JPS5825103B2 - Netsu Antei Seigan Halogen Diyushisobutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a halogen-containing resin composition that is excellent in heat stabilizer, surface gloss, and long-term storage stability, and has an excellent ability to prevent initial discoloration.

Halogen-containing resins, represented by vinyl chloride resins, are one of the most widely used thermoplastic resins, but they alone cannot withstand heat and light during melt molding or during use of molded products. Usually, stabilizers are added during molding to avoid coloring and deterioration of various characteristic values.

Conventionally, various metal compounds have been mainly used for this purpose, namely metal salts of fatty acids such as stearic acid and lauric acid, various inorganic and organic acid salts, and various amines, epoxy compounds, etc. have also been used in combination. Ta.

Heavy metal salts such as cadmium and lead have been mainly used to form these metal salts, but recently, low toxicity or non-toxic stabilizers that do not use these metals have been rapidly developed. As a result, epoxy resin has started to attract attention.

Epoxy resins used as stabilizers for halogen-containing resins are highly effective in capturing hydrochloric acid generated by the decomposition of halogen-containing resins and inhibiting subsequent decomposition.Epoxy resins have particularly good compatibility with the resins, and have excellent bleed resistance. Although it is superior to other stabilizers in terms of stability, heat stability, and water resistance, it has the disadvantage of being inferior in its ability to prevent initial discoloration.

On the other hand, conventional epoxy stabilizers include epoxy fatty acid esters represented by epoxidized soybean oil fatty acids, which have been used in large quantities as plasticizers and stabilizers, especially for soft vinyl chloride resins. Although it exhibited excellent effects in preventing initial discoloration, it was unsatisfactory in terms of thermal stability, storage stability, antibacterial properties, etc.

In other words, it cannot be said that the heat stability is very good compared to other stabilizers, and crystals may precipitate at low temperatures in winter, precipitates may form due to changes over time during long-term storage, and the transparency may decrease due to mold growth. There was a problem.

As a result of our research into a stabilizer that combines the advantages of epoxy resins and epoxy fatty acid esters and eliminates their drawbacks, we have completed the present invention. To the epoxy resin made from the raw material, add 1 to 3 percent by weight of 2-chlorohydrin chlorine as a stabilizer to the halogen-containing resin in its chemical structure. This is a characteristically heat-stable halogen resin composition.

The halogen-containing resins referred to in the present invention include vinyl chloride resins, vinylidene chloride resins, copolymers of vinyl chloride and vinylidene chloride, and copolymers containing vinyl chloride or vinylidene chloride as a main component and other monomers that can be copolymerized therewith. Examples of such other monomers include vinyl acetate, acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, acrylonitrile, and the like.

What is usually called epoxy resin is the so-called Epibis type epoxy resin (epichlorohydrin bisphenol A polycondensation type epoxy resin, hereinafter abbreviated as Epibis type epoxy resin), which accounts for more than 90% of commercially available products, excluding special types. These include its epoxy equivalent, viscosity,
Many types are commercially available, ranging from liquid resins to solid resins, depending on differences in softening points, etc.

Among these, the epoxy resins conventionally used as stabilizers have an average molecular weight of about 380 to 500 and an epoxy equivalent of about 190 to 250, from practical viewpoints such as strength, softening point, and economic efficiency of molded products. For example, most of them were Epotote YD-128, YD-134, manufactured by Tobu Kasei Co., Ltd.).

However, these epoxy resins have the disadvantage that they have poor ability to prevent initial discoloration and can only be used for special purposes.

As a result of conducting numerous experiments to investigate the correlation between the structural composition of these series of epoxy resins and their performance as stabilizers, we found that the initial discoloration prevention performance and thermal stability of halogen-containing resins are related to the presence in the epoxy resin skeleton structure. It has been found that there is an extremely important relationship between the content of 1,2-chlorohydrin chlorine (also referred to as hydrolyzable chlorine).

In general, epoxy resins (excluding aliphatic epoxy resins etc. manufactured using organic peracids as epoxidizing agents) contain about 0.0%, although it varies depending on the type, due to the manufacturing process.
Although it contains less than 2% of 1,2-chlorohydrin chlorine, for the general purpose of obtaining an epoxy cured resin by reacting with a curing agent, the cured product must have high insulation performance and voltage resistance. It is desirable that the content of 1,2-chlorohydrin chlorine be as low as possible in order to fully satisfy electrical applications that require arc resistance, etc. Therefore, typical commercially available liquid epoxy resins (for example, the For Kasei Epoto (YD-128, etc.), it is 0.05% or less.

