JPH01313554A - Polyester rein composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition of an improved rate of crystallization without detriment to its adhesiveness by adding modified polyolefin to a polyester containing an aromatic dicarboxylic acid and an aliphatic glycol as the main components. CONSTITUTION:The title resin composition is formed by adding 5-5000ppm of a modified polyolefin to a polyester resin comprising an acid component mainly consisting of 40-100mol% aromatic dicarboxylic acid component and 60-0mol% aliphatic dicarboxylic acid component or a hydroxy carboxylic acid component and an alcohol component mainly consisting of an aliphatic glycol component. The amount of the aromatic dicarboxylic acid component in the polyester resin should be 40-100mol%. When this amount is below 40mol%, the rate of crystallization is low, and any sufficient rate of crystallization cannot be attained even when the modified polyolefin is contained. When the amount of the modified polyolefin added is below 5ppm, the effect of accelerating crystallization is not sufficient; while when it is above 5000ppm, the rate of crystallization is at most equal to or sometimes lower than that when the amount of addition is smaller.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a polyester resin composition that has improved crystallization speed without impairing adhesive properties, and is particularly suitable for use in hot melt adhesives. The present invention relates to a composition.

(Conventional technology) Polyester resin is used for paints, coatings, etc.
Widely used in the fields of various binders and adhesives. Particularly in the adhesive field, polyester resins have been increasingly used as hot melt adhesives in recent years.
It is used for many adhesive purposes such as adhesive interlining, patch adhesion, honeycomb panel assembly, automobile filters, and heel mat assembly. All of these uses utilize the following features of hot melt adhesives.

That is, since adhesion is completed only by WI melting and assimilation, adhesion is fast and no drying process of solvent or water is required. It is used to take advantage of its features such as no pot life problems.

However, since the crystallization rate of polyester resin is slow, self-locking of cut pellets may occur during pelletization after the completion of the single polycondensation reaction, and when hot melt film is produced, Self-adhesion of the melt film may occur, and furthermore, in the hot melt bonding process, adhesive strength may not be developed instantly after thermocompression bonding.

There are problems such as adhesion defects occurring when removed from the pressure press.

As a method for increasing the crystallization rate of such a polyester resin, for example, a method of adding an inorganic substance such as talc or calcium carbonate is known.

(For example, see Japanese Patent Publication No. 47-4140).

(Problem to be solved by the invention) However, even if the above-mentioned inorganic substances are added to polyester resin, the crystallization rate cannot be sufficiently increased, and the following points still remain as problems to be solved. It was left behind.

Namely.

(2) After the polycondensation reaction is complete, the strands must be immersed in water for several tens of minutes to several hours and allowed to crystallize before being cut and pelletized.

(2) Furthermore, during the production of hot melt film, it is necessary to roll it up with a release paper in between, making it extremely expensive and disadvantageous from a cost standpoint.

(2) In the hot-melt bonding process, even after heat-pressing, the product must be cooled while being pressurized for a while and then taken out after sufficient crystallization has progressed, resulting in poor productivity.

Other issues remained.

The present invention aims to solve the above-mentioned problems, and its purpose is to provide a polyester resin composition that has an improved crystallization rate without impairing adhesive properties.

(Means for Solving the Problems) In order to solve these problems, the present inventors conducted intensive research on promoting crystallization of polyester resins, and as a result, they arrived at the present invention.

That is, 1 the present invention has an aromatic dicarboxylic acid component of 40 to 1
00 mol% and an aliphatic dicarboxylic acid component or oxyacid component 60 to 0 mol% as the main acid component, and a polyester resin containing an aliphatic glycol component as the main alcohol component, mixed with 5 to 5000 ppm of modified polyolefin. The gist is a resin composition.

Hereinafter, nine aspects of the present invention will be described in detail.

To prepare the polyester resin composition of the present invention, the modified polyolefins are uniformly mixed.

They may be mixed in any process. Preferably,
When preparing a slurry by mixing dicarboxylic acid or glycol as raw materials, or by mixing dicarboxylic acid and glycol in the slurry preparation process, a modified polyolefin may also be mixed, or in the esterification reaction process. (or the transesterification reaction step) and immediately before the polycondensation reaction step, the modified polyolefin may be mixed.

