JPS63110238A - Chlorine-containing resin molded article - Google Patents

Abstract

PURPOSE:To obtain a molded article free from Pb, Sn, etc., suitable for semiconductor production equipment etc., by molding a chlorine-contg. resin incorporated with an aminocarboxylic acid, epoxy compound, and e.g., polyhydric alcohol having neopenta type skeleton. CONSTITUTION:The objective article can be obtained by blending (A) 100pts.wt. of a chlorine-contg. resin with an average polymerization degree 600-800 consisting mainly of vinyl chloride, (B) each 0.5-5(pref. 1-3)pts.wt. of an aminocarboxylic acid (pref. beta-aminocrotonic ester) and epoxy compound (pref. glycidyl ether or glycidyl ester), and (C) 1-6pts.wt. (up to 3pts.wt. in case of press molding) of either polyhydric alcohol having neopenta type skeleton (e.g., monopentaerythritol), its ester or trimellitic ester (pref. tristearyl trimellitate) followed by molding into a desired shape.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to various molded products made of chlorine-containing resins, and particularly to molded products made of chlorine-containing resins that do not contain stabilizers made of metal compounds such as Sn or the like.

(Conventional technology) Vinyl chloride (hereinafter referred to as vinyl chloride) is a typical example of chlorine-containing resin.

(abbreviated as PVC) resin is widely used as a synthetic resin molded product because it is inexpensive, tough, and has excellent chemical resistance and secondary processability. Due to the characteristics of the resin structure of the PvC resin, H and C0 elements are liberated and dehydrochlorinated depending on the temperature during molding, causing the molded product to turn yellow or black, so a stabilizer for PVC resin is added to the resin raw material in advance. It is common to add it. As such stabilizers, Sn-based metal compound stabilizers are mainly used in the Pb composition, and this is also true for other chlorine-containing resins other than PvC.

(Problem to be Solved by the Invention) Incidentally, in recent years, there has been remarkable development in electronic components mainly based on semiconductors, but the manufacturing equipment for such semiconductors (especially cleaning equipment, etching equipment, etc.) also requires synthetic resin molding. It is well known that products have come to be used. Such manufacturing equipment must undergo various treatments during the process, and PvC resins containing metal compounds such as PB or Sn as stabilizers are free of these metal elements during the above treatments. It could not be used as a component for high-quality semiconductors, such as semiconductors of 1 megabit or more, because it would be eluted and have an adverse effect on electronic components.

In addition, elution of metals has caused various troubles in biochemical, medical, pharmaceutical, and food-related applications. Under these circumstances, fluororesin, which has extremely high thermal stability, is sometimes used as a synthetic resin for the above-mentioned applications, but fluororesin is expensive and cannot be subjected to secondary processing such as welding. It has the disadvantage of being difficult to use, so it lacks versatility. Therefore, it has been strongly desired to use a chlorine-containing resin that does not have these drawbacks and is suitable for the above-mentioned applications.

The present invention was developed in view of the above-mentioned circumstances, and aims to thermally stabilize chlorine-containing resin with an effective stabilizer that does not contain metal elements such as PB and Sn. We provide molded products, and in addition, we provide molded products that are semitransparent to opaque (hereinafter collectively referred to as non-transparent).
By doing so, it is intended to make it suitable for other uses.

(Means for Solving the Problems) The chlorine-containing resin molded product of the present invention to achieve the above object comprises a polyhydric alcohol stabilized by an aminocarboxylic acid and an epoxy compound, and having a neopenta-type skeleton; It is characterized in that it is formed by molding a chlorine-containing resin containing either an alcohol ester or a trimellitic acid ester into a desired shape.

Here, the chlorine-containing resin refers to resins mainly composed of vinyl chloride, such as chlorinated vinyl chloride resins, ethylenic vinyl chloride resins, and alloys with other resins, in addition to the above-mentioned PvC resins. The degree of polymerization of such a chlorine-containing resin can be selected from various values, including low degrees of polymerization that can lower the processing temperature and do not require much heat resistance;
For example, if one with an average degree of polymerization of 600 to 800 is used, the processing range will be expanded and high quality molded products will be obtained.

