JPH02145677A - Hot-melt adhesive composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent high-temperature adhesivity, storage stability and stability in coating and forming process and suitable for the bonding of metal, glass, plastic, etc., by compounding a specific compound to a resin composition composed of a thermoplastic copolymerized polyester resin and an epoxy resin. CONSTITUTION:The objective composition is produced by compounding (A) a resin composition composed of (i) 90-40wt.% of a thermoplastic copolymerized polyester resin and (ii) 10-60wt.%, preferably 15-45wt.% of an epoxy resin and (B) 10-50wt.% (based on the epoxy resin) of at least one kind of compound selected from 1,1-dimethyl-1-[2-hydroxy-3-(2-butylenyloxy)propyl]amine lactimide, 1,1-dimethyl-1-(2-hydroxy-3-allyloxypropyl)amine lactimide and 1,1-dimethyl-1-(2- hydroxy-3-allyloxypropyl)amine priopionylimide.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a 2 hot melt adhesive composition, more specifically a 2 hot melt adhesive composition that has excellent heat resistant adhesive properties, storage stability, coating and molding process stability. The present invention relates to a hot melt adhesive composition suitable for adhering metals, metallic glasses, plastics, etc.

(Prior art) Conventional hot melt adhesives are used without solvents and have excellent economical properties such as instant adhesiveness and adhesion to a relatively wide range of adherends, as well as good adhesive performance and workability. Therefore, it has come to be used in large quantities in recent years, mainly in the fields of packaging, bookbinding tubes, and light adhesives.

However, hot melt adhesives are usually 1.

For example, if the coating temperature is 100 to 200°C1 or the bonding temperature is 80 to 160°C, the melting point or softening point must be kept quite low, so if the bonded area is exposed to high temperature again, It essentially had the disadvantage of poor heat resistance, such as being difficult to deform due to heat. For this reason, it could not be used in bonding areas where heat is continuously applied, such as bonding metals to metals or metals to plastics.

Conventionally, various attempts have been made to improve the heat resistance and adhesive properties of hot melt adhesives.

For example, a method has been proposed in which an epoxy resin is blended with a copolymerized polyester resin (Japanese Unexamined Patent Publication No. 50-63025). According to this method, it does exhibit strong adhesive strength at room temperature, but the joint strength at high temperatures is insufficient, and gelation occurs when heated at high temperatures for a long time, making it difficult to use in the bonding process. It has the disadvantage that it hardens inside the hot melt coating equipment or the equipment used during molding, making it unusable.

In order to improve the thermal stability during coating and molding, an adhesive composition was proposed in which epoxy and monoamine compounds were blended with a copolymerized polyester resin (Japanese Patent Publication No. 60-3
No. 9712).

However, although this composition has the effect of delaying the thickening or gelation time during coating and molding when used as a hot melt adhesive, it cannot be stored for a long time at room temperature after being formulated. There remains the problem that if left untreated, the time for thickening or gelling during coating and molding is significantly shortened. Furthermore, the adhesive composition bonded using this adhesive composition does not have sufficient heat-resistant adhesive strength.

(Problems to be Solved by the Invention) As mentioned above, various attempts have been made to impart heat resistance to hot melt adhesives while maintaining storage stability and coating/molding stability. No hot melt adhesive having sufficient heat-resistant adhesive strength is known yet.

The present invention aims to solve the problems of the prior art, and its purpose is to provide a material that has high heat-resistant adhesive strength and also maintains excellent coating/molding process stability and storage stability. An object of the present invention is to provide a hot melt adhesive composition that can be used as a hot melt adhesive.

(Means for Solving the Problems) As a result of intensive research aimed at providing a hot melt adhesive with the above-mentioned excellent performance, the present inventors discovered that epoxy resin was added to thermoplastic copolyester resin. The present invention has been achieved by discovering that a composition containing a specific imide compound has high heat-resistant adhesive strength, is stable in storage, and is stable even when heated at high temperatures and for long periods of time. .

