JP2010235647A - Polyether-ester block copolymer, and adhesive and laminate comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyether-ester block copolymer for an adhesive suitable for a flexible flat cable, the copolymer having excellent adhesiveness to metal as well as excellent heat resistance and moisture heat resistance. <P>SOLUTION: The polyether-ester block copolymer comprises a polyether segment (a) and an amorphous polyester segment (b) and is characterized in that: (I) the polyether segment (a) has a number average molecular weight of not less than 200 and comprises polyalkylene glycol; and (II) the amorphous polyester segment (b) comprises a dicarboxylic acid unit containing terephthalic acid, and an alcohol unit containing a polyhydric alcohol having an alkyl group with 1 or more carbon atoms in a side chain; and an amorphous polyester resin (B) obtained by single polymerization of the monomer components constituting the amorphous polyester segment (b) has a glass transition temperature of 40°C or higher when the number average molecular weight of the resin (B) is controlled to 15,000 to 30,000. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polyetherester block copolymer having excellent adhesion to a metal such as copper or copper plated with tin (tin-plated copper), excellent heat resistance, and moist heat resistance. . More specifically, it is useful as an adhesive for electrical appliances and automobile-related wiring materials, and relates to a polyetherester block copolymer having excellent heat resistance and moist heat resistance, an adhesive for wiring materials comprising the same, and a laminate. Is.

Polyester resins represented by polyethylene terephthalate and polybutylene terephthalate are widely used in various fields as fibers, films, molding materials, etc., taking advantage of their excellent mechanical strength, thermal stability, hydrophobicity, and chemical resistance. .

Moreover, it is possible to obtain copolymer polyester resins having various characteristics by changing the types of dicarboxylic acids and glycols that are constituents thereof, and they are widely used in adhesives, coating agents, ink binders, paints, etc. ing. Such a copolyester resin generally has excellent adhesion to plastics such as polyester, polycarbonate and polyvinyl chloride resin, or metal foil such as aluminum and copper.

  Utilizing these characteristics, for example, polyester adhesives are widely used in flexible flat cables and the like that are widely used as wiring materials for digital home appliances or automobiles. It has characteristics such as electrical insulation, flame retardancy, and flexibility (peeling resistance at bent portions).

  The flexible flat cable has a structure in which two layers of an insulation film and an adhesive layer are bonded to each other with the adhesive side facing each other and a conductive wire sandwiched therebetween, and the insulation film is made of polyethylene. A material using terephthalate is often used, and a polyester resin having adhesiveness and flexibility and an adhesive made of the same are preferably used for the adhesive layer.

  In order to give adhesion and flexibility, in general polyester resin can give flexibility and adhesiveness mainly by using materials whose glass transition temperature is lower than room temperature, but under conditions of use under temperature conditions higher than room temperature However, there is a risk of causing dielectric breakdown or shorting of the conductor when the adhesive application surfaces are blocked due to tackiness, or when the flow of the application surface occurs to lower the insulation. In particular, as household appliances become thinner and smaller in recent years, the influence of various heat sources such as backlight heat dissipation and CPU heat dissipation cannot be ignored in liquid crystals, and heat resistance is becoming an essential requirement. . In addition, there is a demand for a material that can maintain adhesion without peeling off the adhesive interface even under high temperature and high humidity.

  With respect to such a problem, in Patent Document 1, a specific polyester glycol copolymerized with a specific alkylene glycol as a dihydric alcohol component is excellent in adhesiveness and heat-and-moisture resistance, but there is a concern about blocking. In response to this, a method has been performed in which a curing agent is blended into a polyester resin to form a cross-linked structure, so that peeling of the adhesive interface does not occur even under high temperature and high humidity. However, when a curing agent is used, curing proceeds gradually before application, so it cannot be stored for a long time, or the reaction proceeds even at room temperature, which may require low-temperature storage. There was difficulty.

On the other hand, when reforming is performed using a resin such as an olefin resin, the heat and moisture resistance is improved, but the adhesiveness and heat resistance tend to be low, which is not satisfactory. Furthermore, a method has been proposed in which a hot melt polyester resin is directly applied to a base film by extrusion molding to form an insulation film. However, a hot melt applicator is required and processing costs are generally high. In some cases, crystallization progresses under wet heat, causing separation from the interface.

