JP5339519B2 - Polyester block copolymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copolyester-based adhesive having both crystallinity and solubility in organic solvents, and excellent in heat resistance and adhesiveness. <P>SOLUTION: This copolyester resin includes an aromatic polyester segment (A) and an aliphatic polyester segment (B); wherein (a) the aromatic polyester segment (A) includes a dicarboxylic acid unit which comprises &ge;20 mol% of terephthalic acid and a diol unit which comprises &ge;50 mol% of butanediol, and (b) the aliphatic polyester segment (B) includes a dicarboxylic acid unit which comprises 0-20 mol% of isophthalic acid and 80-100 mol% of an aliphatic dicarboxylic acid, and a diol unit which comprises &ge;50 mol% of aliphatic diol, and has a glass transition temperature of &lt;-10&deg;C when measured according to JIS-K7121, and satisfies the general formula (I): Q/Tr&gt;1. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

The present invention relates to an adhesive that has both moderate crystallinity and good solubility in an organic solvent, excellent heat resistance and adhesiveness, and less volatile organic compounds after use. The present invention relates to a copolyester adhesive useful for adhesion to a film, cloth, metal or the like.

Polyester resins typified 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, copolymer polyester resins are also suitably used in adhesive applications such as flat cables having a structure in which a linear metal conductor is covered between two polyester films. Such flat cables have come to be widely used in recent years as wiring for AV equipment and computer equipment, which has been increased in density, or as wiring material for automobiles, and the demand for such flat cables is growing rapidly.

In recent years, the chances of electronic parts being exposed to high temperatures have increased, such as the thinning of liquid crystal displays, etc., so with conventional adhesives, the resin flows at high temperatures and moisture enters, causing migration to progress and cause dielectric breakdown. There was a problem that. In such a background, for resin adhesives,
Higher heat resistance is required more than ever.

Therefore, for example, a polyester hot melt adhesive is proposed (see Patent Document 1).
Since the hot melt adhesive has a high melting point and high crystallinity, the resin does not soften unless heated to the melting point. Therefore, higher heat resistance can be imparted than an amorphous resin of a solvent-type adhesive.
However, since it is insoluble in common organic solvents, it is necessary to introduce a dedicated hot-melt applicator, so it is inevitable that the economy will be lower than that of the solvent system, and technical issues to maintain leveling properties There was also a problem that it was somewhat lacking in versatility.

On the other hand, conventional solvent-based polyester adhesives are amorphous polyester resins that have high adhesiveness, but have a problem that the softening temperature is low and the softening occurs at high temperatures, causing the resin to flow and causing dielectric breakdown. It was.

For example, a crystalline solvent-soluble polyester resin using only a linear monomer has been proposed (see Patent Document 2). There was a problem that adhesion, particularly metal adhesion, was low.
This is probably because there is little entanglement of the molecular chain and it is easy to peel off after crystallization.

JP 2003-105302 A JP 2003-327676 A

The present invention relates to an adhesive having both crystallinity and solubility in a general-purpose organic solvent, and excellent in heat resistance and adhesiveness, and is useful for adhesion to resin moldings, resin films, cloths, metals, etc. A polyester adhesive is provided.

As a result of various studies to solve the above problems, the present inventor has reached the present invention. That is, the gist of the present invention is as follows.

(1) an aromatic polyester segment (A), and aliphatic polyester segment (B) Tona Lupo Riesuteru block copolymer,
(A); the aromatic polyester segment (A) comprises 20 mol% or more of dicarboxylic acid units that are terephthalic acid and 50 mol% or more of diol units that are butanediol,
(B); a diol unit in which the aliphatic polyester segment (B) is composed of 0 to 20 mol% isophthalic acid, a dicarboxylic acid unit composed of 80 to 100 mol% aliphatic dicarboxylic acid, and 50 mol% or more aliphatic diol. Consists of
Glass transition temperature as measured according to JIS-K7121 is at -10 ° C. or less, and wherein the to Lupo Riesuteru block copolymer satisfies the following number formula (I).
However, the dihydroxy compound represented by the following general formula (I) and the monohydroxy compound represented by the following general formula (II) are excluded as the components in the aliphatic polyester segment (B).
(Wherein R ¹ and R ² each independently represent an alkylene group, p is 3 or 4, and q and r each independently represent an integer of 0 or more)
(Wherein R ³ represents an alkylene group, s is 2 or 3, and t represents an integer of 0 or more)