That is, 5 the present invention has a resin content of 90 to 40% by weight of a thermoplastic copolymerized polyester resin and 10 to 60% by weight of an epoxy resin, based on the epoxy resin.
% by weight of 1.1-dimethyl-1-(2-hydroxy-3
-(2-butylenyloxy)propyl]amine lactimide, 1,1-dimethyl-1-(2-hydroxy-3-allyloxypropyl)amine lactimide and 1,1-
The gist of the present invention is a hot melt adhesive composition containing at least one compound selected from dimethyl-1-(2-hydroxy-3-allyloxypropyl)amine propionylimide (hereinafter referred to as an imide compound).

The following two inventions will be explained in detail.

The thermoplastic copolymerized polyester resin in the present invention includes 1
It is prepared from one or more kinds of aromatic and/or aliphatic dicarboxylic acids, one or more kinds of glycols, and optionally one or more kinds of lactones, and one or more kinds of polyhydric carboxylic acids can also be added if necessary.

Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, and 2,6-naphthalene dicarboxylic acid. Examples of aliphatic dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, and sebacic acid. , undecanniic acid, dodecanniic acid, cyclo-xanedicarboxylic acid.

Examples include dimer acid, 1,2-polybutadiene dicarboxylic acid, and the like.

Glycols include ethylene glycol, 1°3-propanediol, and 1,4-butanediol.

1.5-bentanediol, 116-hexanediol, 1.9-nonanediol, neopentylene gelicol, diethylene glycol, triethylene glycol, cyclohexane dimetatool, 1.2-polybutadiene glycol, polyolefin glycol, polyethylene glycol, Examples include polytetramethylene ether glycol.

Examples of the lactone include δ-valerolactone and ε-caprolactone.

Polyhydric carboxylic acid is a compound having three or more carboxyl groups in the compound.For example, trimellitic anhydride, trimellitic acid, pyromellitic anhydride, cyclopencune tetracarboxylic dianhydride, butanetetracarboxylic acid. Acids etc.

The epoxy resins used in the present invention include thermoplastic copolymerized polyester resins and bisphenol A epoxy resins that exhibit high heat resistance strength after reacting with the imide compound described below, novolac epoxy resins, resorcinol epoxy resins, and polyoxyalkylene epoxy resins. Resin etc. are used.

In the present invention, l as the imide compound.

1-dimethyl-1-[2-hydroxy-3-(2butylenyloxy)propyl]amine lactimide, 1.1-
Dimethyl-1-(2-hydroxy-3-allyloxypropyl)amine lactimide or 1,1-dimethyl-1-
(2-hydroxy 3-allyloxypropyl)amine propionylimide is used. Such imide compounds may be used alone or in combination of two or more.

The thermoplastic copolyester resin in the hot melt adhesive composition of the present invention is 90-40% by weight, and the epoxy resin is 10-60% by weight, preferably 15-40% by weight.
It is 45 parts by weight. Also.

The amount of imide compound relative to the epoxy resin is 10-50% by weight. The amount of thermoplastic copolyester resin is 4
Less than 0% by weight (epoxy resin is 60% by weight or more),
The adhesive composition becomes hard and its peel strength tends to decrease.

On the other hand, if the thermoplastic copolymerized polyester resin is 90% by weight or more (the epoxy resin is less than 10% by weight), the necessary heat-resistant adhesive strength cannot be obtained. Furthermore, if the amount of the imide compound is 50% by weight or more based on the epoxy resin, a large amount of unreacted imide compound remains, resulting in poor adhesion.

On the other hand, if it is less than 10% by weight based on the epoxy resin,
Coating and molding stability deteriorates.

There are no particular restrictions on the method for producing the thermoplastic copolyester used in the present invention, and any known method can be employed. For example, a method can be adopted in which the above aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and glycol are directly esterified, or dicarboxylic acid, alkyl ester, and glycol are transesterified and then double polymerized. Esterification.

