JP2000198909A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable compsn. with excellent heat resistance, solvent resistance, and workability, which is useful not only as a vehicle for use in a coating, adhesive, coating agent, and ink, but also as a processing agent for use in a fiber, film, paper product, etc. SOLUTION: This compsn. satisfies the following requirements. 1. It comprises a polyester resin (A) soluble in a solvent. 2. It comprises a reactive compd. (B) selected from the group consisting of an epoxy, an acrylate, and an isocyanate. 3. The ratio of the contents of (A) and (B) is: (A)/(B)=20/80-95/5. 4. The adhesion strength of 0.5 kgf/cm or more is achieved, when the curable resin compsn. is subjected to heat sealing with a polyimide film under any of the conditions of a temp. in the range of 100-300 deg.C, and a curing time in the range of 10 sec-180 min.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to heat resistance, solvent resistance, and workability useful as a vehicle for paints, adhesives, coating agents, and inks, or as a processing agent for fibers, films, and paper products. It relates to an excellent curable composition and its production method.

[0002]

2. Description of the Related Art Conventionally, polyester resins have been used as paints, adhesives, coating agents, etc., but most of them are used in a form dissolved or dispersed in a solvent or water. Some are used as solventless types such as molds. Low-molecular-weight unsaturated polyesters are mainly used for casting as liquid polyesters, but these resins have the disadvantage of brittleness, and their use is limited in other applications. The improvement in mechanical properties can be solved by lowering the crosslink density of the polyester resin, and can be improved by increasing the molecular weight. It is difficult to obtain from its high melt viscosity. In view of the above, in response to the recent trend toward solvent-free, while maintaining the original properties such as adhesiveness and mechanical properties, it has been found that polyester resins that are solvent-free and liquid Development was desired.

[0003]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems and to provide a solventless curable resin composition which is excellent in heat resistance and solvent resistance and can obtain high adhesive strength. .

[0004]

Means for Solving the Problems The present inventors have diligently pursued the above-mentioned problems relating to the compatibility between the characteristics of the polyester resin and the liquefaction, and have completed the present invention. That is, the present invention is a curable composition satisfying the following requirements. 1. Polyester resin (A) soluble in solvent 2. Reactive compound (B) selected from epoxy, acrylic, and isocyanate 3. Ratio of (A) / (B) = 20/80 to 95/5 4. When the curable resin composition is heat-sealed to a polyimide film under any of the conditions of 100 to 300 ° C and curing time of 10 seconds to 180 minutes, the adhesive strength is 0.5 kgf / cm or more.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, a polyester resin is plasticized by a reactive compound and becomes liquid at a temperature lower than the original softening point of the resin. Thereafter, the reactive compound is increased in molecular weight by raising the temperature of the composition to a predetermined curing temperature. As a result, the effect of the reactive compound as a plasticizer is lost, and instead, a function of curing the entire composition is exhibited. The mechanism described above makes it possible to achieve both the properties of polyester resin and liquefaction.
It has also been found to be excellent in heat resistance, solvent resistance, workability, and dimensional stability. Each item is explained below.

(Polyester Resin) The copolymerized polyester resin in the present invention preferably has a molecular weight of 5,000 to 100,000 and contains at least 50 mol% of aromatic dicarboxylic acid in all carboxylic acid components. When the content of the aromatic dicarboxylic acid is less than 50 mol%, the adhesion to the substrate and the mechanical properties are reduced. Also, when the aliphatic dicarboxylic acid exceeds 50 mol%,
Since the aliphatic ester bond has a lower hydrolysis resistance than the aromatic ester bond, troubles such as a decrease in the degree of polymerization of the polyester during storage may be caused.

The aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 5-sodium sulfoisophthalic acid and the like. Aliphatic dicarboxylic acids include succinic acid, adipic acid, azelaic acid,
Sebacic acid, dodecanedioic acid, dimer acid, etc. can be cited. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and its acids. Anhydride,
Fumaric acid, maleic acid, maleic anhydride, itaconic acid,
Citraconic acid, 2,5-norbornene dicarboxylic anhydride,
Examples thereof include tetrahydrophthalic anhydride. Further, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, or hydroxycarboxylic acids such as hydroxypivalic acid, γ-butyrolactone, and ε-caprolactone, and polycarboxylic acids having an imide ring can also be used as necessary. . In particular, when the flame retardancy is required for the cured product, the flame retardancy can be improved by using a polycarboxylic acid having an imide ring.