Here, the temperature was raised to 150 ° C., the melted copolyester resin was rapidly cooled and solidified to 25 ° C., held at 25 ° C., and 25 ° C. holding time [h] until crystallization again was Tr, heat of crystal fusion after Tr time holding the [J / g] Q, the heat of crystal fusion at the time of Tr = 0 [h] and _{Q 0.} However, 1 ≦ Tr ≦ 6 and Q ₀ ≦ 10.
(2) The polyester block copolymer according to (1), wherein the softening point is 90 to 150 ° C.
(3) After manufacturing a polymer having the aromatic polyester segment (A) as a constituent component in advance, an aliphatic polyester segment (B) is added to the polymer having the aromatic polyester segment (A) as a constituent component. A monomer component to be mixed is mixed and stirred at a temperature in the kettle of 180 ° C. or higher for 3 hours or longer, and a polymer having the aromatic polyester segment (A) as a constituent component and a monomer component constituting the aliphatic polyester segment (B) are prepared. (1) The manufacturing method of the polyester block copolymer of (2) characterized by performing polycondensation.
(4) A copolyester adhesive obtained by dissolving the polyester block copolymer of (1) or (2) in an organic solvent.
(5) The copolyester adhesive according to (4), wherein the organic solvent is a mixture of toluene and methyl ethyl ketone.

  According to this invention, it has the adhesiveness outstanding with respect to molded objects, such as a polybutylene terephthalate (PBT), a polycarbonate, and a polyethylene terephthalate (PET), a metal plate, a PET film or a PET sheet, or cloth. Also, since it does not soften until it reaches the melting point temperature due to crystallinity, it has higher heat resistance than amorphous polyester resin, and further has solubility in general-purpose organic solvents, so it has good leveling properties (surface smoothness ) And easy-to-handle adhesives. It can be used in a wide range of fields such as electrical, electronic, mechanical, architectural, automotive, and textile fields.

  Hereinafter, the present invention will be described in detail.

The copolymerized polyester resin of the present invention is a polyester block copolymer comprising an aromatic polyester segment (A) and an aliphatic polyester segment (B).
The aromatic polyester segment (A) comprises 20 mol% or more of dicarboxylic acid units which are terephthalic acid and 50 mol% or more of diol units which are butanediol. The terephthalic acid needs to be 20 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more, further preferably 80 mol% or more, and most preferably 95 mol% or more. The butanediol needs to be 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, and most preferably 80 mol% or more.

When the dicarboxylic acid unit contains less than 20 mol% of terephthalic acid, heat resistance and P
Adhesiveness to ET is reduced, and when the content of butanediol is less than 50 mol% as a diol component, the crystallinity is reduced, and the heat resistance and adhesiveness to PET when used as a polyester resin for adhesive materials descend.

Examples of other acid components that can be used in the aromatic polyester segment (A) include isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, 5-sodium sulfoisophthalic acid, and 5-hydroxy- Isophthalic acid, fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, 1,3,4-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, pyromellitic acid, trimellitic acid, shu Examples thereof include dicarboxylic acids such as acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydrophthalic acid, and 2,5-norbornene dicarboxylic 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, 3-
Hydroxycarboxylic acids such as hydroxyvaleric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, 10-hydroxystearic acid, 4- (β-hydroxy) ethoxybenzoic acid, and β-propio Examples thereof include aliphatic lactones such as lactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone.

As a diol component of the aromatic polyester segment (A), in addition to butanediol, ethylene glycol, 1,3-propanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 1,4-cyclohexanedimethanol Polytetramethylene glycol, polyethylene glycol, polypropylene glycol, dimer diol, and hydrogenated dimer diol can be used. Among them, from the viewpoint of maintaining the heat resistance while lowering the glass transition point, it is preferable to use polytetramethylene glycol, hydrogenated dimer diol, or polyethylene glycol, and the blending in that case is preferably 0.1 to 50 mol%, 1-30 mol% is more preferable.

Moreover, as an acid component of the aromatic polyester segment (A), in addition to terephthalic acid,
Naphthalenedicarboxylic acid, isophthalic acid, sebacic acid, adipic acid, azelaic acid, succinic acid, and hexahydroterephthalic acid can be used. Among these, from the viewpoint of maintaining heat resistance, it is preferable to use sebacic acid, isophthalic acid, or naphthalenedicarboxylic acid. In such a case, 0.1 to 80 mol% is preferable, 1 to 50 mol% is more preferable, and 1 More preferred is ˜20 mol%.