In the transesterification type 1 condensation, a known catalyst can be used as necessary.

Other thermoplastic resins, heat stabilizers, stepless fillers, organic fillers, flame retardants, curing accelerators, etc. can be added to the reactive hot melt adhesive composition of the present invention, if necessary.

The hot melt adhesive composition of the present invention can be prepared by applying the hot melt adhesive composition directly to an adherend using a conventional coating device such as an extruder, hot melt applicator, roll coater, etc., and then applying heat and pressure to the adherend; After molding it into a shape or forming it into a nonwoven fabric using the spunbond method or preparing it into a powder,
It is used by sandwiching it between adherends and heat-pressing it. In some cases, the hot melt adhesive composition of the present invention may be dissolved in a solvent, applied to an adherend, dried, and then bonded under heat and pressure.

(Example) The present invention will be specifically explained below using examples.

Note that "parts" in one example mean "parts by weight."

Further, the characteristic values in the nine examples were measured by the first method.

Intrinsic viscosity was measured at 20°C in a 1/1 (weight ratio) mixed solvent of phenol/tetrachloroethane.

(2) Shear adhesive strength (kg/clIt) JIS K-
A shear adhesive test piece was prepared according to 6850, and the shear adhesive strength was measured at 25"C and 100°C.

(3) T-peel adhesive strength (kg/ct) JIS
A T-peel adhesion test piece was prepared based on K-6854,
T-peel adhesion strength was measured at 25°C and 100°C.

(4) Dynamic thermal stability test Laboplast Mill (manufactured by Toyo Seiki Co., Ltd., Type 1O) set to the coating temperature or molding temperature of each adhesive composition.
-150), put the adhesive composition into the mixing part of 2O
The torque was continuously recorded while stirring at rpm, and the time until the torque suddenly increased was observed. however.

The test lasted up to 10 hours.

-(5) Storage stability Each adhesive composition was stored indoors, and a dynamic thermal stability test was conducted every month to determine the time until a rapid increase in torque.

However, the test was limited to a maximum of 10 hours.

Example 1 35 moles of terephthalic acid, 35 moles of isophthalic acid.

0.02 mol of n-butyl titanate as a catalyst was added to 30 mol of dimer acid and 150 mol of 4-butanediol, water was distilled off at 150 to 245°C, and an esterification reaction was carried out. Next, 0.01 mol of n-butyl titanate was added and polycondensation was performed at 245° C. for 4 hours under reduced pressure to produce a thermoplastic copolyester resin (1). The intrinsic viscosity of this resin was 0.55.

50 parts of this thermoplastic copolymerized polyester resin (I) was added to Epikote 1007 (manufactured by Shell Chemical Co., Ltd.).

Bisphenol A type epoxy resin) 50 parts and 1゜1-
28 parts of dimethyl-1-(2-hydroxy-3-allyloxypropyl)amine lactimide (abbreviated as ALI) was blended, and 3
An adhesive composition was prepared by kneading for 0 minutes. In addition, the above AL
As I, Ebicure Y made by Yuka Shell Epoxy■
PH-201 was used (the same applies hereinafter).

This adhesive composition was applied to a hot melt applicator (manufactured by Nippon Epi-Kogyo Co., Ltd.) set at 120°C.

APN-7002) was used to coat a melamine-coated steel plate.

Wrap a melamine-coated steel plate and press it to 160℃ using a hot press.
The adhesive was bonded by heating at ℃ for 30 minutes, and the shear adhesive strength was measured.

In the same manner, aluminum plates were adhered to each other and the T-peel adhesive strength was measured.

Furthermore, a dynamic thermal stability test and a storage stability test were conducted using this adhesive composition.

The measured values are shown in Table 1.

Example 2 50 moles of terephthalic acid, 20 moles of isophthalic acid.