The aminocarboxylic acid used here is a general term for compounds having an amino group and a carboxylic acid group, and examples of compounds having an amino group include ammonia, urea, acrylonitrile, and aminoacetanilide.

Examples include aminoanthraquinone, aminoethanol, aminoethylene, aminoethylbenzene, aminocresol, aminophenol, caprolactam, etc., while compounds with carboxylic acid groups include butyric acid, caproic acid, lauric acid, palmitic acid, stearic acid, croton. acids, oleic acid, lylunic acid, benzoic acid, naphthoric acid, malonic acid.

Examples include succinic acid, adipic acid, maleic acid, and phthalic acid. In addition, typical aminocarboxylic acids that are these compounds include acetylglutamic acid, glycine, alanine, pyrrolidonecarboxylic acid, lysine, alkynine, tryptophan, anthranilic acid, benzoic acid, β-aminocrotonic acid, α-amino Acrylic acid, α-aminoadipic acid, aminomaloic acid, acetylphenylalanine, acetylmethionine, and their ester compounds, as well as ester compounds of acetylamino acid and pentaerythritol or dipentaerythritol, and 2-pyrrolidone-5-carboxylic acid. Examples include ester compounds with pentaerythritol. Among these aminocarboxylic acids, β-aminocrotonic acid ester.

General formula % Formula %) R: Represented by a residue of a mono- to hexavalent alcohol. Further, specific examples of R+0H)n constituting this ester include methanol, ethanol, propatool, isoproptool, butanol,
-Ethylhexanol, isooctatool, octatool, isononanol, decanol, lauryl alcohol, myristyl alcohol, valmityl alcohol, stearyl alcohol, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1. 6-hexanediol, 1,10-decanediol, diethylene glycol, thiodiethanol,
Trimethylolpropane, glycerin, tris(2-hydroxyethyl)isocyanurate, triethanolamine, pentaerythritol, ditrimethanolpropane, diglycerin, sorbitol.

Examples include mannyl, xylitol, dipentaerythritol, and the like. And these alcohols and β-
The ester of the present invention is obtained by condensation polymerization with aminocrotonic acid, and desirable specific examples of the ester include stearyl alcohol β-aminocrotonic acid ester, 1,4
Butanediol diβ-aminocrotonate, thiodiethanol diβ-aminocrotonate, trimethylolpropane triβ-aminocrotonate,
Examples include pentaerythritol tetraβ-aminocrotonic acid ester, dipentaerythritol hexaβ-aminocrotonic acid ester, and the like.

Examples of the epoxy compound include epoxidized animal and vegetable oils, epoxidized fatty acid esters, epoxidized alicyclic compounds, glycidyl ether or glycidyl ester compounds, epoxidized polymer compounds, and other epoxy compounds. Specifically, examples of epoxidized animal and vegetable oils include epoxidized soybean oil, epoxidized linseed oil, epoxidized flower oil, epoxidized sunflower oil, and epoxidized cottonseed oil, and examples of epoxidized fatty acid esters include epoxidized stearic acid. Examples include methyl, epoxidized butyl stearate, epoxidized octyl stearate, epoxidized linseed oil butyl fatty acid, etc. Epoxidized alicyclic compounds include epoxidized tetrahydrophthalate (alcohols include butanol, octatool, decanol, etc.) Examples of glycidyl ether or glycidyl ester compounds include bisphenol A glycidyl ether, glycidyl methacrylate, and polymers thereof; further examples of epoxy polymer compounds include epoxidized polybutadiene, epoxidized acrylonitrile-butadiene rubber, and the like.

Among the combinations of these aminocarboxylic acids and epoxy compounds, the combination of β-aminocrotonic acid ester and glycidyl ether or glycidyl ester has good thermal stability and is best.