Aliphatic polyester segment (B) is 0-20 mol% isophthalic acid, 80-100
It consists of dicarboxylic acid units composed of at least mol% aliphatic dicarboxylic acid and diol units composed of at least 50 mol% aliphatic diol. Isophthalic acid is 0-20 mol%,
If it exceeds 20 mol%, the properties of the aliphatic polyester segment (B) are impaired, and the block copolymerization when copolymerized with the aromatic polyester segment (A) is reduced. This is a problem because the crystallinity of the polyester block copolymer is lowered. In the present invention, as the dicarboxylic acid unit of the aliphatic polyester segment (B), it is necessary to use 80 to 100 mol% or more of aliphatic dicarboxylic acid.

Examples of the aliphatic dicarboxylic acid that can be used as the dicarboxylic acid unit of the aliphatic polyester segment (B) include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and undecanedioic acid. , Dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, docosanedioic acid, hexahydroterephthalic acid, etc. . Of these, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, octadecanedioic acid, eicosanedioic acid, and hexahydroterephthalic acid are preferably used.

Examples of the diol component of the aliphatic polyester segment (B) include ethylene glycol,
1,2-propylene glycol, 1,3-propanediol, 1,2-dihydroxybutane, 1,3-dihydroxybutane, 1,4-butanediol, 2-methyl-1,3-propanediol, 2,2 ′ -Diethyl-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol,
Neopentyl glycol, 3-methyl-1,5-pentanediol, 3-oxapentane-1,5-diol, 2,2 ′-(1,2-ethanediylbis (oxy))-bisethanol, bis (2-hydroxy Propyl) ether, 2- (2- (2-hydroxypropoxy) propoxy) -1-propanol, bisphenol A, bisphenol S, bisphenol C, bisphenol Z, bisphenol AP, ethylene oxide adduct of 4,4′-biphenol or propylene Oxide adduct, 1,3-bis (β-hydroxyethoxy) benzene, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, poly (oxyethin-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, Examples include sorbitol.

Further, in order to impart the elasticity of the resin, the polyether may be block copolymerized with the copolymerized polyester. Polyethers include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dibutylene glycol,
Tributylene glycol, tetrabutylene glycol, polytetramethylene glycol,
Examples thereof include bistrimethylene glycol and polytrimethylene glycol.

These do not necessarily need to be used alone, and may be used in combination of two or more according to the properties desired to be imparted to the resin.

Moreover, monocarboxylic acid may be copolymerized with the polyester block copolymer . 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. It is done.

Furthermore, the polyester block copolymer of the present invention includes, as necessary, heat stabilizers such as phosphoric acid and phosphate esters, antioxidants such as hindered phenol compounds, hindered amine compounds and thioether compounds, talc and silica, etc. Conventional additives such as lubricants, pigments such as titanium oxide, fillers, antistatic agents, and foaming agents may be included.

Further, the softening point of the port Riesuteru block copolymer of the present invention is preferably from 90 ° C. to 150 DEG ° C., preferably from 95 ° C. to 140 ° C., more preferably 100 ° C. to 130 DEG ° C.. If the softening point is less than 90 ° C., the heat resistance is insufficient, and if it exceeds 150 ° C., the adhesiveness decreases, which is not preferable.

  The softening point in the present invention refers to a thermomechanical analyzer (TMA), the resin is cut to a thickness of about 2 mm, a probe having a diameter of 3 mmΦ is placed on the resin, and a force of 177 mN is applied in a nitrogen atmosphere at −50 ° C. Shows the temperature of the intersection obtained by drawing a tangent to the inflection point when the temperature is raised at a rate of 2 ° C / min.

Further Po Riesuteru block copolymer a glass transition temperature of the present invention (Tg) of must be -10 ° C. or less, preferably -15 ° C. / min or less, laid more is -20 ° C. / min or less, -25 ° C. The following are more preferable, and −30 ° C. or lower is most preferable. When Tg exceeds −10 ° C., the tackiness of the polyester block copolymer is lowered, and the adhesive strength is lowered.