On the other hand, the glycol component comprises an aliphatic glycol having 2 to 10 carbon atoms and / or an alicyclic glycol having 6 to 12 carbon atoms and / or an ether bond-containing glycol. Examples of the aliphatic glycols of the formulas 2 to 10 include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,2-butanediol.
1,3-butanediol, 2,3-butanediol, 1,5-pentaneddiol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,6-hexanediol , 3-methyl-1,5-pentaneddiol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, neopentyl glycol hydroxypivalate, dimethylol heptane, glycerin monoallyl ether, trimethylol Examples thereof include propane monoallyl ether, dimer diol, hydrogenated dimer diol, and the like.
Examples of the alicyclic glycol include 1,4-cyclohexanedimethanol, tricyclodecanedimethylol, cyclohexanediol, alkylene oxide adducts of bisphenols, hydrogenated bisphenol A, and the like. Examples of the glycol containing an ether bond include diethylene glycol, triethylene glycol, dipropylene glycol and the like. Polyethylene glycol, polypropylene glycol and polytetramethylene glycol may be used if necessary. Other glycols such as polycaprolactone diol, polyvalerolactone diol, and polyols having an imide ring can also be used as appropriate. In particular, when the flame retardancy is required for the cured product, the flame retardancy can be improved by using a polyol having an imide ring. These can be used alone or as a mixture of two or more.

In the polyester resin used in the present invention,
About 0 to 5 mol% of trifunctional or more polycarboxylic acid and / or
Alternatively, a polyol is copolymerized, and the tricarboxylic or more functional polycarboxylic acids include (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) benzophenonetetracarboxylic acid, trimesic acid, ethylene glycol bis (anhydride) Hydrotrimellitate) and glycerol tris (anhydrotrimellitate) are used. On the other hand, trifunctional or higher polyols include glycerin, trimethylolethane,
Trimethylolpropane, pentaerythritol and the like are used. The polycarboxylic acid and / or polyol having three or more functional groups is preferably copolymerized in an amount of 0 to 5 mol%, preferably 0 to 3 mol%, based on all the acid components or all the glycol components. . If it exceeds 5 mol%, sufficient workability may not be provided.

The polyester resin in the present invention preferably has a weight average molecular weight in the range of 5,000 to 200,000, preferably has a weight average molecular weight in the range of 7,000 to 180,000, and more preferably has a weight average molecular weight in the range of 8,000 to 150,000. . When the weight average molecular weight is less than 5,000, various physical properties are deteriorated. When the weight average molecular weight is more than 1,000,000, the solubility in a solvent is lowered, and the workability is increased because the solution viscosity of the curable composition becomes too high. It is not preferable because it decreases.

The polyester resin of the present invention can be polymerized in a solution in addition to polymerization in a molten state. Known carboxylic acid components, glycol components, polymerization catalysts and polymerization conditions can be used.

(Reactive Compound) As the reactive compound used in the present invention, various compounds can be used, and examples thereof include an epoxy compound, an unsaturated compound, and an isocyanate compound.

Examples of the epoxy compound include polyglycidyl ethers and polyglycidyl esters of low molecular weight compounds, such as diglycidyl ether of bisphenol A and its oligomer, diglycidyl ether of bisphenol F and its oligomer, and bisphenol S of bisphenol S. Diglycidyl ether and its oligomers, diglycidyl ether of hydrogenated bisphenol A and its oligomers, diglycidyl ether of alkylene oxide adduct of bisphenol compound, diglycidyl orthophthalate, diglycidyl isophthalate, diglycidyl terephthalate, p -Diglycidyl oxybenzoate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, Click acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether,
1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,
4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, sorbitol tetraglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate, glycerol alkylene oxide Triglycidyl ether of adduct, polyglycidyl ether of diaminodiphenylmethane, N, N-
Diglycidylamino-1,3-glycidylphenyl ether, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, diphenyl ether type epoxy resin,
Novolak type epoxy resin, dicyclopentadiene phenol type epoxy resin, naphthalene type epoxy resin, amine type epoxy resin, alicyclic diepoxy acetal, alicyclic diepoxy adipate, alicyclic diepoxy carboxylate, vinylcyclohexene dioxide, etc. However, it is desirable that the above-mentioned polyimide resin can be dissolved uniformly, and it is also desirable that the polyimide resin is liquid at around the bonding temperature.