The aromatic dicarboxylic acid component of the polyester resin in the polyester resin composition of the present invention includes:

Examples include terephthalic acid, isophthalic acid, and 2,6-naphthalene dicarboxylic acid. Examples of di-aliphatic dicarboxylic acids include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, eicosandicarboxylic acid, and examples of oxyacids include P-oxybenzoic acid. acid, ε-oxycaproic acid (ε-caprolactone), and the like. moreover,
Examples of the aliphatic glycol component include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and the like.

The proportion of the aromatic dicarboxylic acid component in the polyester resin is 40 to 100 mol%, and if it is less than 40 mol%, even if modified polyolefin is blended, the crystallization rate is slow and it is difficult to obtain a sufficient crystallization rate. I can't.

Next, the modified polyolefins used in the polyester resin composition of the present invention include maleic anhydride copolymerized polyethylene, maleic anhydride copolymerized polypropylene, (
Examples include meth)acrylic acid copolymerized polyethylene, styrene copolymerized polyethylene, oxidized polyethylene, and M-modified polypropylene.

The amount of the modified polyolefin added needs to be 5 to 5000 ppm, preferably 20 to 2000 ppm, based on the polyester resin.

If the amount of modified polyolefin added is less than 5 ppm, the effect of promoting crystallization will be insufficient.

On the other hand, if the amount exceeds 5,000 ppm, the crystallization rate may be equal to or slower than that when the amount added is small.

A polyester resin composition blended with a modified polyolefin is used as a hot melt adhesive or the like after adding an antioxidant, a flame retardant, a plasticizer, a filler, etc., if necessary.

According to the polyester resin composition of the present invention, although the crystallization rate is greatly improved, the adhesion is not impaired in any way, and properties suitable as a hot melt adhesive are provided.

(Example) The present invention will be explained in detail below by way of nine examples.

In the examples, the crystallization rate of the polyester resin composition was determined by heating the polyester resin composition to 200°C at a rate of 320°C/min for 5 minutes using a PerkinElmer Dsc-2C differential scanning calorimeter, and then maintaining the temperature at 320°C for 5 minutes. The temperature was lowered to 35°C at a rate of C/min and maintained at the same temperature.

It is expressed as the time to the top of the exothermic peak caused by crystallization.

Also, what is the intrinsic viscosity of the polyester resin composition?

It was determined by measuring at 120° C. in a mixed solvent of phenol:tetrachloroethane=674 (weight ratio).

Examples 1-6. Comparative Examples 1 to 2 80 parts by weight of terephthalic acid, 43 parts by weight of isophthalic acid, 38 parts by weight of adipic acid, 144 parts by weight of 1,4-butanediol, and the modified polyolefin shown in Table 1 were charged into a reaction vessel and heated under a nitrogen stream. The esterification reaction was carried out at 160-200°C. Next.

After adding 0.2 parts by weight of n-butyl titanate as a catalyst, a polycondensation reaction was carried out at 240°C under a reduced pressure of 0.1 mmHg to produce a polyester resin, and the polyester resin composition shown in Table 1 was prepared. .

Table 1 From Table 1, it can be seen that resin compositions satisfying the amount of modified polyolefin of the present invention have a high crystallization rate.

Comparative example 3 Using talc instead of modified polyolefin.

A polyester resin composition was prepared in the same manner as in Example 4, and the crystallization rate was measured to obtain the results shown in Table 2.

Comparative Example 4 A polyester resin was prepared in the same manner as in Example 1 without adding modified polyolefin, and the crystallization rate was measured.
The results shown in the table were obtained.

Table 2 Crystallization rates of the resin compositions of Examples 1 to 6 in Table 1 and Table 2
When compared with that of Comparative Example 3.4 in the table.

It can be seen that the crystallization speed of the resin compositions of Examples 1 to 6 is extremely fast.

Example 7 91 parts by weight of terephthalic acid, 50 parts by weight of isophthalic acid, 30 parts by weight of sebacic acid, 126 parts by weight of 1,4-butanediol, and the modified polyolefin shown in Table 3 were charged into a reaction vessel, and the mixture was heated at 160 parts by weight under a nitrogen stream. The esterification reaction was carried out at 200°C. Next.