Further, the polyester block copolymer of the present invention is heated to 150 ° C. in a differential scanning calorimeter furnace, and the completely melted polyester block copolymer is rapidly cooled and solidified to 25 ° C. and then held at 25 ° C. Then, the 25 ° C. holding time Tr [h] until crystallization is again 1 ≦ Tr ≦ 6, and then the temperature is lowered to −50 ° C., and then the temperature is raised from −50 ° C. to 200 ° C. at 10 ° C./min. When the heat quantity of the melting endotherm when scanned at a speed is Q [J / g], Q / Tr needs to exceed 1, preferably 1.5 or more, more preferably 2 or more, and further 3 or more preferable. When Q / Tr is 1 or less, the crystallinity is too low and the heat resistance is lowered, which is not preferable.

Further, the heat of crystal melting Q ₀ [J / g] when Tr = 0 [h], that is, rapidly melted to −50 ° C. after melting at 200 ° C., and re-heated at a temperature rising rate of 10 ° C./min. The amount of heat immediately after the melting endotherm needs to be Q ₀ ≦ 10 J / g, preferably 7 J / g or less, more preferably 5 J / g or less, and most preferably 3 J / g or less. When Q ₀ exceeds 10 J / g, the initial crystallinity of the polyester block copolymer is too high, and the tackiness is lowered.

This onset Ming Po Riesuteru block copolymer has a crystallinity, a moderately crystalline need to proceed, heat of crystal fusion at the time of _{Tr = 0 [h] Q 0} [J / g] is Q ₀ ≦ 10 J / g, and then heated up to 150 ° C., and after the completely melted polyester block copolymer was rapidly cooled and solidified to 25 ° C., it was maintained at 25 ° C. When the temperature holding time Tr [h] is 1 ≦ Tr ≦ 6 and Q / Tr> 1 , the initial crystallization sufficiently proceeds with the passage of time 1 ≦ Tr ≦ 6. Indicates. When such a polyester block copolymer is used as an adhesive material, the initial tack is sufficient, and the crystallization of the polyester block copolymer proceeds sufficiently within a short time of 1 to 6 hours, Due to the excellent adhesiveness and the high crystallinity after the adhesive is cured, the adhesiveness at high temperatures can be maintained.

The molecular weight of Po Riesuteru block copolymer of the present invention, preferably in 7000 to 100,000 in number average molecular weight, more preferably from 10,000 to 70,000, most preferably 20,000 to 50,000. When the molecular weight is lower than 7000, the cohesive force is lowered, and when the molecular weight is higher than 100,000, the solvent solubility is lowered, which is not preferable.

Described next process for producing a port Riesuteru block copolymer of the present invention.

The aromatic polyester segment (A) can be produced as a polymer (a) by putting necessary raw materials into a reaction vessel, performing esterification or transesterification, and then polycondensing by a known method. it can.

1000-35000 are preferable, as for the number average molecular weight of the said polymer (a), 1500-30000 are more preferable, 2500-25000 are more preferable, 5000-20000 are the most preferable. The number average molecular weight decreases the softening point becomes high random copolymerization of Po Riesuteru block copolymer is less than 1000, causes a reduction in the thus heat resistance. On the other hand, if the number average molecular weight exceeds 35,000, the polycondensation time becomes long, which is not economical.

Next, the aliphatic polyester segment (B), the polymer for constituting minutes structure formed of a port Riesuteru block copolymer of a monomer component that is missing components constituting the (a) (b), heavy The monomer component (b) and the polymer (a) can be charged into the above-mentioned reaction can where the combination (a) is present, or in a separate reaction can.

Here, the monomer component (b) to be added is a raw material such as carboxylic acid or alcohol as described above, but part or all of them are converted into the polymer (b) by esterification or transesterification reaction. May be included.

In addition, the monomer component (b) to be charged is polymerized alone in advance to obtain a polymer (b), which is then mixed with the polymer (a) and esterified and / or transesterified by a predetermined method (
A post-blocking reaction) may be performed.

  The polymer (b) can be produced by a known method, but the number average molecular weight is preferably 30000 or less, more preferably 20000 or less, further preferably 10,000 or less, and most preferably 5000 or less.

The characteristics of the time obtained Lupo Riesuteru block copolymer, all the raw material in comparison with the copolymer polyester resin when prepared by methods known in one step from monomers, crystallization is fast (of the present invention Q / As a result, the softening point is increased and the heat resistance tends to be increased while maintaining the solubility and the adhesiveness.

The polymer (a) mainly having the role of imparting heat resistance and adhesiveness by the subsequent blocking reaction and the polymer (b) mainly imparting solubility and adhesiveness should keep the block copolymerization moderately. It is possible to maintain heat resistance, adhesion, and solubility without offsetting each other's performance. If there is no subsequent blocking reaction, block copolymerization becomes too strong, crystallization is too fast, adhesiveness may be lowered, and dissolution may not be preferable.