Preferred epoxy compounds include diglycidyl ether of bisphenols and polyglycidyl ether of diaminodiphenylmethane. These can be used alone or as a mixture of two or more.

The unsaturated compounds include (meth) acrylates, vinyl compounds such as styrene, vinyl esters such as vinyl acetate, vinyl ethers, (meth)
Examples thereof include acrylamides and allyl compounds. However, when a compound having a low boiling point is used, it is not preferable because it is volatilized at the curing temperature, and a compound having a sufficiently high boiling point is preferable. Preferred unsaturated compounds include esters of (meth) acrylic acid with alcohols having a boiling point of 100 ° C. or higher, (meth) acrylamides, vinyl compounds and the like. These can be used alone or as a mixture of two or more.

As the isocyanate compound, aromatic,
There are aliphatic diisocyanates and trivalent or higher polyisocyanates, which may be low molecular weight compounds or high molecular weight compounds. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate or trimers of these isocyanate compounds, and excess of these isocyanate compounds Amounts and, for example, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine,
Examples thereof include a terminal isocyanate group-containing compound obtained by reacting a low molecular active hydrogen compound such as diethanolamine and triethanolamine or a high active hydrogen compound such as various polyester polyols, polyether polyols and polyamides. Also, isocyanate compounds blocked with various compounds can be used. These can be used alone or as a mixture of two or more.

In the present invention, these compounds preferably function as a plasticizer or a solvent for the polyester resin before the reaction, and function as a crosslinking agent by increasing the molecular weight after the reaction by heating.

The reactive compound in the present invention preferably has a viscosity of 200 poise or less at 25 ° C. and a boiling point of 100 ° C. or more before the reaction. When the viscosity of the reactive compound is 200 poise or less, the plasticizing effect is very high, and the workability is also good. Conversely, if the viscosity is too low, the viscosity is lowered by heating during curing, and phase separation of the polyester resin is likely to occur. It is desirable that the reactive compound hardly volatilizes by heating during curing, and has a boiling point of 10%.
It is preferably at least 0 ° C.

The curable resin composition of the present invention has a temperature of 100 to 300 ° C.
In the case where the curable resin composition is heat-sealed (seal pressure 10 kg / cm ² ) to the polyimide film under any conditions within the range of 10 seconds to 180 minutes by using a tensile tester, etc. 0.5 kgf when evaluated by 90 degree peeling
It must be at least / cm. The adhesive strength is preferably 0.8 kgf / cm or more, more preferably 0.9 kgf / cm or more,
Particularly preferably, it is 1.0 kgf / cm.

The curable resin composition has an adhesive strength of 0.5 kgf / cm
In order to achieve the above, it is necessary that the polyester resin is sufficiently plasticized with the reactive compound. In the process of curing the curable resin composition by heating, before the curable resin composition cures and loses fluidity, the viscosity of the curable resin composition is reduced to a degree sufficient to wet the base material. Need to be there. 10 is the viscosity that can secure sufficient adhesive strength
It is less than about 00poise.

The effect as a plasticizer is preferably such that Tg is reduced by 10 ° C. or more by DSC, TMA, dynamic viscoelasticity measurement or the like. In order for the polyester resin to be plasticized by the reactive compound, it is necessary that the polyester resin is uniformly dissolved in the reactive compound. The present invention is characterized by using a polyester resin having high solvent solubility, which is important for imparting solubility to a reactive compound. It is preferable that the polyester resin is uniformly dissolved in the reactive compound. However, when the polyester resin and the reactive compound are not uniformly dissolved, the plasticization by the reactive compound is hardened. Is small. In addition, from the viewpoint of solubility of the polyester resin, since the polyester resin has an aromatic ring, the reactive compound is preferably an aromatic compound.

[0022] The mixing ratio is a polyester resin / weight ratio by weight.
Reactive compound = 20/80 to 95/5. If the content of the polyester resin is less than 20%, the properties of the cured product are equivalent to those of the cured product of the reactive compound alone, which is not preferable. When the polyester resin content is 95% or more, the effect of plasticization is small. The apparent Tg of the plasticized polyester resin is 100.
It is characteristic that it is below ℃. If the Tg is higher than 100 ° C, it is not suitable for the purpose of the present invention in view of the improvement of the adhesion by plasticization.

As the reactive compound used in the present invention, an epoxy compound is preferred in view of the fact that it has a high boiling point and that no gas is generated during the reaction.