However, we are not using this kind of epoxy cured resin for almost all uses of epoxy resins, but rather for using it as a stabilizer for halogen-containing resins. They have found that when the content of body chlorine is in the range of 2 to 10 weight percent, the initial discoloration prevention ability is much better than that of conventional products.

In general, stabilizers for halogen-containing resins need to have both initial discoloration prevention ability and very good thermal stability.

From this point of view, we investigated the correlation between the 1,2-chlorohydrin chlorine content and these two performances, and found that the 1,2-chlorohydrin chlorine content was 2.
If the content is less than 10%, the thermal stability is good, but the initial coloring prevention ability is weak (and as the content increases, the initial coloring prevention ability improves). It was observed that although the temperature improved, the thermal stability decreased.

According to our experiments, the range in which both performances are compatible and excellent is when the content is 3 to 7% by weight, but from a practical standpoint, it is 2 to 10% by weight. It was found that it has sufficient efficacy.

This performance is extremely superior compared to epoxidized soybean oil fatty acids, which have been widely used in the past.

We have found that the same tendency exists for epivis type epoxy resins with different average molecular weights.

Next, we will introduce special types of epoxy resins other than epibis type epoxy resins, namely various glycidyl ethers, glycidyl esters, and glycidyl ethers synthesized from phenols, carboxylic acids, and epichlorohydrin.
Similar research was conducted on ester-type epoxy resins, and as detailed in one example, results similar to those of Epibis-type epoxy resins were obtained.

There are generally two production methods for obtaining an epoxy resin containing a suitable 1,2-chlorohydrin chlorine as described above.

One method is to control the conditions of the ring-closing reaction to keep the content at a set level when the chlorohydrin product once formed is ring-closed with an alkali during the epoxidation process using epichlorohydrin. This is a method in which, for example, a calculated amount of hydrochloric acid is reacted with a product whose ring-closing reaction has been almost completely completed.

Since the latter hydrochloric acid addition reaction is extremely easy and can be carried out quantitatively, the desired 1,2-chlorohydrin chlorine content can be set and produced as desired.

Generally, the latter is preferred because it is easier to perform.

As is clear from the examples, the composition according to the present invention has 1.
It has better initial discoloration prevention ability than ordinary epoxy resins with low 2-chlorohydrin chlorine content, and at the same time has better thermal stability than conventional epoxidized soybean oil fatty acid esters.

Furthermore, all of the molded products according to the present invention have excellent gloss (particularly in the case of sheets, they also have excellent transparency).

Furthermore, the epoxy resin according to the present invention has no hygroscopicity (,
There is no crystal precipitation at low temperatures or during long-term storage, and therefore molded products have better plate-out properties, processability, and bleed resistance than epoxidized soybean oil fatty acid esters.

This will be explained in more detail below using examples.

Examples 1 to 5, Comparative Examples 1 to 2 Average molecular weight 380, epoxy equivalent 190, ■2-chlorohydrin chlorine (hereinafter simply referred to as chlorine content 5) 0.05
% Epibis type epoxy resin (Tobu Kasei Epototo Y
D-128) as raw material, 1 mol (380F) of this
was dissolved in 1000 TIL of isobutyl methyl ketone.

Maintain this at 60°C and add a calculated amount of 34% of 19% hydrochloric acid while stirring.
．． 3 ml was added at a rate of 0.311 LlZ min.

The reaction product was washed until neutral, and isobutyl methyl ketone was distilled off under reduced pressure.

The added hydrochloric acid was added quantitatively and the epoxy equivalent was 215,
A product with a chlorine content of 2.00 and a Gardner color tone of 1 or less was obtained.

Using the same raw materials, the chlorine content was 3.5.7.10%.
These were prepared and mixed according to the following formulations.

Vinyl chloride resin 100 parts Dioctyl phthalate 30" Ba-Zn stabilizer * 2" Epoxy stabilizer 3 u * 1 part each of Sakai Chemical Industries' LBZ, 797L and OW-497M 0, 1 in roll
The mixture was kneaded for 1 hour at a thickness of mm.

The obtained sheet was placed in a gear oven at 180° C. and its initial coloring ability and thermal stability were examined.

Thermal stability was expressed as the time (minutes) until blackening.

Comparative Example 1 is a raw material epoxy resin, and Reference Example 2 is an epoxidized soybean oil fatty acid ester.