JP 2001-200041 A

  The present invention relates to an adhesive suitable for a heat-resistant polyetherester-based flexible flat cable having a rating of UL 60 ° C. or higher, and superior to metals such as copper or copper (tin-plated gold copper) whose surface is plated with tin. An object of the present invention is to provide a polyetherester block copolymer having both adhesiveness, excellent heat resistance and heat-and-moisture resistance, an adhesive for wiring materials, and a laminate.

  As a result of intensive research in order to solve such problems, the present inventors, in a polyether ester block copolymer having a glass transition temperature of less than 40 ° C., comprising a polyether segment and an amorphous polyester segment, By forming a polyester ester block copolymer having a specific number average molecular weight and a glass transition temperature, an amorphous polyester resin obtained by polymerizing a monomer component constituting an amorphous polyester segment alone, the above object is achieved. We have found that this can be achieved and have reached the present invention.

  That is, the gist of the present invention is as follows.

(1) A polyether ester block copolymer comprising a polyether segment (a) and an amorphous polyester segment (b) and having a glass transition temperature of less than 40 ° C. and soluble in general-purpose organic solvents,
(I) The polyether segment (a) has a number average molecular weight of 200 or more and is made of polyalkylene glycol,
(II) the amorphous polyester segment (b) comprises a dicarboxylic acid unit containing terephthalic acid, and an alcohol unit containing a polyhydric alcohol having an alkyl group having 1 or more carbon atoms in the side chain;
When the amorphous polyester resin (B) obtained by polymerizing the monomer component forming the amorphous polyester segment (b) alone has a number average molecular weight of 15000 to 30000, the glass transition temperature is 40 ° C. or higher. A polyether ester block copolymer.
(2) A polyether ester block copolymer characterized in that the difference between the glass transition temperature of the polyether ester block copolymer of (1) and the glass transition temperature of the amorphous polyester resin (B) is 30 ° C. or more. Coalescence.
(3) A hydrocarbon having 1 or more carbon atoms bonded to the main molecular chain of the polyetherester block copolymer of (1) or (2) is bonded at a concentration of 1000 equivalents / 10 ⁶ g or more. A polyetherester block copolymer.
(4) The manufacturing method of the polyetherester block copolymer of (1)-(3).
(5) The manufacturing method of the adhesive agent formed by melt | dissolving the polyetherester block copolymer of (1)-(3) in a general purpose organic solvent.
(6) An adhesive obtained using the method for producing an adhesive according to (5).
(7) A laminate formed by applying the adhesive of (6).
(8) The flexible flat cable which consists of a laminated body of (7).

According to the present invention, it consists of a polyether segment and an amorphous polyester segment,
In a polyetherester block copolymer having a glass transition temperature of less than 40 ° C, the amorphous polyester resin obtained by polymerizing the monomer component forming the amorphous polyester segment alone has a specific number average molecular weight and glass transition temperature. Since the polyether ester block copolymer is used, it is possible to provide an adhesive having excellent adhesiveness when used as an adhesive and having excellent heat resistance and heat and moisture resistance.

The polyether ester block copolymer of the present invention comprises a polyether segment (a) and an amorphous polyester segment (b) and has a glass transition temperature of less than 40 ° C. and is soluble in a general-purpose organic solvent. Coalesce,
(I) The polyether segment (a) has a number average molecular weight of 200 or more and is made of polyalkylene glycol,
(II) the amorphous polyester segment (b) comprises a dicarboxylic acid unit containing terephthalic acid, and an alcohol unit containing a polyhydric alcohol having an alkyl group having 1 or more carbon atoms in the side chain;
The amorphous polyester resin (B) obtained by polymerizing the monomer component forming the amorphous polyester segment (b) alone has a number average molecular weight of 15000 to 30000 and a glass transition temperature of 40 ° C. or higher. It is a featured polyetherester block copolymer.

The polyether component that can be used as the polyether segment (a) of the polyetherester block copolymer of the present invention must have a number average molecular weight of 200 or more and consist of a polyalkylene glycol. Examples of such a polyalkylene glycol include polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol and the like. The number average molecular weight of the polyalkylene glycol needs to be 200 or more, preferably 500 to 10,000, more preferably 800 to 5000, and most preferably 1000 to 2500. When the number average molecular weight is less than 200, the heat resistance is undesirably lowered.