The curable composition of the present invention has a gel fraction of 30 to 90.
%. The gel fraction can be measured by heating the curable composition at 150 ° C for one hour and then immersing the cured product in Soxhlet extraction or solvent. If the gel fraction is too low, the heat resistance decreases, which is not preferable. If the gel fraction is too high, the characteristics of the cured product such as dimensional stability and stress relaxation properties of the cured composition of the present invention are lost, which is not preferable.

The cured product of the present invention has excellent adhesiveness to various substrates, and is particularly suitable for resins such as polyester, polyamide, polyimide, PPS, epoxy and polycarbonate, and metal substrates. Has excellent adhesion. The excellent adhesiveness of the curable composition of the present invention is attributed to the good adhesion at the bonding interface due to plasticization by the reactive compound, which is caused by heating during curing. This is considered to be due to the fact that the water content is sufficiently reduced, and that the film is cured after ensuring sufficient wettability at the interface.

(Blending) In the present invention, in order for the polyester resin to be plasticized by the reactive compound, it is necessary that the polyester resin is dissolved in the reactive compound. As a method of dissolving the polyester resin in the reactive compound, a method of mixing, heating, and dissolving the polyester resin and the reactive compound can be used. Alternatively, a method of dissolving the polyester resin in a common good solvent can also be used. In this case, the solvent can be removed if necessary. In this method, the polyester resin can be dissolved in the reactive compound at a relatively low temperature in a short time. Known common solvents can be used,
Aromatic hydrocarbons, ketones, esters, ethers (cyclic ethers, glycol ethers, etc.), N-
Organic solvents such as substituted amides, alcohols, carboxylic acids, amines, and chlorinated solvents, water, and mixtures of two or more thereof can be used, but solvents that do not easily react with the reactive compound are preferred. When the solvent is removed, a solvent having a boiling point of 100 ° C. or less is preferred from the viewpoint of ease of removal, and the main components are ketones, ethers, alcohols, and chlorine-based solvents. .
These can be used alone or as a mixture of two or more.

The curable composition of the present invention can be obtained by adding various reaction catalysts of the reactive compound to the composition in which the polyester resin is dissolved in the reactive compound, if necessary. Becomes If the reactive compound is an epoxy compound, a curing agent is required. Examples of curing agents for epoxy compounds include amines, mercaptans, acid compounds, acid anhydrides, phenols, and isocyanates. Dicyandiamide, various amine adducts, sulfonium salts, imidazoles, etc. can also be used as latent curing agents, and these can be used alone or as a mixture of two or more. From the viewpoint of storage stability, it is preferable to use a latent curing agent. The compounding amount and the like can be mixed according to a known formulation, but the addition amount is suitably 1 to 50 phr with respect to the reactive compound. When a latent curing agent is used, the presence of a solvent in the composition causes problems such as a decrease in storage stability. It is preferable to use a non-solvent type for the reactive composition or to use a poor solvent for the latent curing agent.

When the reactive compound is an unsaturated compound,
A polymerization initiator that generates radicals by heat is required. As polymerization initiators, peroxides, azo compounds,
Persulfates and other redox initiators can be used. These can be used alone or as a mixture of two or more.

When the reactive compound is an isocyanate compound, amines, polyols and the like can be used. These can be used alone or as a mixture of two or more.

Although the curable composition of the present invention can be used as it is, other curatives, fluidity modifiers, inorganic powders such as colloidal silica, flame retardants, pigments,
Various additives such as dyes and other inorganic / organic compounds can be blended. Examples of other curing agents include phenol formaldehyde resin, amino resin, and polyfunctional aziridine compound. These crosslinking agents can be used in combination with a curing agent or an accelerator.
The curable composition of the present invention may contain a flame retardant.

The curable composition of the present invention can be used by mixing with another resin. Further, paints, inks, coating agents, adhesives, surface treatment agents, and various processing agents based on the curable composition of the present invention are used for dip coating, brushing, roll coating, spraying, various methods. It has applicability to all printing methods.

[0032]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. (Examples) The present invention will be described below using examples. In the examples, “parts” means “parts by weight”, and “%” means “% by weight”. Each measurement item followed the following method.

(1) Reduced viscosity 0.01 g of a polyester resin was dissolved in 25 cc of a mixed solvent of phenol / tetrachloroethane (weight ratio: 6/4) and measured at 30 ° C.

