JPH0625635A - Non-halogen adhesive composition - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide an aromatic polycarbonate resin-based adhesive agent that is effective for adhering a heat-resistant film such as a heat transfer film and does not use a halogen-based solvent. A halogen-free adhesive composition obtained by dissolving an amorphous aromatic polycarbonate resin having a specific molecular weight in a specific aromatic hydrocarbon solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition, and more specifically, an aromatic polycarbonate resin adhesive which does not use a halogen solvent and is suitable for adhering a heat resistant film such as a thermal transfer film. It relates to a composition.

[0002]

2. Description of the Related Art Conventionally, a bisphenol A polycarbonate resin obtained by reacting 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A] with phosgene or diphenyl carbonate is transparent, heat resistant, mechanically It is widely used in many fields as an engineering plastic due to its excellent dimensional stability. It is also practiced to dissolve this aromatic polycarbonate resin in a halogenated hydrocarbon solvent and use it as an adhesive for heat-resistant films such as thermal transfer films. However, in recent years, the use of halogenated hydrocarbon solvents has been restricted due to environmental hygiene problems and equipment corrosion problems, and the development of adhesives that do not use halogenated hydrocarbon solvents is desired. In addition, polyethylene terephthalate resin, bisphenol A polycarbonate resin, and the like are often used as materials for heat-resistant films such as thermal transfer films.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an aromatic polycarbonate resin adhesive which is effective in adhering a heat resistant film such as a heat transfer film and which does not use a halogenated hydrocarbon solvent. To do.

The present inventor, as a result of extensive studies aimed at achieving the above object, has found that if an amorphous aromatic polycarbonate resin having a specific molecular weight is dissolved in a specific non-halogen solvent, it will be used as an adhesive. It has been found that when used, it exhibits good adhesion performance, and has reached the present invention.

[0005]

The present invention provides (A) 6 carbon atoms.
~ 12 aromatic hydrocarbons 100 parts by weight, (B) carbon number 3 ~
0 to 100 parts by weight of the aliphatic cyclic ether compound of 6 and
(C) at least one solvent selected from acetic acid, methyl isobutyl ketone, and n-butanol in a solvent consisting of 0 to 2 parts by weight,
A non-halogen adhesive composition comprising 0.7 g of methylene chloride dissolved in 100 ml of methylene chloride and 1 to 50% by weight of an amorphous aromatic polycarbonate resin having a specific viscosity of 0.12 to 1.04 measured at 20 ° C. It is related to.

The solvent used in the adhesive composition of the present invention is
(A) A non-halogenated aromatic hydrocarbon having 6 to 12 carbon atoms, particularly low-boiling point aromatic hydrocarbons such as benzene, toluene and xylene. Further, the aromatic hydrocarbon may be mixed with an equal amount or less of (B) an aliphatic cyclic ether compound having 3 to 6 carbon atoms, that is, 100 parts by weight of the aromatic hydrocarbon is mixed with the aliphatic cyclic compound. 100 parts by weight or less of ether may be mixed, and at least one selected from the group consisting of (C) acetic acid, methyl isobutyl ketone, and n-butanol.
You may mix in the quantity below a weight part. As the aliphatic cyclic ether compound having 3 to 6 carbon atoms (B), tetrahydrofuran, dioxane, trioxane and the like are preferable.

The polycarbonate resin used in the present invention is an amorphous aromatic polycarbonate resin, which is obtained by reacting the following dihydric phenol with a carbonate precursor. Usually, it is obtained by an interfacial polycondensation using phosgene or a transesterification method using diphenyl carbonate.

As the dihydric phenol used here,
For example, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1, 1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis Examples include (4-hydroxyphenyl) butane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane. Among them 1,1-
Bis (4-hydroxyphenyl) cyclohexane [common name bisphenol Z] and 1,1-bis (4-hydroxyphenyl) -1-phenylethane [common name bisphenol]
AP] is particularly preferred. These dihydric phenols may be used alone or in combination of two or more.
In addition, if the amount is within the range where the crystallinity is not expressed, 2,2-
A dihydric phenol that gives a crystalline aromatic polycarbonate resin such as bis (4-hydroxyphenyl) propane [commonly called bisphenol A] may be copolymerized. The copolymerization method uses two or more dihydric phenols at the same time,
An ordinary method such as mixing and polymerizing separately synthesized oligomers can be used.

A crystalline aromatic polycarbonate resin composed of 2,2-bis (4-hydroxyphenyl) propane [commonly called bisphenol A] is used as a main component without using an amorphous aromatic polycarbonate resin. In the adhesive composition described above, a whitening phenomenon occurs on the adhesive surface and the transparency is impaired, which is not preferable.

Amorphous aromatic polycarbonate used in the present invention
The molecular weight of the bonnet resin is 0.7 g of polymer to 100 ml.
Dissolved in methylene chloride and measured at 20 ° C. to give a specific viscosity of 0.12 to 1.04, and 0.23 to
0.90 is preferred. If the specific viscosity is less than 0.12, the adhesive strength is weak, and if the specific viscosity is higher than 1.04, it is difficult to dissolve in the solvent and the workability is deteriorated.
Further, additives such as a stabilizer and a weathering agent can be added to the aromatic polycarbonate resin within a range that does not impair the adhesiveness.

The interfacial polycondensation reaction using phosgene is usually carried out in the presence of an aqueous solution of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as pyridine, sodium hydroxide or potassium hydroxide is used. As the solvent, for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. Further, for the purpose of accelerating the reaction, for example, a tertiary amine, a catalyst such as a quaternary ammonium salt can be used, and as a molecular weight regulator, for example, phenol,
It is desirable to use a terminating agent such as p-tert-butylphenol. Further, phosgenation may be carried out in a nitrogen gas atmosphere by using a solvent that has been degassed in advance or by adding a small amount of an antioxidant such as hydrosulfite to the aqueous solution.