The amorphous polyester component that can be used as the amorphous polyester segment (b) of the polyetherester block copolymer of the present invention may contain terephthalic acid as a dicarboxylic acid unit from the viewpoint of improving heat resistance. is necessary. The content is preferably 20 mol% or more, more preferably 40 mol% or more, still more preferably 60 mol% or more, and most preferably 70 mol% or more with respect to 100 mol% of the dicarboxylic acid.

As dicarboxylic acid components other than terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, and hexahydroterephthalic acid can be used. These may be used in combination. Among these, from the viewpoint of maintaining heat resistance, it is preferable to use isophthalic acid, naphthalenedicarboxylic acid, and hexahydroterephthalic acid. In such a case, 0.1 to 80 mol% is preferable, and 1 to 60 mol% is more preferable. Preferably, 10-40 mol% is more preferable.

The amorphous polyester segment (b) needs to contain an aliphatic polyhydric alcohol having an alkyl group having 1 or more carbon atoms in the side chain as an alcohol unit. The content is preferably 2 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, and most preferably 30 mol% or more. If the aliphatic polyhydric alcohol having an alkyl group having 1 or more carbon atoms is not contained in the side chain, the adhesive strength is lowered, which is not preferable.

  Examples of the polyhydric alcohol having an alkyl group having 1 or more carbon atoms in the side chain include 2-methyl-1,3-propanediol, 2,2'-diethyl-1,3-propanediol, and 2-ethyl-2-methyl. -1,3-propanediol, 2-butyl-2-ethyl-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,2-propylene glycol, ethylene oxide adduct of bisphenol A, bisphenol Examples include propylene oxide adducts. These may be used in combination. Among them, neopentyl glycol, 1,2-propylene glycol, an ethylene oxide adduct of bisphenol A, and a propylene oxide adduct of bisphenol are highly effective in increasing the glass transition temperature and are preferable from the viewpoint of improving heat resistance.

  Other alcohols include ethylene glycol, butanediol, hexanediol, diethylene glycol, triethylene glycol, propanediol, 1,4-cyclohexanedimethanol, 1,5-pentanediol, tricyclodecane dimethanol and the like.

In the present invention, when the amorphous polyester resin (B) obtained by polymerizing the monomer component forming the amorphous polyester segment (b) alone has a number average molecular weight of 15000 to 30000, the glass transition temperature Needs to be 40 ° C or higher. When the glass transition temperature is less than 40 ° C., the softening point of the polyester is lowered, the adhesive strength in the high temperature region is lowered, and the heat resistance in the case of a flexible flat cable is lowered, which is not preferable. Here, the reason why the number average molecular weight is increased to 15000 to 30000 as a model is that, when the number average molecular weight is low, the glass transition temperature decreases due to the influence of the hydroxyl end groups and cannot be correctly evaluated. It is because it ends up.

  The polyether ester block copolymer of the present invention comprises the polyether segment (a) and the amorphous polyester segment (b), and has a glass transition temperature of less than 40 ° C. and is soluble in a general-purpose organic solvent. It must be a copolymer.

Specifically, the polyether ester block copolymer of the present invention needs to have a glass transition temperature of less than 40 ° C, preferably less than 30 ° C, and more preferably less than 20 ° C. When the glass transition temperature exceeds 40 ° C., the adhesiveness is lowered, and the flexibility when the flexible flat cable is formed is lowered, and delamination may occur when bent, which is not preferable. The lower limit of the glass transition temperature is not particularly limited, but is preferably −40 ° C. or higher, more preferably −30 ° C. or higher, and further preferably −20 ° C. or higher. Below -40 ℃, it is very sticky and difficult to handle.

  Furthermore, the polyether ester block copolymer of the present invention must be dissolved in a general-purpose organic solvent. The concentration of the solid content in the general-purpose organic solvent is preferably 10% by mass or more, more preferably 20% by mass or more, and most preferably 30% by mass or more. preferable.

The general-purpose organic solvent mentioned here is a non-halogen solvent, and is not limited to those exemplified below. For example, aromatic solvents such as toluene, xylene, solvent naphtha and solvesso, methyl ethyl ketone and methyl isobutyl ketone , Ketone solvents such as cyclohexanone, alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol and isobutyl alcohol, ester solvents such as ethyl acetate and normal butyl acetate, acetate solvents such as cellosolve acetate and methoxyacetate,
Or the solvent is a mixture of two or more. From the viewpoint of VOC, methyl ethyl ketone and ethyl acetate having a low boiling point are preferred.