Therefore, it is preferable to carry out esterification and / or transesterification (post block reaction) by the monomer component (b) or the polymer (b) and the polymer (a).

Further, as the next step, polymer (a) and monomer component (b) or polymer (b
The reaction vessel containing () is heated and stirred to carry out esterification and / or transesterification (subsequent blocking reaction).

As this latter block formation reaction, it is necessary to stir for 3 hours or more in a molten state of 180 ° C. or more, preferably 190 ° C. or more and 4 hours or more, 200 ° C. or more and less than 250 ° C., 4 hours or more and 10
Most preferred is less than h. When the temperature is less than 180 ° C. or less than 3 hours, the terephthalic acid residue, isophthalic acid, and aliphatic dicarboxylic acid increase in block copolymerization, and the solution viscosity increases and the solubility decreases, which is not preferable. Moreover, adhesiveness also falls.

During the subsequent blocking reaction, the gas phase inside the reactor is preferably in an inert gas atmosphere or in a vacuum. In the air, oxidative decomposition is severe. The inert gas is nitrogen, helium, argon, hydrogen, etc., but economically inexpensive nitrogen is generally used.

  The pressure is preferably in the range of 0.1 to 5000 hPa, more preferably 1.5 to 3500 hPa, still more preferably 10 to 1000 hPa, and most preferably 50 hPa to 500 hPa.

After subsequent blocking reaction, by polycondensation by known methods, of the present invention
It can be produced port Riesuteru block copolymer. For example, it is possible to obtain the port Riesuteru block copolymer complete the polycondensation reaction until the desired molecular weight at a temperature of 220 to 280 ° C. under a reduced pressure of not more than 1.3HPa.

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 catalyst is preferably used in an amount of 0.1 to 20 × 10 −4 mol per 1 mol of the acid component.

In addition, after the above polycondensation reaction is completed, a predetermined amount of a polybasic acid component, a polyvalent glycol component, or the like is added, and the depolymerization reaction can be performed in an inert atmosphere.

Po Riesuteru block copolymer of the present invention can be dissolved in a general-purpose organic solvents. Of these, methyl ethyl ketone and toluene are preferable.

  The resin concentration is preferably 10 to 40% by mass, and more preferably 20 to 30% by mass.

  The solution viscosity is preferably 5000 mPa · s or less, more preferably 4000 mPa · s or less, further preferably 3000 mPa · s or less, and most preferably 2000 mPa · s or less when measured at 25 ° C. with a B-type viscometer. When it exceeds 5000 mPa · s, it is necessary to use it in a heated state, which may cause problems during handling.

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

(1) Copolyester resin composition 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 copolyester resin.

(2) Number average molecular weight of copolymerized polyester resin The number average molecular weight is determined by GPC analysis (using a liquid feeding unit LC-10ADvp type and a differential refractometer RID-6A type manufactured by Shimadzu Corporation, solvent: tetrahydrofuran, polystyrene conversion). It was.

(3) Glass transition temperature (Tg) of copolymer polyester resin
Using 10 mg of copolymer polyester resin as a sample, measurement was performed under a temperature rising rate of 10 ° C./min using a differential scanning calorimeter [DSC] (diamond DSC type manufactured by PerkinElmer Co.) according to JIS-K7121. The glass transition temperature (extrapolated glass transition start temperature) in the temperature rise curve of 2nd scan was defined as Tg.

(4) Heat of fusion of copolyester resin (Q)
Using a copolymerized polyester resin 10 mg as a sample, a differential scanning calorimeter [DSC] (Diamond DSC type manufactured by PerkinElmer Co.) was used, and the measurement was performed at a temperature rising rate of 10 ° C./min. The heat of fusion of the endothermic peak in the 2nd scan was designated as Q. Measurement was started from room temperature, held at 150 ° C. for 3 minutes, rapidly cooled to 25 ° C., and endothermic peak area of 2nd scan when held at 25 ° C. for a maximum of 10 hours was obtained as heat of fusion Q. . The unit is J / g. Note that the heat quantity of the heat of fusion peak when Tr = 0 is Q ₀ (J / g).

