is preferably coated with coating fluid of the invention.
In laminated body of the invention, it is preferably formed uniformly film on the whole in substrate surface, but in substrate surface
When a part forms film, for example, it is preferable to substantially evenly form dotted, band-like film in substrate surface.
In laminated body of the invention, film area can be adjusted suitably depending on the application relative to the ratio of substrate area
It is whole.The ratio of film area is smaller, and the preventing adhesiving effect of laminated body is higher, but there are the trend that cementability reduces.Accordingly, it is considered to
To cementability, film area is preferably 20% or more relative to the ratio of substrate area, wherein preferably 50% or more.
Film formed on the substrate preferably comprises the polyester resin of the invention of 70 mass % or more, wherein preferably contains
There are 80 mass % or more.
As the substrate for constituting laminated body of the invention, can enumerate by polyester resin, polycarbonate resin or polyvinyl chloride
The film or sheet material or the metal foils such as aluminium foil or copper foil etc. that the resins such as resin are constituted.As substrate, can be used it is a variety of these
Film, sheet material, metal foil etc..
Other substrates can be further laminated in laminated body of the invention on the film being formed on substrate.It is formed in substrate
On film and other substrates can according to need by heating, pressurization be bonded.
Other substrates are not particularly limited, can be and be formed with the substrate of film substrate of the same race, be also possible to different
The substrate of kind.
As other substrates, can enumerate polyethylene terephthalate, poly terephthalic acid Isosorbide-5-Nitrae-cyclohexanedimethanol ester,
Polyethylene naphthalate, polyphenylene sulfide, polystyrene, polypropylene, polysulfones, aramid fiber, polycarbonate, polyvinyl alcohol, glass
The resin films such as the cellulose derivatives such as paper, cellulose acetate, polyethylene, polyvinyl chloride, nylon, polyimides, ionomer, resin
Formed body；The stationeries such as braided fabric, non-woven fabrics, glass cloth, kraft capacitor paper, waxed paper, synthetic paper, comprising paper, non-woven fabrics it is compound
Material etc. has the porous substrate in gap；Metal etc..Other substrates also can be used a variety of such as above-mentioned a variety of materials.
The manufacturing method of polyester resin of the invention, coating fluid is illustrated.
Polyester resin of the invention can pass through after polymerizeing above-mentioned polyester resin (A) and polyester resin (B) respectively
In polymeric kettle melting mixing or using extruder carry out melting mixing and manufacture.Furthermore, it is possible to by polyester resin (A) and poly-
After ester resin (B) is dissolved separately in organic solvent, manufactured and mixing these solution.As organic solvent, can be used
Organic solvent same as the organic solvent of coating fluid is constituted.It should be noted that coating fluid of the invention be containing polyester resin and
The coating fluid of organic solvent, therefore preferably use the manufacturing method of the latter.
In addition, coating fluid of the invention can manufacture by the following method: simultaneously by polyester resin (A) and polyester resin (B)
The method for being added in organic solvent and dissolving；It dissolves in organic solvent and melts polyester resin (A) and polyester resin (B)
Melt the method for polyester resin of the invention obtained from being kneaded.
Laminated body of the invention makes it dry as needed and carries out by the way that coating fluid of the invention to be coated on substrate
The removing of organic solvent can form film on substrate.
It is coated on the method on substrate as by coating fluid, is not particularly limited, reverse roll coating method, intaglio plate can be used to apply
Method well known to cloth method, die coating method, comma rubbing method or spray coating method etc..
The preventing adhesiving effect of film containing polyester resin of the invention is excellent.Therefore, it is laminated on base material film by this
Even if roll is made in the laminated body for the film that the coating fluid of invention is formed, the film on base material film also not be overlapped base on it
Material film bonding and can with roll it is long during store.
Embodiment
Hereinafter, further specifically describing the present invention by embodiment.The present invention is not limited to these embodiments.
1. measuring method
(1) composition of polyester resin
Using NMR measurement device (the JNM-LA400 type of Japan Electronics Corporation), carry out1H-NMR measurement, by each list
The peak intensity of body ingredient finds out the composition of polyester resin.It should be noted that using deuterated trifluoroacetic acid as measurement solvent.
(2) glass transition temperature (Tg) of polyester resin, fusing point (Tm), watery fusion heat
By polyester resin at 25 DEG C or more after aging 1 week, according to JIS-K 7121, according to using power-compensation differential to sweep
It retouches calorimetry device (the DIAMONDDSC type of PerkinElmer corporation) and is warming up to 200 DEG C from -50 DEG C with 10 DEG C/min
Figure, using the intermediate point of 2 bending point temperature from glass transition as glass transition temperature (Tg), when will heat up
Fusing point (Tm) of the peak of melting temperature as polyester resin.In addition, finding out watery fusion heat by the peak area of melting temperature.