The adhesive composition of the present invention is prepared by dissolving the above amorphous aromatic polycarbonate resin in the above solvent. As a dissolution method, a usual method such as adding a resin while stirring a solvent is used. The amount of dissolution is 1 to the above resin concentration
The amount is 50% by weight. When the resin concentration is less than 1% by weight, a sufficient adhesive effect cannot be obtained, and when it exceeds 50% by weight, it takes time to dissolve in a solvent and the solution viscosity becomes too large, which is not suitable for handling. As the method for adhering with the adhesive composition of the present invention, a usual method such as applying a solution to the surface of an object to be adhered and then performing pressure bonding is used.

[0013]

EXAMPLES The present invention will be further described with reference to the following examples. In the examples, parts and% are parts by weight and% by weight, respectively.
Is. Specific viscosity: 0.7 g of polymer was dissolved in 100 ml of methylene chloride and measured at 20 ° C. Tensile adhesive strength: measured according to ASTM D-897, 10
A grade of 0 kg / cm ² or more was accepted.

[0014]

[Synthesis Example 1] 346.4 parts of ion-exchanged water and 58.38 parts of 48.5% sodium hydroxide aqueous solution were charged into a reaction tank equipped with a phosgene blow-in tube and a reflux condenser, and after dissolving 42.34 parts of bisphenol Z. , Methylene chloride 169.
Add 7 parts of phosgene 1 at 25 ° C with vigorous stirring.
About 9.5 parts was required for about 40 minutes to carry out a reaction by blowing. Then, the internal temperature was raised to 30 ° C., and p-tert-butylphenol 0.
After adding 727 parts and emulsifying, triethylamine 0.05
Part of the mixture was added and stirring was continued for 2 hours to complete the reaction.

After completion of the reaction, the organic phase is separated, diluted with methylene chloride, washed with water, neutralized with hydrochloric acid, and repeatedly washed with water. When the conductivity of the aqueous phase becomes almost equal to that of ion-exchanged water, the organic phase is separated. Was separated and pulverized while evaporating methylene chloride to obtain a powder. The specific viscosity of this powder is 0.3.
It was 64.

[0016]

[Synthesis example 2] Ion-exchanged water 2 was added to the apparatus used in synthesis example 1.
3800 parts, 48.5% sodium hydroxide aqueous solution 27
38.4 parts were charged and bisphenol AP3566.1 parts was dissolved. Then, 16700 parts of methylene chloride was charged, and 1400 parts of phosgene was added to about 45 in the same manner as in Synthesis Example 1.
It took a minute to blow. Then, 129.1 parts of p-tert-butylphenol and a 48.5% aqueous sodium hydroxide solution 5
Powder was obtained in the same manner as in Synthesis Example 1 by adding 06.8 parts. The specific viscosity of this powder was 0.234.

[0017]

Example 1 A polyethylene terephthalate film [manufactured by Teijin Ltd.] having a thickness of 0.5 mm was cut into 20 mm × 100 mm, and a solution prepared by dissolving 25% of the polycarbonate synthesized in Synthesis Example 1 in toluene was cut into a 5 mm edge portion. They were applied, overlapped and adhered under a load of 12 kg / cm ² for 7 days. No whitening or foaming was observed in the adhesive test piece, and the tensile adhesive strength was acceptable.

[0018]

Example 2 Using a 0.5 mm thick bisphenol A polycarbonate film [manufactured by Teijin Chemicals Ltd.], the polycarbonate synthesized in Synthesis Example 2 was mixed with 100 parts of toluene /
25 parts in a mixed solution of 80 parts of tetrahydrofuran / 1 part of acetic acid
% Solution was applied and adhered as in Example 1.
No whitening or foaming was observed in the adhesive test piece, and the tensile adhesive strength was acceptable.

[0019]

Comparative Example 1 Toluene was applied to the same film as used in Example 1 and evaluated in the same manner as in Example 1, but the adhesive strength in this case was unacceptable.

[0020]

Comparative Example 2 In Example 2, bisphenol A polycarbonate [Panlite L-1225 manufactured by Teijin Kasei Co., Ltd.] was used in place of the polycarbonate synthesized in Synthesis Example 2, and otherwise the same as in Example 2. Tested.
This product was not practical because the adhesive surface was white and the appearance was poor.

[0021]

Comparative Example 3 The same adhesive composition as used in Example 2 was used in the same film as used in Example 1 and tested in the same manner as in Example 1. This product was not practical because the adhesive surface was white and the appearance was poor.

[0022]

The non-halogen adhesive composition of the present invention comprises
Since it uses a heat-resistant polycarbonate resin that has excellent adhesive strength of the film and transparency of the adhesive surface without using a harmful halogenated solvent, it can be suitably used for adhesion of heat-resistant films such as thermal transfer films. .

Claims (1)

[Claims] 1. (A) Aromatic hydrocarbon 1 having 6 to 12 carbon atoms
00 parts by weight, (B) 0 to 100 parts by weight of an aliphatic cyclic ether compound having 3 to 6 carbon atoms, and (C) at least one selected from acetic acid, methyl isobutyl ketone and n-butanol 0
~ 2 parts by weight of solvent in 0.7 g of methylene chloride
It has a specific viscosity of 0.12
1 to 5 of 1.04 amorphous aromatic polycarbonate resin
A non-halogen adhesive composition in which 0% by weight is dissolved.