  The softening point of the polyetherester block copolymer of the present invention is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, and most preferably 60 ° C. or higher. A softening point of less than 30 ° C. is not preferable because the heat resistance decreases. If the heat resistance is lowered, the resin starts to move in an environment where the flexible flat cable is exposed to high temperatures, and the conductor may be peeled off to cause dielectric breakdown, which is not preferable.

The polyether ester block copolymer of the present invention can potentially increase the glass transition temperature by selecting the monomer structure of the amorphous polyester segment (b), and the softening point of the polyether ester block copolymer. Contributes to the maintenance or improvement of In addition, even in a high temperature region that exceeds the glass transition temperature and softening point of the polyetherester block copolymer to some extent, the polyester segment part retains elasticity and plays a role of preventing flow out, so the high temperature region It has the property of being tenacious and maintaining adhesiveness. Therefore, it contributes to the improvement of heat resistance in the case of a flexible flat cable. The potential glass transition temperature of the amorphous polyester segment (b) is obtained by synthesizing the amorphous polyester resin (B) having a composition obtained by taking out only the segment and measuring the glass transition temperature. It is possible to make it manifest.

Although increasing the potential glass transition temperature of the amorphous polyester segment (b) contributes to heat resistance, on the other hand, the viscosity decreases at room temperature, and the adhesion near room temperature decreases. Further, when the flexible flat cable is used, the adhesive layer becomes brittle and causes delamination when bent. Therefore, by introducing a polyether segment (a) having a certain segment length, that is, a molecular weight, to make a block copolymer, the flexibility of the resin is maintained so as not to impair the heat resistance of the amorphous polyester segment (b). Property and viscosity can be imparted and adhesive force can be developed. In addition, the amorphous polyester segment (b) may be reduced in solubility in a low-boiling organic solvent such as methyl ethyl ketone if a monomer having a high glass transition temperature is selected. Can do.

Further, the segment length and blending amount of the polyether segment (a) are adjusted so that the difference between the glass transition temperature of the polyether ester block copolymer and the glass transition temperature of the amorphous polyester resin (B) is 30 ° C. or more. It is preferable to adjust, more preferably 40 ° C. or higher, and further preferably 50 ° C. or higher. This difference can be adjusted by balancing the balance between the polyether segment (a) component and the amorphous polyester segment (b) component, and the mixing ratio. If this difference is less than 30 ° C., the adhesiveness may decrease due to a decrease in viscosity, and the solubility may also decrease.

  The blending ratio of the polyether segment (a) component is incorporated in the alcohol component of the polyether ester block copolymer, and therefore refers to the introduction rate with respect to 100 mol% of the alcohol component, preferably 3 mol% or more, preferably 4 mol%. The above is more preferable.

  The resin of the present invention may contain the following components in addition to the components listed above in a category that does not greatly affect the properties.

  As other carboxylic acid components constituting the acid component of the amorphous polyester segment (b) used in the present invention, various aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and hydroxycarboxylic acids listed below can be used. Examples of aromatic dicarboxylic acids and aliphatic dicarboxylic acids include phthalic acid, 4,4′-dicarboxybiphenyl, 5-sodium sulfoisophthalic acid, 5-hydroxy-isophthalic acid, fumaric acid, maleic acid, itaconic acid, mesacone Acid, citraconic acid, 1,3,4-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, pyromellitic acid, trimellitic acid, oxalic acid, 1,3-cyclohexanedicarboxylic acid, 1,2 -Dicarboxylic acids such as cyclohexanedicarboxylic acid and 2,5-norbornenedicarboxylic acid. These may use anhydride as a monomer raw material.

Examples of hydroxycarboxylic acids include tetrahydrophthalic acid, lactic acid, oxirane, glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid,
2-hydroxyisobutyric acid, 2-hydroxy-2-methylbutyric acid, 2-hydroxyvaleric acid,
Hydroxycarboxylic acids such as 3-hydroxyvaleric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, 10-hydroxystearic acid, 4- (β-hydroxy) ethoxybenzoic acid, malic acid, and And aliphatic lactones such as β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone.