(3) number-average molecular weight of polyester resin
Use transfusion unit (the LC-10ADvp type of Shimadzu Seisakusho Ltd.'s corporation) and ultraviolet-visible spectrophotometer (Shimadzu
Manufacturing company's SPD-6AV type), the number-average molecular weight of polyester resin is found out in terms of polystyrene conversion by gpc analysis.It answers
Explanation is given, as gpc analysis condition, wavelength is will test and is set as 254nm, use tetrahydrofuran as solvent.
(4) quantity and temperature of inflection point
Resulting coating fluid is coated on Teflon (registered trademark) sheet material, heat treatment in 30 minutes is carried out at 60 DEG C and is removed
It after removing mixed solvent, carries out being dried in vacuo for 24 hours at 80 DEG C, forms 200 μm of thickness of film on Teflon sheet material.
The film of formation is removed from Teflon sheet material, using film as sample, by according to the thermomechanical of JISK7196
Softening temperature test method measuring temperature-deflection curve of analysis (signal of temperature-deflection curve is illustrated in Fig. 1).
Measurement is using thermo-mechanical analysis device (TAInstruments corporation, " TMA2940 "), in load 500mN, heating rate 5
DEG C/min, 0 DEG C front end probe diameter 1mm, measurement of temperature, carry out under conditions of 200 μm of sample thickness.
Then, the temperature-quantity of deflection point of inflexion on a curve and the temperature of inflection point of measurement are read.
(5) anti-blocking properties
By resulting coating fluid using polyester film (S-50 of UNITIKA corporation, 50 μm of thickness, inner face sided corona treatment, outside
The non-sided corona treatment in face), aperture is overlapped into clathrate in a manner of becoming the 50% of spreading area in its inner face sided corona treatment face
After polyester film, desk-top apparatus for coating (the stick apparatus for coating of peace Tian Jingji corporation, film applicator No.542-AB type) coating is used
Resulting coating fluid.Thereafter, the polyester film of overlapping is removed, carries out being heat-treated for 30 seconds at 100 DEG C, mixed solvent is dry, from
And obtain the laminated body 1 that 10 μm of thickness of film is formed on substrate.
Next, on the film of resulting laminated body 1, by as the polyester film of other substrates (UNITIKA corporation
S-50,50 μm of thickness, inner face sided corona treatment, the non-sided corona treatment in outside) the non-corona process face in outside using hot press, (woods is mechanical
Making made) load that applies 0.1MPa under 30 DEG C, the atmosphere of 70%RH makes its bonding obtain laminated body 2.
After laminated body 2 is placed 24 hours under the atmosphere of 23 DEG C × 50%RH, it is cut to length 10cm, width 25mm,
Using instron (the Autograph AG100B type of Shimadzu Seisakusho Ltd.'s corporation), carried out in 23 DEG C of thermostat
180 degree disbonded test measures peel strength, calculates sample number 5 average value.
According to the value of peel strength, according to following 4 Phase Evaluation anti-blocking properties.
◎: less than 0.1N/25mm.
Zero: 0.1N/25mm more than and less than 1.0N/25mm.
△: 1.0N/25mm more than and less than 2.0N/25mm.
×: 2.0N/25mm or more.
(6) bond processing under low temperature
For by it is being made in embodiment, comparative example, be formed with the laminated body 1 of film on substrate and other substrates exist
70, the laminated body 2 for squeezing 10 seconds and making at pressure 0.2MPa under the conditions of 85,100,120 DEG C of each temperature, 23 DEG C ×
After being placed 24 hours under the atmosphere of 50%RH, it is cut to length 10cm, width 25mm, uses instron (Shimadzu system
Make the Autograph AG100B type of institute's corporation), 180 degree disbonded test is carried out in 23 DEG C of thermostat, measurement removing is strong
Degree calculates sample number 5 average value.
According to the value of peel strength, according to the bond processing under following 4 Phase Evaluation low temperature.
◎: 20N/25mm or more.
Zero: 10N/25mm more than and less than 20N/25mm.
△: 5N/25mm more than and less than 10N/25mm.
×: less than 5N/cm.
In the present invention, the laminated body of the evaluation of △ or more is judged as the laminated body with practicability, will × laminated body
It is judged as do not have practicability.
In addition, judging in extruding temperature 70 C, 85 DEG C of any disbonded test, the evaluation of cementability is ◎ or zero
The bond processing of laminated body at low temperature is very excellent.