(5) Softening point (Ts)
Using a thermomechanical analyzer (TMA) manufactured by TA Instruments, the copolymer polyester resin is cut into a sheet having a thickness of about 2 mm, a probe having a diameter of 3 mmΦ is placed on the sheet of the copolymer polyester resin, and 177 mN in a nitrogen atmosphere. The temperature at the intersection point where the tangent line was drawn at the inflection point when the temperature was increased from −50 ° C. to 2 ° C./min by applying a force was measured.

(6) Solubility Using a mixed solution of toluene / methyl ethyl ketone (8/2 w / w) as a solvent, dissolving the copolymerized polyester resin at a solid content concentration of 15% by mass to prepare a 30 g solution, then at 55 ° C. Heated and dissolved with stirring. The solution is transferred to a cell of a B-type viscometer, the cell is set in a B-type viscometer at an ambient temperature of 25 ° C., the rotor is rotated, and the pressure is 1 mPa · s / min or less after 20 to 40 minutes. The solution viscosity at the time when the fluctuation settled was read. 3000 mPa · s or less was considered good.

(7) Adhesiveness Using a mixed solution of toluene / methyl ethyl ketone (8/2 w / w) as a solvent, the copolymerized polyester resin was dissolved at a solid content concentration of 30% by mass to obtain 300 g of a solution. The solution was applied to the non-corona surface of a 100 μm PET sheet using a bar coater and then heat treated at 120 ° C. for 2 minutes to produce a laminate sheet having an adhesive of about 30 μm thickness. A copper plate was placed on the adhesive surface of the laminating sheet, and the coated surfaces were laminated at 150 ° C. using a laminator (Lamipacker LPD330, manufactured by Fuji Plastic Co., Ltd.). Laminate sheet side is cut to 25cm width, and the PET sheet side is cut and left at room temperature for 24h or longer, then a 180 degree peel test is performed with 5N, 10N force, and if it is peeled off at 5N, it will be defective and unsuitable. It was good if it was not peeled off at 5N, and very good if it was not peeled off even at 10N.

Production Example 1
In a polymerization kettle, dimethyl terephthalate, 1 mol, so that the composition after polymerization is 100 mol% terephthalic acid, 80 mol% 1,4-butanediol, and 20 mol% polytrimethylene glycol.
, 4-butanediol 80 mol%, polytrimethylene glycol 1000 (molecular weight 100
0) and a transesterification reaction and then a polycondensation reaction were carried out by a conventional method to obtain polybutylene terephthalate (A-1) in which 20 mol% of polytrimethylene glycol having a number average molecular weight of 20000 was copolymerized. The results are shown in Table 1.

Production Example 2
A polymerization kettle is charged with dimethyl terephthalate and 1,4-butanediol so that the molar amount of terephthalic acid is 100 mol% and 1,4-butanediol is 100 mol%. Of polybutylene terephthalate (A-2) was obtained.
The results are shown in Table 1.

Production Example 3
In a polymerization kettle, adipic acid and 1,4-butanediol were charged so as to be 100 mol% of adipic acid and 100 mol% of 1,4-butanediol, and transesterification was performed by a conventional method.
Subsequently, polycondensation reaction is performed, and polybutylene adipate having a number average molecular weight of 18000 (A-3)
Got. The results are shown in Table 1.

Production Example 4
Polyethylene terephthalate (A-4) having a number average molecular weight of 1500 is charged in a polymerization kettle by adding dimethyl terephthalate and ethylene glycol to 100 mol% of terephthalic acid and 100 mol% of ethylene glycol, and performing a transesterification by a conventional method Got. The results are shown in Table 1.

Production Example 5
In a polymerization kettle, terephthalic acid 20 mol%, isophthalic acid 40 mol%, adipic acid 40 mol%
, Terephthalic acid, isophthalic acid, adipic acid and 1,4-butanediol were charged so as to be 100 mol% of 1,4-butanediol, esterified by a conventional method, and then subjected to polycondensation to obtain a number average molecular weight. Of 8,000 copolyester (A-5) was obtained. The results are shown in Table 1.

Production Example 6
In the polymerization kettle, 80 mol% terephthalic acid, 10 mol% isophthalic acid, 10 mol% adipic acid
, Dimethyl terephthalate, isophthalic acid, adipic acid, 1,4-butanediol, ethylene glycol were charged so that the amount of 1,4-butanediol was 50 mol% and ethylene glycol was 50 mol%, and the ester exchange reaction was carried out by a conventional method. Subsequently, a polycondensation reaction was performed to obtain a copolyester (A-6) having a number average molecular weight of 25,000. The results are shown in Table 1.