  Other alcohol components constituting the alcohol component of the amorphous polyester segment (b) used in the present invention include 1,2-dihydroxybutane, 1,3-dihydroxybutane, 3-oxapentane-1,5- Diol, 2,2 '-(1,2-ethanediylbis (oxy))-bisethanol, bis (2-hydroxypropyl) ether, 2- (2- (2-hydroxypropoxy) propoxy) -1-propanol, bisphenol S Bisphenol C, bisphenol Z, bisphenol AP, ethylene oxide adduct or propylene oxide adduct of 4,4′-biphenol, 1,3-bis (β-hydroxyethoxy) benzene, 1,2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, poly (oxyethyne-1,2-diyl), poly (oxybutane-1,4-diyl), poly (oxypropane-1,3-diyl), glycerol 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, trimethylolpropane, pentaerythritol, α-methylglucose, mannitol, sorbitol and the like.

  It is not always necessary to use one type of the above monomers, and a mixture of two or more types may be used depending on the properties to be imparted to the resin.

  The polyether ester block copolymer of the present invention may be copolymerized with a monocarboxylic acid or a monoalcohol as necessary. Examples of monocarboxylic acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexane acid, 4-hydroxyphenyl stearic acid, and the like. Examples of the alcohol include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, 2-phenoxyethanol and the like.

  Furthermore, the polyether ester block copolymer of the present invention includes, as necessary, a heat stabilizer such as phosphoric acid and phosphate ester, an antioxidant such as a hindered phenol compound, a hindered amine compound, and a thioether compound, and talc. Conventional additives such as lubricants such as silica and silica, pigments such as titanium oxide, fillers, antistatic agents, and foaming agents may be included.

In the polyetherester block copolymer of the present invention, a hydrocarbon having 1 or more carbon atoms is preferably bonded to the molecular chain as a side chain at a side chain group concentration of 1000 equivalents / 10 ⁶ g or more. Bonding is preferably performed at a concentration of not less than 10 ⁶ g, more preferably not less than 2000 equivalent / 10 ⁶ g. More preferably, they are bound at a concentration of 2500 equivalents / 10 ⁶ g or more. When the side chain group concentration is less than 1000 equivalents / 10 ⁶ g, the adhesion of the polyetherester block copolymer is lowered, which is not preferable.

  The number average molecular weight of the polyetherester block copolymer of the present invention is preferably from 10,000 to 100,000, more preferably from 15,000 to 60,000, and even more preferably from 20,000 to 40,000. When the number average molecular weight is low, the cohesive force is lowered and the adhesive force is lowered, and when the molecular weight is higher than 100,000, the solvent solubility is lowered.

  A method for producing a polyetherester block copolymer will be described.

  After putting the raw materials necessary for the amorphous polyester segment (b) into the reaction vessel, after performing the esterification reaction at a temperature of 180 ° C. or more for 3 hours or more, after adding the polyether forming the polyether segment (a) The polyether ester block copolymer can be produced by polycondensation by a known method, for example, by proceeding the polycondensation reaction at a temperature of 220 to 280 ° C. under a reduced pressure of 130 Pa or less until the desired molecular weight is reached. Can be obtained.

  The polyether ester block copolymer must be block copolymerized, and when it is not block copolymerized, for example, polyethylene glycol is ethylene glycol, and polytetramethylene glycol is 1,4- Butanediol has a chemical structure and properties that are close to each other, so the softening point increases and adhesiveness decreases, and the softening point decreases and heat resistance may decrease. This is a problem for the application of the present invention because it causes performance degradation. Whether or not block copolymerization is performed can be confirmed by performing NMR (nuclear magnetic resonance spectrum) measurement and confirming the presence of the polyether group. Further, if the same monomer component as the resin composition of the block copolymer is batch-charged and a polyether ester copolymer is obtained, the heat resistance is inferior to the polyether ester block copolymer, and the present invention. It cannot be used as an adhesive.

In esterification and polycondensation reactions, titanium compounds such as tetrabutyl titanate, metal acetates such as zinc acetate, magnesium acetate, and zinc acetate, antimony trioxide, hydroxybutyltin oxide, tin octylate, etc. Polymerization can be carried out using the organotin compound. In this case, the amount of catalyst used is preferably 0.1 to 20 × 10 ⁻⁴ mol per 1 mol of the acid component.