2. the preparation of polyester resin
Preparation example 1
By terephthalic acid (TPA) 58g (35mol%), M-phthalic acid 58g (35mol%), decanedioic acid 61g (30mol%), second
Glycol 42g (67mol%), neopentyl glycol 71g (68mol%) and as polymerization catalyst butyl titanate 0.1g be packed into
Reactor will be replaced into nitrogen in system.Then, these raw materials are stirred on one side with 1000rpm, is reacted on one side in 245 DEG C of heating
Device makes its melting.After reactor temperature reaches 245 DEG C, 3 hours esterifications are carried out.It, will be in system after 3 hours
Temperature be set as 250 DEG C, to being depressurized in system.Reach high vacuum (pressure: 0.1~10 in system-5Pa after), further
3.0 hours polymerization reactions are carried out, polyester resin (A1) is obtained.
Preparation example 2~26
Other than being changed to as shown in table 1,2 by the raw material of polyester resin composition, similarly grasp with preparation example 1
Make, obtains polyester resin (A2)~(A15), polyester resin (B1)~(B11).By polyester resin obtained in preparation example 1~26
In, the raw material of monomer composition, final composition and resin properties are shown in table 1 and table 2.
In addition, the abbreviation in Tables 1 and 2 respectively indicates following compound.
TPA: terephthalic acid (TPA)
IPA: M-phthalic acid
ADA: adipic acid
AZA: azelaic acid
SEA: decanedioic acid
EG: ethylene glycol
BD:1,4- butanediol
NPG: neopentyl glycol
BEPG:2,2- butyl ethyl propylene glycol
MPD:2- methyl-1,3-propanediol
PEG1000: polyethylene glycol
NEE: polyoxyethylene bisphenol A ether
PTMG1000: polytetramethylene glycol
Embodiment 1
The polyester resin being made of 60 mass parts of polyester resin (A1) and 40 mass parts of polyester resin (B1) is added to first
In the mixed solvent (toluene/methyl ethyl ketone=8/2 (mass ratio)) of benzene and methyl ethyl ketone, vibrated using paint shaker,
Production in the mixed solvent contains the coating fluid of the polyester resin of 30 mass %.
It uses polyester film (S-50 of UNITIKA corporation, 50 μm of thickness, inner face sided corona treatment, the non-sided corona treatment in outside)
As substrate, using desk-top apparatus for coating, (peace Tian Jingji is public in the whole face (spreading area 100%) in its inner face sided corona treatment face
Take charge of the stick apparatus for coating of system, film applicator No.542-AB type) the above-mentioned coating fluid of coating.Thereafter, heat treatment 30 is carried out at 100 DEG C
Second, mixed solvent is dry, thus be produced on be formed on substrate 10 μm of thickness film laminated body 1.
Next, on the film of resulting laminated body 1, by as the polyester film of other substrates (UNITIKA corporation
S-50,50 μm of thickness, inner face sided corona treatment, the non-sided corona treatment in outside) inner face sided corona treatment face use hot press (woods machinery system
Make made), under the conditions of 70,85,100,120 DEG C of each temperature, with pressure 0.2MPa extruding 10 seconds, production was laminated with other bases
The laminated body 2 of material.
Embodiment 2~26, comparative example 1~8
Other than being changed to as shown in table 3~5 by polyester resin (A), the type of (B), content, carry out and embodiment 1
Same operation, coating fluid of the production containing polyester resin, laminated body 1 and the laminated body 2 for being laminated with other substrates.
Embodiment 27~29
In embodiment 27, in substrate surface applied coating solution, on substrate be overlapped aperture at clathrate polyester film, with
The mode for the spreading area that area relative to substrate surface is 20% is coated with, and after coating, removes aperture into the poly- of clathrate
Ester film makes laminated body 1 similarly to Example 1 and is laminated with the laminated body 2 of other substrates in addition to this.In embodiment
In 28, it is with spreading area in embodiment 29 at the polyester film of clathrate using aperture in such a way that spreading area is 50%
80% mode, at the polyester film of clathrate, in addition to this, makes laminated body 1, stacking using aperture similarly to Example 27
There is the laminated body 2 of other substrates.
It is commented by the characteristic value of the polyester resin made in embodiment, comparative example, using the laminated body 2 for being laminated with other substrates
The result of valence various characteristics is shown in table 3~5.
The glass transition temperature of the polyester resin of Examples 1 to 29 is -40~40 DEG C, and the quantity of inflection point is 2~7, is turned
The maximum value of the temperature of point is 5~55 DEG C, therefore preventing adhesiving effect is excellent, and the bond processing under low temperature is excellent.
The maximum value of the temperature of the inflection point of the polyester resin of comparative example 1 is less than 5 DEG C, therefore preventing adhesiving effect is poor.Comparative example 2
The maximum value of the temperature of the inflection point of~5 polyester resin be greater than 55 DEG C, in addition, in comparative example 5 glass transition temperature also greater than
40 DEG C, therefore the bond processing under low temperature is poor.
The glass transition temperature of the polyester resin of comparative example 6 is less than -40 DEG C, therefore preventing adhesiving effect is poor.