(2) Glass transition temperature (Tg) Determined by dynamic viscoelasticity measurement. Sample size 4 × 15mm
(Thickness: 0.2 mm), frequency: 110 Hz, temperature rise rate: 5 ° C / min. For the preparation of the sample, the curable composition was sandwiched between Teflon sheets and pressed at a predetermined temperature for a predetermined time by a heat press with a 0.2 mm stainless spacer. The obtained cured product was used as a cut sample.

(3) Heat Adhesive The curable composition is applied as a substrate on a biaxially stretched PET film (E5100, manufactured by Toyobo Co., Ltd.) or a polyimide film (Upilex R), and dried to a thickness of 30 μm. Was provided. Next, the substrate (untreated surface in the case of PET film) was overlaid on the coated surface and heat-sealed under the specified conditions. Then, the adhesiveness of the sample cut into 2 cm width was measured by a tensile tester.

(4) Gel Fraction The curable composition is sandwiched between Teflon sheets at a predetermined temperature for a predetermined time.
It was cured with a heat press machine to give a cured product with a thickness of 500 μm. 2 g of the cured product was immersed in DMF at room temperature for one week. Then, the sample was taken out and dried at 200 ° C for 4 hours, and the gel fraction was determined from the weight loss.

(5) Breaking Elongation of Cured Product A curable composition cured in the same manner as in the measurement of the glass transition point was cut out into a width of 2 cm, and measured by a tensile tester.

Example 1 A stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser was charged with 485 parts of dimethyl terephthalate, 485 parts of dimethyl isophthalate, 443 parts of ethylene glycol, 348 parts of neopentyl glycol and 348 parts of tetrapentyl glycol.
Charge 0.5 parts of -n-butyl titanate, up to 180 ° C to 220 ° C
The transesterification was performed for 4 hours. Then 260 ° C
The temperature of the reaction system was gradually reduced while increasing the temperature to 0.2 mmH.
g under reduced pressure for 1 hour and 30 minutes.
1) was obtained. The obtained polyester resin was pale yellow and transparent. Table 1 shows the characteristics of the obtained resin. 30 g of polyester resin obtained, liquid epoxy EP4530 (made by Asahi Denka) 70
g and 100 g of tetrahydrofuran, and after it became homogeneous, the solvent was removed under heating. Add 10g of dicyandiamide, latent curing agent (manufactured by Ajinomoto, Amicure PN2
3) 1 g was added and mixed well to obtain a curable composition (B-1). Table 2 shows the composition of the curable composition.

Example 2 30 g of the polyamideimide (A-1) obtained in Example 1, 30 g of dimethylacrylamide, 40 g of ethylene glycol dimethacrylate, and 1 g of lauroyl peroxide were thoroughly mixed, and the curable composition (B-2) was obtained. ). Example 3 In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 485 parts of dimethyl terephthalate, 195 parts of dimethyl isophthalate, 443 parts of ethylene glycol, 348 parts of neopentyl glycol and 348 parts of tetrapentyl glycol were added.
Charge 0.5 parts of -n-butyl titanate, up to 180 ° C to 220 ° C
The transesterification was performed for 4 hours. Sebacic acid 3
Add 03 parts, carry out the esterification reaction by raising the temperature to 240 ° C, and then gradually raise the temperature to 260 ° C, then gradually reduce the pressure of the reaction system, and react for 1 hour 30 minutes under a reduced pressure of 0.2 mmHg. Resin (A-2) was obtained. The obtained polyester resin was pale yellow and transparent. Table 1 shows the characteristics of the obtained resin. 45 g of polyester resin obtained, liquid epoxy EP4
The solution was dissolved in 55 g of 530 (made by Asahi Denka) and 100 g of tetrahydrofuran, and after the mixture became homogeneous, the solvent was removed. Add 10g of dicyandiamide, latent curing agent (Ajinomoto, AMICURE P
N23) 1 g was added and mixed well to obtain a curable composition (B-3). Table 2 shows the composition of the curable composition.

Example 4 485 parts of dimethyl terephthalate, 485 parts of dimethyl isophthalate, 465 parts of ethylene glycol, 465 parts of ethylene glycol and bisphenol A ethylene oxide adduct (Sanyo) were placed in a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser. 1120 parts of Kasei Chemicals (BPE-20F) and 0.5 part of tetra-n-butyl titanate were charged and transesterification was carried out at 180 ° C to 220 ° C for 4 hours. Then, the temperature of the reaction system was gradually reduced while the temperature was raised to 260 ° C., and the reaction was carried out under a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes to obtain a polyester resin (A-3). The obtained polyester resin was pale yellow and transparent.
Table 1 shows the characteristics of the obtained resin. The resin was dissolved in 40 g of the obtained polyester resin, 60 g of liquid epoxy EP4530 (manufactured by Asahi Denka) and 100 g of methyl ethyl ketone, and after the mixture became homogeneous, the solvent was removed under heating. To this, 20 g of a latent curing agent (Ajinomoto, Amicure PN23) was added and mixed well to obtain a curable composition (B-4). Table 2 shows the composition of the curable composition.