The above stabilizers stabilize the chlorine-containing resin by adding 0.5 to 5.0 parts by weight of an aminocarboxylic acid and 0.5 to 5.0 parts by weight of an epoxy compound to 100 parts by weight of the chlorine-containing resin. This mixture as a stabilizer is characterized by the absence of any metallic elements such as Pb or Sn.

The appropriate amount of compound i to be added to the chlorine-containing resin is as described above, but if both of the above stabilizers are less than 0.5 parts by weight, sufficient thermal stability will not be obtained; If the amount exceeds 0 parts by weight, the thermal stability will be improved accordingly, but it will be economically disadvantageous, so both are preferably used in the range of 1.0 to 3.0 parts by weight.

In addition, the chlorine-containing resin stabilized by the above stabilizer has
Contains either a polyhydric alcohol having a neopenta-type skeleton, an ester thereof, or a tris-1-acid ester. As a polyhydric alcohol with a neopenta-type skeleton,
monopentaerythritol, dipentaerythritol,
Tripentaerythritol, tetrapentaerythritol, etc., those in which the polyhydric alcohols mentioned above are partially ether bonded within the molecule, those in which the intermediate methylol group is ether bonded to other molecules, and those in which the polyhydric alcohols are connected in a network.

Examples include those in which the molecule becomes large and has a macrocyclic ether structure at various locations. Furthermore, their ester compounds are also used, but polybasic acids and long chain fatty acids are used as acids, and polybasic acids include maleic acid, phthalic acid, succinic acid, adipic acid, sepatic acid, tartaric acid, citric acid, etc. As long chain fatty acids, capric acid, lauric acid, stearic acid, linoleic acid, etc. are used. On the other hand, as the trimellitic acid ester, tristearyl trimellitate is preferably employed. As mentioned above, these do not contain any metallic elements, and when dispersed in a chlorine-containing resin, they color the chlorine-containing resin white and give the resin lubricity, so that it can be used with a mold during pressing or extrusion molding. It also has the function of a lubricant that improves mold release properties and improves moldability, and is added in an amount of 1 to 6 parts by weight per 100 parts by weight of the rosin.

However, in the case of press molding, up to 3 parts by weight is appropriate, and in the case of extrusion molding, up to 6 parts by weight is considered appropriate. In addition, catalysts such as phosphorus are used in the synthesis of such lubricants, and since some of this is contained in the composition, the lubricant must be washed with a metal removal device or pure water to remove the catalytic gold IJC before use. It is desirable to keep it.

As mentioned above, thermal stability of the chlorine-containing resin can be obtained by combining the above-mentioned stabilizers, but other metal-free stabilizing aids and additives can also be freely added. Examples of the stabilizing agent include organic phosphites, phenol derivatives, polyhydric alcohols, nitrogen-containing compounds, sulfur-containing compounds,
Examples include keto compounds. Additives include amine-based, phenolic-based, sulfur-based, and phosphorus-based antioxidants, light stabilizers such as ultraviolet absorbers, polyols, auxiliary agents such as β-diketo compounds, nitrogen-containing compounds, and phthalate esters. , plasticizers such as aromatic carboxylic acid esters and aliphatic dibasic esters, reinforcing agents such as ABS and MBS for transparency, halogen-based and phosphoric ester-based flame retardants, pigments, antifungal agents, and foaming agents. It can help stabilize chlorine-containing resins, improve processability, improve weather resistance, improve mechanical properties, and can be plasticized and foamed.

(Function) As mentioned above, the chlorine-containing resin containing aminocarboxylic acid and epoxy stabilizer can be molded into plates, sheets, pipes, It is molded into angles, welding rods, piping joints, valves, and other industrial materials. During this molding, the temperature of the chlorine-containing resin is 150-200°C. Therefore, if the resin does not contain a stabilizer, H and CQ in the resin structure are liberated and dehydrochlorinated, resulting in yellowing or blackening of the resin. However, in the molded product of the chlorine-containing resin of the present invention, due to the action of the stabilizer consisting of an aminocarboxylic acid and an epoxy compound, the action of preventing the release of CQ by the epoxy group and the action of preventing double bond formation by the amino group are synergistic, and the polyol Since thermal stability is imparted by preventing oxidation, there is no discoloration even when the temperature rises during molding.