Reference Examples 1-7
Aliphatic polyester segment for carrying out copolymerization by mixing with aromatic polyester segments (A-1) to (A-6) obtained in Production Examples 1 to 6 when the copolymer polyester resin of the present invention is obtained. The monomer composition of (B) is shown in Table 2.

Production Examples 7 to 10
Aliphatic polyester segment for carrying out copolymerization by mixing with aromatic polyester segments (A-1) to (A-6) obtained in Production Examples 1 to 6 when the copolymer polyester resin of the present invention is obtained. The monomer composition of (B) is shown in Table 3. In Production Examples 7 to 10, the aliphatic polyester was polymerized in advance based on the composition shown in Table 3 before copolymerization with the aromatic polyester segments (A-1) to (A-6). Table 3 summarizes the composition of the aliphatic polyester segment (B) and the number average molecular weight of the obtained aliphatic polyester.

Example 1
The polybutylene terephthalate (A-1) obtained in Production Example 1 is used as the aromatic polyester segment (A), and the aliphatic polyester segment (B) is a dicarboxylic acid component and a glycol component monomer according to the formulation in Table 2, Aromatic polyester segment (A) 5
The esterification reactor was charged with 0 mol% and the aliphatic polyester segment (B) at 50 mol%, nitrogen was introduced into the gas phase part, air was removed, and the rotation speed of 200 rpm with an anchor blade stirrer. While stirring the mixture, the esterification reaction was carried out at 230 ° C. for 5 hours while adjusting the introduction of nitrogen and depressurization so that the gas phase pressure was 2500 hPa. Thereafter, it is transferred to a polycondensation can, 0.0004 mol of tetrabutyl titanate is added to 1 mol of the acid component constituting the copolyester, and a polycondensation reaction is performed at 240 ° C., and stirring is stopped at a predetermined viscosity. The sheet was discharged in the form of a sheet to obtain a copolymer polyester (P-1) sheet. Table 4 summarizes the blending of the aromatic polyester segment (A) and the aliphatic polyester segment (B) and the production conditions for block copolymerization.
As a result of measuring the composition of the obtained copolyester resin by NMR, the resin composition was as prepared. The obtained copolymer polyester resin has a number average molecular weight of 25000, a softening point of 105 ° C., a glass transition point of −40 ° C. or less, Q / Tr of 2.1, and Q ₀ of 6.3 J / g. The solubility in the solvent was good, and the adhesion of the obtained coating film was also good. The results are shown in Table 6.

Examples 2-7
In the same manner as in Examples, the aromatic polyester segments prepared according to the formulations in Table 1, the formulations based on the formulations in Table 2, or the aliphatic polyester segments prepared according to the formulations in Table 3 are shown in Table 4.
These were mixed according to the formulation of Table 5 to prepare copolymer polyester resins (P-2) to (P-7), and various evaluations were performed. The results are shown in Table 6.

Comparative Examples 1-5
In the same manner as in Examples, the aromatic polyester segments prepared according to the formulations in Table 1, the formulations based on the formulations in Table 2, or the aliphatic polyester segments prepared according to the formulations in Table 3 are shown in Table 4.
These were mixed according to the formulation of Table 5 to prepare copolymer polyester resins (P-8) to (P-12), and various evaluations were made. The results are shown in Table 7.

Example 8
The composition was the same as in Example 1, except that the aliphatic polyester segment (B-8) was an aliphatic polyester that had been previously polymerized, and the final copolymerized polyester resin (P-13).
) And various evaluations were performed. The results are shown in Table 5.

Comparative Example 6
A dicarboxylic acid component and a glycol component, which are the same as the final composition of the copolymerized polyester resin (P-1) obtained in Example 1, were mixed at once, polymerized, and copolymerized polyester resin (P-14). ) And various evaluations were performed. The results are shown in Table 6.

In Examples 1-8, the copolymerized polyester resin was prepared in accordance with the prescription prescribed in the present invention, so that it has appropriate crystallinity, excellent solubility in general-purpose organic solvents, heat resistance and adhesiveness. An excellent copolymerized polyester resin as an excellent polyester resin for an adhesive material could be obtained.