What is the intrinsic viscosity of the thermoplastic copolyester resin (n) prepared in the same manner as in Example 1 using 30 moles of adipic acid and 150 moles of 4-butanediol?

It was 0.69.

70 parts of this thermoplastic copolyester resin (n) and Epikote 1009 (manufactured by Shell Chemical Co., Ltd.).

Bisphenol A type epoxy resin, resin) 30 parts and 1゜1-
12 parts of dimethyl-1-(2-hydroxy-3-allyloxypropyl)amine rough 1-imide (ALI) was blended and kneaded for 30 minutes in a Labo Plastomill (set temperature 160°C) to prepare an adhesive composition. did.

This adhesive composition was tested in the same manner as in Example 1, and the measured values were determined and shown in Table 1. The temperature setting of the hot melt applicator is 160°C.

The hot pressing conditions were 200°C x 15 minutes.

Example 3 40 moles of terephthalic acid, 40 moles of isophthalic acid.

The intrinsic viscosity of thermoplastic copolymerized polyester resin (III) prepared in the same manner as in Example 1 using 20 moles of sebacic acid and 150 moles of 1,4-butanediol is as follows.

It was 0.75.

90 parts of this thermoplastic copolymerized polyester resin (III) was added with Epikote 1004 (manufactured by Shell Chemical Co., Ltd.).

10 parts of bisphenol A type epoxy resin) and 5 parts of H-11-dimethyl-1-(2-hydroxy-3-allyloxypropyl)amine propionylimide (abbreviated as API) were mixed and extruded using a twin-screw extruder (temperature setting 140-160). ℃)
The mixture was kneaded to obtain an adhesive composition. Then 160°C
100μ by an extruder with a T-die set at a temperature of
A film was produced.

This film was sandwiched between a melamine-coated steel plate and a melamine-coated steel plate, and the films were bonded together by heating in a hot press at 200° C. for 15 minutes, and the shear adhesive strength was measured. Glue the aluminum plates together in the same way.

T-peel adhesion strength was measured. Furthermore, a dynamic thermal stability test and a storage stability test were conducted using this adhesive composition.

The measured values are shown in Table 1.

Example 4 Thermoplastic copolymerized polyester resin of Example 3 - (III
), 30 parts of Epicote 1009 and 6 parts of 1,1-dimethyl-1-(2-hydroxy-3allyloxypropyl)amine lactimide (All) were mixed into 70 parts of Laboplastomil (set temperature 160"c). The mixture was kneaded for 30 minutes to prepare an adhesive composition.

Next, 1 in a hot press set at a temperature of 180°C.
A film of 00μ was produced.

This film was sandwiched between a melamine-coated steel plate and a melamine-coated steel plate, and the films were bonded together by heating in a hot press at 200° C. for 15 minutes, and the shear adhesive strength was measured. Glue the aluminum plates together in the same way.

T-peel adhesion strength was measured. Furthermore, a dynamic thermal stability test and a storage stability test were conducted using this adhesive composition.

The measured values are shown in Table 1.

Comparative Example 1 Thermoplastic copolymerized polyester resin obtained in Example 1 (
I) 30 parts and 70 parts of Epicote 1007 and 1.1-
30 parts of dimethyl-1-(2-hydroxy-3-allyloxypropyl)amine lactimi)' (ALI) was blended and heated in a Laboplastomill (set temperature 120°C) for 30 minutes.
An adhesive composition was prepared by kneading.

This adhesive composition was applied onto a melamine coated steel plate using a hot melt applicator (same as in Example 1) set at 120''C.

Wrap a melamine-coated steel plate and press it to 160℃ using a hot press.
The adhesive was bonded by heating at ℃ for 30 minutes, and the shear adhesive strength was measured.

Two aluminum plates were bonded together in the same manner and the T-peel adhesive strength was measured. Also.

A dynamic thermal stability test and a storage stability test were conducted using this adhesive composition.

The measured values are shown in Table 1.