Also, for chlorine-containing resins stabilized as described above.

Contains a substance that also acts as a lubricant and imparts non-translucent properties, making the molded product white and non-transparent, improving moldability during press or extrusion molding, and giving it a glossy finish. It has an extremely excellent appearance.

As described above, a molded product obtained by molding a chlorine-containing resin stabilized with an aminocarboxylic acid and an epoxy compound that does not contain metal elements does not substantially contain metal.

Even when used in the aforementioned semiconductor-related manufacturing equipment (especially cleaning equipment, etc.), there is no concern that harmful metal elements such as PB and Sn will be leached, and the low cost, tough characteristics and chemical resistance of chlorine-containing resins are maintained. Medical, pharmaceutical, and biochemistry other than the semiconductor-related manufacturing equipment mentioned above.

If it is applied to food manufacturing equipment, related equipment, etc., it will bring great economic benefits. The term "substantially free of metals" is used here to mean that trace amounts of metals are unintentionally but unavoidably contained in the production of chlorine-containing resins, stabilizers, lubricants, colorants, etc. However, it cannot be said that there are no metals in the final molded product, and the amount of each metal may be several ppm.
This is because it may be included.

In addition, chlorine-containing resins can be cut, cut, welded, or welded.

Because secondary processing such as hot oiling is extremely easy, it is more versatile than conventional fluororesin molded products, and promises a variety of uses related to the above.

Furthermore, as mentioned above, the molded product itself becomes non-transparent due to the non-transparent properties, and since these substances do not contain the above-mentioned metal elements, the chemical resistance mentioned above (pickling, water washing) Therefore, it is not desirable to see through the inside of the above-mentioned electronic component manufacturing equipment, or medical, pharmaceutical, biochemical, and food-related substances that are prone to photochemical reactions. It is also extremely suitable for manufacturing equipment, etc.

(Example) Next, examples will be described.

(i) Preparation of Sample (i-1) A chlorine-containing resin for obtaining a molded article of the present invention was prepared according to the formulation shown in Table 1 below.

(Left below) Measures - 1 - Person (1) to (6) in the column of sample shame in Table 1
) indicates Nα of the example.

(i-2) A sample as a comparative example was prepared with the formulations shown in Table 2 below.

Table 2 (ii) Measurement of thermal stability Calendar roll (160"C) for each sample above
After creating a sheet using a press (160°C) for 3 minutes and 10 minutes, the sheet was heated and molded to a thickness of 5 nn+. Thermal stability was measured. The results are shown in Table 3.

■' 辣＆ As understood from this Table 3, Example (L) (2)
(4) and (5) have changed from white to milky opaque, but in light of Comparative Example (2), they are evaluated as having sufficient thermal stability. Further, Examples (3) and (6) did not change color, but they contained large amounts of dipentaerythritol and tristearyl trimellitate.

It is thought that discoloration is suppressed because the whiteness is strong.

The appearance of Examples (1) to (6) was glossy and extremely excellent.

(ni) - Measurement of film physical properties The general physical properties of the press-molded products of Examples (1), (4) and Comparative Example (1) were measured. The results are shown in Table 4.

Table 4 However, in Table 4, "actual" and "ratio" indicate Examples and Comparative Examples, respectively. As understood from this Table 4, Example (1
) It can be seen that Comparative Example (4) has almost the same physical property values as Comparative Example (1) and can be used in the same way as conventional PvC boards. Further, it is understood that the heat distortion temperatures of Examples (1) and (4) are higher than that of Comparative Example (1), and that they are suitable for use at relatively high temperatures.