After adding 0.2 parts by weight of n-butyl titanate as a catalyst, a polycondensation reaction was carried out at 240°C under a reduced pressure of 0.1 wHg to produce a polyester resin, and the polyester resin compositions shown in Table 3 were prepared. .

Example 8 108 parts by weight of terephthalic acid, 33 parts by weight of isophthalic acid,
17 parts by weight of ε-caprolactone, 107 parts by weight of 1,4-butanediol, and the modified polyolefin shown in Table 3 were charged into a reaction vessel, and an esterification reaction was carried out at 160 to 200°C under a nitrogen stream.

Next, after adding 0.2 parts by weight of n-butyl titanate as a catalyst, 0.2 parts by weight of n-butyl titanate was added. A polyester resin was produced by carrying out a polycondensation reaction at 240° C. under a reduced pressure of ln+0 g, and the polyester resin compositions shown in Table 3 were prepared.

Comparative Example 5 A polyester resin was prepared in the same manner as in Example 7 without adding modified polyolefin, and the crystallization rate was measured.
The results shown in the table were obtained.

Comparative Example 6 A polyester resin was prepared in the same manner as in Example 8 without adding modified polyolefin, and the crystallization rate was measured.
The results shown in the table were obtained.

Comparative Example 7 33 parts by weight of terephthalic acid, 17 parts by weight of isophthalic acid, 71 parts by weight of sebacic acid, 51 parts by weight of adipic acid, 1,4-
126 parts by weight of butanediol and the modified polyolefin shown in Table 3 were charged into a reaction vessel, and 160 to 2 parts by weight of
The esterification reaction was carried out at 00°C. Next, after adding 0.2 parts by weight of n-butyl titanate as a catalyst, 0.2 parts by weight of n-butyl titanate was added.
Under reduced pressure of 1 mmHg.

A polyester resin was produced by carrying out a polycondensation reaction at 240°C, and the polyester resin compositions shown in Table 3 were prepared.

Table 3 From Table 3, Comparative Example 5 in which modified polyolefin is not blended
, 6 had a slow crystallization rate, and the resin composition of Comparative Example 7, which had a small proportion of the aromatic dicarboxylic acid component, had an extremely low crystallization rate even if the amount of the modified polyolefin of the present invention was satisfied. It turns out it's late.

Further, using the polyester resin composition prepared in Example 4 and the polyester resin prepared in Comparative Example 4, an unstretched film with a thickness of 50 μm was prepared.
After adhering at 200℃ between μ aluminum plates, J
Changes in shear adhesive strength over time were measured according to Is-6850, and the results shown in Table 4 were obtained.

Table 4 As is clear from Table 3, the polyester resin composition of the present invention exhibits high adhesive strength immediately after adhesion, and the adhesive strength does not decrease.

(Effect of the invention) Since the polyester resin composition of the present invention is made by blending a specific amount of modified polyolefin with a polyester resin,
The crystallization rate is significantly improved, and the adhesion is not impaired in any way. Therefore, in the polyester resin composition of the present invention, self-adhesion of cut pellets is less likely to occur during pelletization after completion of the single polycondensation reaction, and the polyester resin composition of the present invention is less likely to cause self-adhesion of cut pellets, and can be used in hot melt films wound up during production of hot melt films. Self-adhesion may occur.<<,
Furthermore, in the hot melt bonding process.

After thermocompression bonding, adhesive strength can be developed in a short period of time.

The polyester resin composition of the present invention can be particularly suitably used as a hot melt adhesive that exhibits high adhesive strength immediately after bonding.

Patent applicant: Uni-Tei Riki Co., Ltd.

Claims (1)

[Claims] (1) 40 to 100 mol% aromatic dicarboxylic acid component and 60 to 0 mol% aliphatic dicarboxylic acid component or oxyacid component
A polyester resin composition prepared by blending 5 to 5000 ppm of a modified polyolefin into a polyester resin containing mol % as a main acid component and an aliphatic glycol component as a main alcohol component.