The results are shown in Table 1. Example 6, Comparative Example 3 Average molecular weight 500, epoxy equivalent weight 250, chlorine content 0.
01% Epibis type epoxy resin (Tobu Kasei Epo) -
) YD-134) was used as a raw material, and in the same manner as in Example 1, an epoxy equivalent having an epoxy equivalent of 420 and a chlorine content of 5% was obtained.

A vinyl chloride resin sheet was produced in the same manner as in Example 1 except that this was used as a stabilizer.

Comparative Example 3 is a case where the above raw material epoxy resin was used.

The results are shown in Table 1. Example 7, Comparative Example 4 Average molecular weight 450, epoxy equivalent weight 150, chlorine content 0.
2% trimethylolpropane type epoxy resin (Tobu Kasei Epi) -) YH-301) with a chlorine content of 5%
The same test as in Example 1 was conducted except that the same test was used.

Comparative Example 4 is a case where a trimethylolpropane type epoxy resin was used as a raw material.

The results are shown in Table 1. Example 8, Comparative Example 5 Average molecular weight: 3501, epoxy equivalent: 175, chlorine content: 0.
The same test as in Example 1 was conducted except that a 2% phthalic acid type epoxy resin (manufactured by Yotetsu Kagaku) with a chlorine content of 6.6 was used.

Comparative Example 5 is a case where a phthalic acid type epoxy resin was used as a raw material.

The results are shown in Table 1. Example 9, Comparative Example 6 Average molecular weight 600, epoxy equivalent weight 220, chlorine content 0.
Similarly, 2% cresol novolak type epoxy resin (Epototo YDCN-220 manufactured by Tobu Kasei Co., Ltd.) was mixed with 5% chlorine content.
The same test as in Example 1 was conducted except that the same test was used.

Comparative Example 6 is a case where a cresol novolak type epoxy resin was used as the raw material.

The results are shown in Table 1. Table 1 1″-f′ stabilizer Initial coloration Thermal stability, equivalent weight, base.

Amount Prevention ability (min) Example 1 215
2 0 135112 250
3 0 130//3 2
90 5 ◎ 95//
4 340 7 ◎
85/15 550 10
◎ 75 Comparative Example 1 190
0.05 △ 135//2
230 0 0 75 Example 6 420 5 ◎
85 Comparative Example 3 250 0.01
△ 135 Example 7 210
5 ◎ 95 Comparative Example 4
150 0.2 △ 135
Example 8 310 6.6 ◎
90 Comparative Example 5 175 0.
2 △ 130 Example 9 34
5 5 ◎ 95 Comparative Example 6
220 0.2 △
130△ Coloring begins in about 15 to 30 minutes, and the degree of coloring increases each time the bottle is uncorked.

It becomes slightly colored in about 30 to 60 minutes, but hardly any progress is made after that.

◎ No change until it turns black.

Example 10 Example 3 Epoxy equivalent used: 290, chlorine content: 5%
Table 2 shows the results of a similar test using the same epoxy resin and varying the amount added.

As is clear from the results, even when 1.5 parts were added, the same effect as epoxidized soybean oil fatty acid ester was observed.

Table 2 A B C Vinyl chloride resin (parts) 100 100
100 dioctyl phthalate // 30
30 30Ba-Zn stabilizer
2 2 2 Epoxy stabilizer
// 1.5 2 3 Initial discoloration prevention ability ◎ ◎ ◎ Thermal stability (min) 75 85.
95 Example 11, Comparative Example 7 100 parts of vinyl chloride resin, 30 parts of dioctyl phthalate, epoxy equivalent used in Example 3 290, chlorine content 5
A sheet was prepared in the same manner as in Example 1 by adding 5 parts of 5% epoxy resin, and the same test was conducted.

As Comparative Example 7, the same amount of epoxidized soybean oil fatty acid ester was used instead of the above-mentioned epoxy resin.

In either case, the coloring started after 5 minutes and the brown color gradually became darker, but the time until it turned black was 90 minutes in the case of the present example, but 75 minutes in the case of Comparative Example 7.

This shows that the stabilizer according to the present invention is superior to conventional epoxidized soybean oil fatty acid esters even when a metal soap is not used in combination.

Claims (1)

[Claims] 1 Adding 2 to 10 percent by weight of l-2-chlorohydrin chlorine in its chemical structure to an epoxy resin made from epichlorohydrin as a raw material, and adding 1 to 3 percent by weight to the halogen-containing resin as a stabilizer. A thermostable chlorine-containing resin composition.