(iv) Measurement of optical properties The total light transmittance and diffused light rate of the press-molded products (thickness, 3 mm) of the samples of Examples (1) to (6) and Comparative Example (1) were measured. . The results are shown in Table 5.

As understood from Table 5, the total light transmittance of Examples (1) to (6) is lower than that of Comparative Examples (1) and (2), and the amount of diffused light is also large, indicating that they are non-transparent. is understood. Therefore, it is fully applicable to the above-mentioned applications requiring non-transparent properties.

(v) Separately from the above, trace amounts of total dioptric elements contained in the test pieces of Example (1) and Comparative Example (1) were analyzed by atomic absorption spectrometry (S n, P b) and ICP emission spectrometry (Ca
, Zn, Ti, Mg). The results are shown in Table 6.

However, the unit is ppm.

As understood from Table 6, in Example (1), pb and Sn
Almost no metal elements were detected.

(vi) Elution test The above Example (1), Comparative Example (1) and separately prepared Pb
Regarding a sample of PVC resin [comparative example (2)] containing PVC as the main stabilizer, pure water 10
A sample with a surface area of 18 aJ was immersed in 0 mR for 24 hours, and trace metals eluted were analyzed by atomic absorption spectrometry and ICP emission spectrometry. The results are shown in Table 7.

(Unit: ppm) As understood from Table 7, no metal was eluted from Example (1). Moreover, Sn or Pb contained in the stabilizer was eluted from Comparative Examples (1) and (2).

Incidentally, when PvC resins using aminocarboxylic acids and epoxy compounds other than those in the above examples were also tested in the same manner as above, substantially the same results were obtained.

In addition, injection (the blending amount of the above lubricant is 0.5 to 3
When the appearance of the molded products obtained by extrusion (1 to 6 parts by weight) was observed, it was found that they were both extremely excellent, confirming good moldability. Furthermore, when a chlorinated vinyl chloride resin is used in place of the PvC resin, the heat distortion temperature increases to approximately 100°C, and when an alloy is used, the secondary processability is improved.

(Effects of the Invention) As mentioned above, the chlorine-containing resin molded product of the present invention does not contain a total bending compound such as PB or Sn as a stabilizer unlike conventional chlorine-containing resins of this kind, so it is suitable for semiconductors, biochemistry, etc. There is no possibility that metal elements will be leached out even if it is used in manufacturing equipment for medical, pharmaceutical, food, etc., and it also has the inherent properties of chlorine-containing resin, such as being inexpensive and strong, as well as having excellent chemical resistance and secondary processability. Since it is added to this, it is very suitably used for the above-mentioned purpose.

Furthermore, since thermal stability is imparted by the aminocarboxylic acid and epoxy compound, the original appearance is maintained without yellowing or blackening even when the temperature rises during molding. Furthermore, since a substance that does not contain metal elements and also serves as a lubricant that imparts non-transparent properties is added, the molded product itself remains non-transparent while maintaining the property that metals do not elute, requiring transparent inspection. It is extremely suitable for the above-mentioned applications where optical effects are not required or where it is desired to eliminate optical effects. In particular, the non-translucent imparting substance identified above has a low total organic carbon content (T○C), so even if the molded product of the present invention is used in semiconductor-related processing equipment, bacteria will grow in the processing solution. Therefore, in this sense as well, it can be said that it is extremely suitable for high-quality semiconductor manufacturing equipment. In addition, its lubriciousness improves moldability and provides an extremely excellent appearance.

The chlorine-containing resin molded product of the present invention having such excellent performance is extremely useful.

one or more one

Claims (1)

[Claims] 1. A polyhydric alcohol stabilized by an aminocarboxylic acid and an epoxy compound and having a neopenta-type skeleton;
A chlorine-containing resin molded product obtained by molding a chlorine-containing resin containing either an ester of the polyhydric alcohol or a trimellitic acid ester into a desired shape.