  In addition, after the polycondensation reaction is completed, a predetermined amount of a polybasic acid component or an anhydride thereof is added and reacted to modify the terminal hydroxyl group to a carboxyl group or to a carboxyl group in the molecular chain by transesterification. An appropriate acid value can be imparted by introducing.

  Amorphous polyester resin (B) can also be obtained by the same method.

  The polyether ester block copolymer of the present invention can be dissolved in an appropriate general-purpose organic solvent to form an adhesive solution. The concentration of the resin is about 20 to 50 wt%.

  A flame retardant, a flame retardant aid, a curing agent, and the like can be added to the adhesive solution composed of the polyether ester block copolymer and the general-purpose organic as necessary.

  Examples of the flame retardant include, but are not limited to, decabromodiphenyl ether, bis (pentabromophenyl) ethane, tetrabromobisphenol, hexabromocyclododecane, hexabromobenzene and other halides, triphenyl phosphate, triphenyl Cresyl phosphate, 1,3-phenylenebis (diphenyl phosphate), ammonium polyphosphate, polyphosphate amide, phosphorus compounds such as guanidine phosphate, halogen-containing phosphate esters such as tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, red Phosphorus, nitrogen flame retardants such as triazine, melamine cyanurate and ethylene melamine, inorganic flame retardant aids such as tin dioxide, antimony pentoxide, antimony trioxide, aluminum hydroxide and magnesium hydroxide, There are corn powder and so on. In order to reduce the environmental load, it is preferable to select a flame retardant from the viewpoint of non-halogen, non-phosphorus, and deuterated metal.

In addition, the above adhesive solution contains, as necessary, epoxy resin, acid anhydride, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate,
Isocyanates such as isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, and hardeners such as blocked isocyanates, uretdiones, β-hydroxyalkylamides, curing catalysts such as tin octylate, triethylenediamine, triethylamine, titanium dioxide Additives such as pigments such as calcium carbonate and zinc oxide, talc, polyethylene wax, paraffin wax, and tackifier can be used.

  A laminate can be obtained by coating the substrate film with a solvent-type adhesive comprising the polyetherester block copolymer of the present invention and drying it by a known coating method. Examples of the coater that can be used include a bar coater, a comma coater, a die coater, a roll coater, a reverse roll coater, a gravure coater, a gravure reverse coater, and a flow coater. In these coating methods, the thickness of the adhesive layer can be arbitrarily controlled. Further, the adhesive resin may be laminated by a plurality of coating methods.

  For example, a flexible flat cable can be produced as follows.

  That is, an adhesive containing the polyether ester block copolymer of the present invention is dried to a thickness of about 2 to 100 μm on a base film of about 10 to 200 μm of a polyester such as polyethylene terephthalate as a base. Apply and dry the film in the range of 80-150 ° C to create an insulation film, and sandwich a conductor such as tin-plated copper with a thickness of about 20-100 µm between the two adhesive film adhesive layers. A flexible flat cable can be produced by processing for about 1 to 20 seconds at a pressure of 0.2 to 0.8 MPa at a temperature of about 150 to 180 ° C. with a heat sealer.

  Moreover, you may provide a primer layer in an insulation film as needed.

  The present invention will be specifically described below with reference to examples.

1. Raw materials used Hereinafter, polyether was used as a polyether component.
PTMG-1: molecular weight 1000
PTMG-2: molecular weight 600
PEG: molecular weight 200
TEG: molecular weight 150

2. Measuring method

(1) Resin composition of polyetherester block copolymer ¹ H-NMR measurement was performed using an NMR measuring apparatus JNM-LA400 manufactured by JEOL Ltd., and the composition was determined from the peak intensity of each copolymer component. Deuterated trifluoroacetic acid was used as a measurement solvent for measuring the composition of the polyetherester block copolymer.

(2) Number average molecular weight of polyetherester block copolymer and amorphous polyester resin The number average molecular weight was determined by GPC analysis (liquid feeding unit LC-10ADvp type and UV-visible spectrophotometer SPD-6AV type manufactured by Shimadzu Corporation). , Detection wavelength: 254 nm, solvent: tetrahydrofuran, polystyrene conversion).