Example 5 Trimellitic anhydride was added to a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser.
153 g, ethylene glycol 200 g, ethanolamine 48.8
g was added, and trimellitic acid and ethanolamine were reacted at room temperature. After imidization at 150 ° C or less, 180 ° C
The esterification reaction was carried out until the inside of the system became uniform. Thereafter, the mixture was cooled to 150 ° C., and 33.2 g of terephthalic acid, 23.6 g of hexanediol, and 0.05 g of zinc acetate dihydrate were added.
After the temperature was raised, the esterification reaction was continued. After the esterification reaction was completed, 0.3 g of trimethyl phosphate was added, and while raising the temperature to 280 ° C, the reaction system was gradually reduced in pressure, and then reacted under a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes to obtain a polyester having an imide ring ( A-4) was obtained. Table 1 shows the characteristics of the obtained resin. The resulting polyester resin was dissolved in 70 g, liquid epoxy EP4530 (Asahi Denka) 30 g, and dimethylformamide 200 g, and after uniformity, the solvent was removed under heating. to this,
10 g of dicyandiamide was added and mixed well to obtain a curable composition (B-5). Table 2 shows the composition of the curable composition.

Comparative Example 1 In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 485 parts of dimethyl terephthalate, 485 parts of dimethyl isophthalate, 682 parts of ethylene glycol and 0.5 part of tetra-n-butyl titanate were added. , And transesterification was carried out from 180 ° C to 220 ° C over 4 hours. Subsequently, the temperature of the reaction system was gradually reduced while the temperature was raised to 260 ° C., and the reaction was carried out under a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes to obtain a polyester resin (A-4). The obtained polyester resin was pale yellow and transparent. Table 1 shows the characteristics of the obtained resin. 50 g of obtained polyester resin, 50 g of liquid epoxy EP4530 (made by Asahi Denka), dimethylformamide 1
00g was mixed under heating, but the polyimide resin was DMF
It did not dissolve in water and did not become a homogeneous solution. The Tg was measured for the film, but no change was observed in the Tg, and no plasticization effect was observed with the epoxy compound.

Comparative Example 2 100 g of the polyester resin (A-1) obtained in Example 1, 5 g of liquid epoxy EP4530 (manufactured by Asahi Denka), and tetrahydrofuran 10
After dissolving in 0 g and becoming homogeneous, the solvent was removed under heating. The Tg of the film was measured, but the decrease in Tg was very small within the measurement error range, suggesting that the effect of plasticizing the epoxy compound was small.

Comparative Example 3 10 g of the polyester resin (A-1) obtained in Example 1, 90 g of liquid epoxy EP4000 (manufactured by Asahi Denka), tetrahydrofuran 1
After dissolving in 100 g and becoming uniform, the solvent was removed under heating. To this, 10 g of dicyandiamide and 1 g of a latent curing agent (manufactured by Ajinomoto, Amicure PN23) were added and mixed well to obtain a curable composition (B-6). Table 2 shows the composition of the curable composition.

[0045]

[Table 1]

[0046]

[Table 2]

Tables 3 and 4 show the properties of the curable resin compositions of Examples and Comparative Examples.

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

As described above, the curable composition of the present invention is plasticized by a reactive compound, so that it is liquid even in a solventless type and has excellent workability. The properties after curing are not only excellent in adhesive strength and mechanical properties, but also excellent in heat resistance and solvent resistance, and can be used as an excellent heat resistant adhesive.

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Claims (1)

[Claims] 1. A curable composition that satisfies the following requirements: 1. Contains a polyester resin (A) soluble in a solvent. 2. Contains a reactive compound (B) selected from epoxy, acrylic, and isocyanate. 3. The content ratio of (A) and (B) is (A) / (B) = 20 / 80-95 / 5. 4.100-300 ℃, curing time within 10 seconds-180 minutes. The adhesive strength when the curable resin composition is heat-sealed to the polyimide film under any of the conditions is 0.5 kgf / cm or more.