Comparative Example 2 Thermoplastic copolymerized polyester resin obtained in Example 2 (
TI), 30 parts of Epikote 1009, and 10 parts of aniline were mixed together, and a Laboplastomill (set temperature: 16
An adhesive composition was prepared by kneading at 0°C for 30 minutes.

This adhesive composition was tested in the same manner as in Example 1, and the measured values were determined and shown in Table 1.

Note that the set temperature of the hot melt applicator and the pot press conditions were the same as in Example 2.

Comparative Example 3 Thermoplastic copolymerized polyester resin obtained in Example 2 (
IT) 70 parts and 30 parts of Epicote 1009 and 1,1
- 50 parts of dimethyl-1-(2-hydroxy-3-allyloxypropyl)amine lactimide (ALI) was blended, and 30
An adhesive composition was prepared by kneading.

This adhesive composition was tested in the same manner as in Example 1, and the measured values were determined and shown in Table 1.

In addition, the set temperature of the pot melt applicator.

The hot pressing conditions were the same as in Example 2.

Comparative Example 4 Thermoplastic copolymerized polyester resin obtained in Example 2 (
n) 70 parts and 30 parts of Epicote 1009 and 1,1-
2 parts of dimethyl-1-(2-hydroxy, droxy-3-allyloxypropyl)amine lactimide (ALT) are blended,
An adhesive composition was prepared by kneading for 30 minutes in a laboplasto mill (temperature set at 160°C).

This adhesive composition was tested in the same manner as in Example 1, and the measured values were determined and shown in Table 1.

In addition, the set temperature of the hot melt applicator.

The hot pressing conditions were the same as in Example 2.

Comparative Example 5 Thermoplastic copolymerized polyester resin obtained in Example 3 (
III) 96 parts and 4 parts of Epicote 1004 and 1.1 parts
- Blend 1 part of dimethyl-1-(2-hydroxy-3-allyloxypropyl)amine propionylimide (API) and use a twin-screw extruder (set temperature 140-160°C)
The mixture was kneaded to prepare an adhesive composition.

Next, a 100μ film was produced using an extruder with a T-guy set at a temperature of 160°C.

This film was sandwiched between a melamine-coated steel plate and a melamine-coated steel plate, and the films were bonded together by heating in a hot press at 200° C. for 15 minutes, and the shear adhesive strength was measured. Glue the aluminum plates together in the same way.

T-peel adhesion strength was measured. Furthermore, a dynamic thermal stability test and a storage stability test were conducted using this adhesive composition.

The measured values are shown in Table 1.

(Effects of the Invention) Since the hot melt adhesive composition of the present invention has the above-mentioned structure, it has high heat-resistant adhesive strength, and also has good storage stability after manufacturing one composition and subsequent molding process. It has excellent properties and is stable even when exposed to high temperatures for long periods of time. Therefore, it can be used as a film formed by an extruder or the like, and can also be applied by a conventional hot melt applicator. Moreover, 1. It also has excellent initial adhesion to adherends, so it can be easily applied to bonding processes in the field of assembling various industrial products.

Thus, the hot melt adhesive composition of the present invention can be handled in the same manner as conventional hot melt adhesives,
Furthermore, it has excellent adhesive strength and durability at high temperatures, so it can be suitably used in various applications, including, for example, assembling automobile and electrical parts.

Claims (1)

[Claims] (1) A resin component consisting of 90 to 40% by weight of thermoplastic copolymerized polyester resin and 10 to 60% by weight of epoxy resin,
10 to 50% by weight of 1,1 based on the above epoxy resin
-dimethyl-1-[2-hydroxy-3-(2-butylenyloxy)propyl]amine lactimide, 1,1-
Dimethyl-1-(2-hydroxy-3-allyloxypropyl)amine lactimide and 1,1-dimethyl-1
A hot melt adhesive composition comprising at least one compound selected from -(2-hydroxy-3-allyloxypropyl)amine propionylimide.