(3) Glass transition temperature (Tg) of polyetherester block copolymer and amorphous polyester resin
The glass transition temperature (extrapolated glass transition start temperature) was determined according to JIS-K7121 using an input compensation type differential scanning calorimeter (Diamond DSC manufactured by PerkinElmer).

(4) Softening point of polyetherester block copolymer (Ts)
Measurement was performed in accordance with JIS-K7196 using a TA Instruments thermomechanical analyzer (TMA).

(5) Solubility Polyether ester block copolymer is dissolved in methyl ethyl ketone so that the solid content concentration is 30% by mass, placed gently in a transparent glass bottle for 2 hours, and visually evaluated for solubility and uniformity. did. A sample that was completely dissolved and uniform was marked with ◯, and a sample that remained undissolved was marked with ×.

(6) Heat resistance The polyether ester block copolymer is dissolved in a mixed solvent of toluene / methyl ethyl ketone 8/2 (mass ratio) so as to have a solid concentration of 30% by mass, and the solution is 0.3 mm thick. A copper plate was coated with a bar coater and heat treated at 120 ° C. for 2 minutes to prepare a laminate sheet of an adhesive layer having a dry thickness of 20 μm. The laminating sheet was overlaid with a non-corona surface of a PET film having a thickness of 100 μm, and pressed and laminated at 120 ° C. for 1 minute and at a pressure of 100 kPa for 1 minute. The obtained laminate sheet was 25 mm wide and subjected to a 180 ° peel test at 80 ° C. to measure the peel strength. 15N / 25mm or more was accepted.

(7) Adhesiveness Polyether ester block copolymer is dissolved in a mixed solvent of toluene / methyl ethyl ketone 8/2 (mass ratio) so as to have a solid content concentration of 30% by mass, and the solution is 0.3 mm thick. The laminate was coated on a copper plate using a bar coater and heat-treated at 120 ° C. for 2 minutes to produce an adhesive layer laminating sheet having a dry thickness of 20 μm. The laminating sheet was overlaid with a non-corona surface of a PET film having a thickness of 100 μm, and pressed and laminated at 120 ° C. for 1 minute and at a pressure of 100 kPa for 1 minute. The obtained laminate sheet was made 25 mm wide and subjected to a 180 ° peel test at 23 ° C. to measure the peel strength. 15N / 25mm or more was accepted.

(8) Moisture and heat resistance Using a constant temperature and humidity chamber (manufactured by Nakatsu Kagaku Kikai Seisakusho, model LH-30-13M), the copolyester resin is held for 1000 hours under conditions of a temperature of 85 ° C. and a relative humidity of 85%. Heat treatment was performed. The number average molecular weight of the copolyester resin after the wet heat treatment was measured by the above method (e), and the decrease rate relative to the number average molecular weight before the wet heat treatment (untreated) was calculated. When the rate of decrease is 50% or less, the heat and humidity resistance is acceptable.

Example 1
The raw materials were put into the esterification reactor so that 90 mol% of terephthalic acid, 10 mol% of isophthalic acid, 19 mol% of ethylene glycol, 19 mol% of neopentyl glycol, and 57 mol% of tricyclodecane dimethanol were used. While stirring at a rotation speed of 100 rpm with a stirrer, esterification was performed at 250 ° C. for 5 hours under a pressure of 0.25 MPa,
Transfer to a polycondensation can, put polytetramethylene glycol with a molecular weight of 1000 into a polymerization can, put in a polymerization catalyst, gradually reduce pressure to 1.3 hPa over 60 minutes, to a predetermined molecular weight A polycondensation reaction was carried out at 260 ° C. until reaching a polyether ester block copolymer (A1). The number average molecular weight of the obtained polyetherester block copolymer (A1) was 18000, Tg was 35 ° C., and Ts was 79 ° C. Table 1 shows the evaluation results of the side chain group concentration, solubility, adhesiveness, and heat resistance.

  Further, the glass transition temperature of the amorphous polyester resin obtained by polymerizing the monomer component forming the amorphous polyester segment alone was evaluated by polymerizing the amorphous polyester resin in the following synthesis example. . The results are shown in Table 2 and also in Table 1. The Tg2-Tg1 for the glass transition temperature (Tg1) of the polyetherester block copolymer and the glass transition temperature (Tg2) of the amorphous polyester resin. Was calculated.