The quantity of the inflection point of the polyester resin of comparative example 7,8 is 1, and preventing adhesiving effect is poor in comparative example 7, in comparative example 8
Bond processing under low temperature is poor.
Symbol description
1 temperature-deflection curve
2 differential maps
3 inflection points
4 peaks
The maximum value of the temperature of 5 inflection points
The median of the temperature of 6 inflection points
The minimum value of the temperature of 7 inflection points
Claims (5)
1. a kind of polyester resin, which is characterized in that containing glass transition temperature be -10~40 DEG C, watery fusion heat is less than 1J/
The polyester resin (B) that the polyester resin (A) and glass transition temperature of g is -40~-10 DEG C, fusing point is 25~68 DEG C, two kinds of trees
Mass ratio (A)/(B) of rouge is 20/80~95/5, and the glass transition temperature of the polyester resin is -40~40 DEG C, passes through root
In temperature-deflection curve according to the softening temperature test method measurement of the thermo-mechanical analysis of JIS K7196, the quantity of inflection point is
2~7, the maximum value of the temperature of inflection point is 5~55 DEG C.
2. polyester resin according to claim 1, which is characterized in that as dicarboxylic acid component, containing selected from terephthaldehyde
Acid, M-phthalic acid, adipic acid, azelaic acid, at least three kinds of dicarboxylic acids in decanedioic acid, as diol component, containing being selected from second
Glycol, butanediol, neopentyl glycol, butyl ethyl propylene glycol, 2- methyl-1,3-propanediol, polyethylene glycol, polyoxyethylene bisphenol A
At least three kinds of glycol in ether, polytetramethylene glycol.
3. a kind of coating fluid, which is characterized in that of any of claims 1 or 2 poly- containing 5 mass % or more in organic solvent
Ester resin forms.
4. a kind of laminated body, which is characterized in that form the film for containing polyester resin of any of claims 1 or 2 on substrate
It forms.
5. laminated body according to claim 4, which is characterized in that other substrates are further laminated on film on base material
It forms.
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| PCT/JP2015/072840 WO2016024612A1 (en) | 2014-08-15 | 2015-08-12 | Polyester resin, coating solution, and laminate |
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| TW201802179A (en) * | 2016-03-15 | 2018-01-16 | 東亞合成股份有限公司 | Polyester based resin composition |
| CN108779378A (en) * | 2016-04-15 | 2018-11-09 | 尤尼吉可株式会社 | Adhesive composite |
| CN109651604B (en) * | 2017-10-10 | 2021-09-07 | 中国石油化工股份有限公司 | Preparation method of low-melting-point elastic polyester |
| CN108559069B (en) * | 2018-05-11 | 2020-10-09 | 黄山嘉恒科技有限公司 | Low-temperature curing type polyester resin, preparation method and powder coating |
| KR102554218B1 (en) * | 2018-06-29 | 2023-07-10 | 코오롱인더스트리 주식회사 | Low melting point polyester resin for composite filament and composite filament using thereof |
| WO2021153390A1 (en) * | 2020-01-30 | 2021-08-05 | Dic株式会社 | Pressure-sensitive adhesive tape |
| KR102570661B1 (en) * | 2021-06-11 | 2023-08-23 | 도레이첨단소재 주식회사 | Organic solvent soluble polyester resin, coating agent for supporting layer of water treatment membrane and water treatment membrane comprising the same |
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| CN101735574A (en) * | 2008-11-11 | 2010-06-16 | 尤尼吉可株式会社 | Polyester resin composition |
| CN102575131A (en) * | 2009-10-20 | 2012-07-11 | 日东电工株式会社 | Pressure-sensitive adhesive tape for masking |
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| JPH04164957A (en) * | 1990-10-30 | 1992-06-10 | Toyobo Co Ltd | Polyester resin composition and production thereof |
| JPH06122809A (en) * | 1992-10-13 | 1994-05-06 | Unitika Ltd | Polyester resin composition for extrusion molding |
| JP5181601B2 (en) | 2007-09-28 | 2013-04-10 | 東洋紡株式会社 | Adhesive composition, laminate and flexible flat cable using solvent-soluble crystalline polyester resin |
| JP5340100B2 (en) * | 2009-09-30 | 2013-11-13 | ユニチカ株式会社 | Polyester resin composition, adhesive comprising the polyester resin composition, and laminate using the adhesive |
| JP5398456B2 (en) * | 2009-09-30 | 2014-01-29 | ユニチカ株式会社 | Polyester resin composition, adhesive comprising the polyester resin composition, and laminate using the adhesive |
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| CN101735574A (en) * | 2008-11-11 | 2010-06-16 | 尤尼吉可株式会社 | Polyester resin composition |
| CN102575131A (en) * | 2009-10-20 | 2012-07-11 | 日东电工株式会社 | Pressure-sensitive adhesive tape for masking |
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