In particular, as is clear from the comparison between Example 1 and Example 8, the aliphatic polyester used to obtain the copolymer polyester resin may be (1) mixed with an aromatic polyester as a monomer component. (2) After the aliphatic polyester is polymerized in advance, it may be led to a copolyester resin by mixing an aromatic polyester and an aliphatic polyester. However, (1) the method of obtaining a copolymerized polyester resin by mixing with an aromatic polyester as a monomer component is more optimal for obtaining a copolymerized polyester resin having excellent adhesion while maintaining heat resistance. .

Comparative Example 1
Since terephthalic acid was not introduced into the molecular chain of the aromatic polyester (A), the adhesion of the copolymerized polyester resin to the PET film was rejected. It is assumed that the amount of terephthalic acid was too small and the compatibility with the PET film was lowered.

Comparative Example 2
Since 1,4-butanediol was not introduced into the molecular chain in the aromatic polyester (A), the crystallinity was lowered and the softening point was lowered. Moreover, the glass transition temperature was high, the tackiness was low, and the adhesiveness was lowered.

Comparative Example 3
Block copolymerization may be due to the increase in compatibility with the aromatic polyester (A) due to the introduction of isophthalic acid into the aliphatic polyester (B) as much as 30 mol% with respect to 100 mol% of the acid component of the aliphatic polyester (B). The crystallinity was lowered and the softening point was lowered.

Comparative Example 4
Crystallization of the copolyester resin was too fast, and it was not possible to adhere to the initial stage of adhesion, resulting in a decrease in adhesion.

Comparative Example 5
When the copolymerized polyester resin is used, the blocking temperature is low and the time is insufficient. Therefore, the block copolymerization is increased, the crystallinity is increased, the solubility is lowered, and adhesion is caused by interfacial peeling in the adhesion test. Became unfit.

Comparative Example 6
In order to obtain the same composition as the copolymerized polyester resin of Example 1, all the monomers were put into a reaction can at once, esterified by a known method, then subjected to a polycondensation reaction, and the compositions shown in Table 7 were prepared. A polymerized polyester resin was obtained. The crystallinity was low and the softening point was lowered due to poor block copolymerization.

Claims (5)

Aromatic polyester segment (A), and aliphatic polyester segment (B) a Tona Lupo Riesuteru block copolymer,
(A); the aromatic polyester segment (A) comprises 20 mol% or more of dicarboxylic acid units that are terephthalic acid and 50 mol% or more of diol units that are butanediol,
(B); a diol unit in which the aliphatic polyester segment (B) is composed of 0 to 20 mol% isophthalic acid, a dicarboxylic acid unit composed of 80 to 100 mol% aliphatic dicarboxylic acid, and 50 mol% or more aliphatic diol. Consists of
Glass transition temperature as measured according to JIS-K7121 is at -10 ° C. or less, and wherein the to Lupo Riesuteru block copolymer satisfies the following number formula (I).
However, the dihydroxy compound represented by the following general formula (I) and the monohydroxy compound represented by the following general formula (II) are excluded as the aliphatic polyester segment (B) component.
(Wherein R ¹ and R ² each independently represent an alkylene group, p is 3 or 4, and q and r each independently represent an integer of 0 or more)
(Wherein R ³ represents an alkylene group, s is 2 or 3, and t represents an integer of 0 or more)
Here, the temperature was raised to 150 ° C., the melted copolyester resin was rapidly cooled and solidified to 25 ° C., held at 25 ° C., and 25 ° C. holding time [h] until crystallization again was Tr, heat of crystal fusion after Tr time holding the [J / g] Q, the heat of crystal fusion at the time of Tr = 0 [h] and _{Q 0.} However, 1 ≦ Tr ≦ 6 and Q ₀ ≦ 10. The polyester block copolymer according to claim 1, wherein the softening point is 90 to 150 ° C. A monomer that constitutes the aliphatic polyester segment (B) with respect to the polymer that comprises the aromatic polyester segment (A) as a constituent component after a polymer comprising the aromatic polyester segment (A) as a constituent component is manufactured in advance. The components are mixed and stirred at a temperature in the kettle of 180 ° C. or higher for 3 hours or longer to polycondense the polymer comprising the aromatic polyester segment (A) and the monomer component constituting the aliphatic polyester segment (B). The method for producing a polyester block copolymer according to claim 1 or 2, wherein: A copolyester adhesive obtained by dissolving the polyester block copolymer according to claim 1 or 2 in an organic solvent. 5. The copolyester adhesive according to claim 4, wherein the organic solvent is a mixture of toluene and methyl ethyl ketone.