Examples 2-6
As shown in Table 1, the same procedure as in Example 1 was performed except that the mixing ratio and molecular weight of the raw materials were changed. The results are shown in Table 1.

(Synthesis Example B1) Amorphous polyester simple substance An esterified product was prepared in the same manner as in Example 1, then transferred to a polycondensation can, charged with a polymerization catalyst, and gradually reduced in pressure to 1.3 hPa over 60 minutes. Then, a polycondensation reaction was carried out at 260 ° C. until a predetermined molecular weight was reached to obtain an amorphous polyester resin (B1). The obtained amorphous polyester resin (B1) has the same composition ratio as the resin (A1) of Example 1 except for polytetramethylene glycol, and the number average molecular weight is 18000,
Tg was 93 ° C., and the difference in Tg between the polyetherester block copolymer (A1) and the amorphous polyester resin (B1) was 58 ° C. The results are shown in Table 2.

Synthesis examples B2 to B8
The same operations as in Synthesis Example 1 were performed to synthesize amorphous polyester resins (B2) to (B8), and the number average molecular weight and glass transition temperature were evaluated. The results are shown in Table 2.

Comparative Examples 1-4
As shown in Table 3, the same procedure as in Example 1 was performed except that the blending ratio and molecular weight of the raw materials were changed. The results are shown in Table 3.

  In Examples 1 to 6, since the polyether ester block copolymer was polymerized within the specified range of the present invention, it was excellent in solubility, heat resistance and adhesiveness, and could be suitably used as an adhesive.

  In Comparative Example 1, the glass transition temperature of the amorphous polyester resin B was low, the adhesive strength at 80 ° C. was lowered, and the heat resistance was lowered. Further, it did not contain polyether A, and the difference in glass transition temperature (Tg2-Tg1) between the amorphous polyester resin B and the polyetherester block copolymer was also less than 30 ° C., and the adhesiveness was also lowered.

  In Comparative Example 2, the copolymerization ratio of the side chain alkyl group-containing alcohol having 1 or more carbon atoms was small, the side chain concentration was lowered, and the adhesiveness was lowered.

  In Comparative Example 3, the number average molecular weight of the polyether was small, the polyether segment length was short, the block copolymerization was lowered, and the heat resistance of the amorphous polyester segment was impaired, or the heat resistance was also lowered.

In Comparative Example 4, since the blending amount of the polyether was small, the difference in glass transition temperature between the amorphous polyester resin B and the polyether ester resin (Tg2-Tg1) was also less than 30 ° C., and the adhesiveness was lowered. Further, it was not completely dissolved in methyl ethyl ketone, and the solution part also became cloudy.

Claims (8)

A polyether ester block copolymer comprising a polyether segment (a) and an amorphous polyester segment (b) and having a glass transition temperature of less than 40 ° C. and soluble in a general-purpose organic solvent,
(I) The polyether segment (a) has a number average molecular weight of 200 or more and is made of polyalkylene glycol,
(II) the amorphous polyester segment (b) comprises a dicarboxylic acid unit containing terephthalic acid, and an alcohol unit containing a polyhydric alcohol having an alkyl group having 1 or more carbon atoms in the side chain;
When the amorphous polyester resin (B) obtained by polymerizing the monomer component forming the amorphous polyester segment (b) alone has a number average molecular weight of 15000 to 30000, the glass transition temperature is 40 ° C. or higher. A polyether ester block copolymer.   The polyether ester block copolymer, wherein the difference between the glass transition temperature of the polyether ester block copolymer according to claim 1 and the glass transition temperature of the amorphous polyester resin (B) is 30 ° C or more. . The hydrocarbon having 1 or more carbon atoms bonded to the main molecular chain of the polyetherester block copolymer according to claim 1 or 2 is bonded at a concentration of 1000 equivalents / 10 ⁶ g or more. Polyether ester block copolymer.   The manufacturing method of the polyetherester block copolymer of Claims 1-3.   The manufacturing method of the adhesive agent formed by melt | dissolving the polyetherester block copolymer of Claims 1-3 in a general purpose organic solvent.   The adhesive obtained using the manufacturing method of the adhesive of Claim 5.   A laminate formed by applying the adhesive according to claim 6.   The flexible flat cable which consists of a laminated body of Claim 7.