JP2627416B2 - Chlorine-containing resin molded product - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a molded article of a chlorine-containing resin, and particularly to a facility for manufacturing electronic parts such as semiconductors, a packaging container, an equipment case thereof, and furthermore, biochemistry, medicine, and medicine. The present invention relates to a novel chlorine-containing resin molded product suitably used for food-related applications and the like.

(Prior art) A typical example of chlorine-containing resin is vinyl chloride (hereinafter referred to as PVC).
Resins are widely used as synthetic resin molded articles because of their low cost, toughness, and excellent chemical resistance and secondary workability. Due to the characteristics of the resin structure, the PVC resin releases and dehydrogenates hydrogen and chlorine elements depending on the temperature at the time of molding,
Because the molded product turns yellow or black, PVC is used in advance in the resin material.
It is common to add a resin stabilizer. As such a stabilizer, a Pb or Sn-based metal compound stabilizer is mainly used, and similar metal-based stabilizers have been used in chlorine-containing resins other than PVC.

(Problems to be Solved by the Invention) By the way, recently, there has been remarkable development of electronic components mainly composed of semiconductors. However, such semiconductor manufacturing facilities, packaging containers for semiconductor components, and devices using the semiconductors have been developed. It is well known that synthetic resin molded products have come to be used for related devices such as cases. In the manufacturing process of electronic components using such manufacturing equipment, various processes such as washing with water and pickling must be performed, and the same applies to packaging containers, equipment cases, and the like. Alternatively, a chlorine-containing resin containing a metal compound such as Sn as a stabilizer may elute these metal elements during the above-described treatment and adversely affect electronic components, etc. Could not be used as a semiconductor member. Furthermore, if the chlorine-containing resin containing a metal element is also used for the exterior material of the above manufacturing equipment, the exterior material may be peeled off due to abrasion or the like, or the metal element may be deposited, and this may be scattered in the atmosphere to be used for electronic components and the like. There was also the problem of having an adverse effect. In addition, elution or scattering of metals has caused various troubles in biochemical, medical, pharmaceutical, and food-related applications. Under such circumstances, a fluororesin having extremely excellent thermal stability may be used as a synthetic resin applied to the above applications, but the fluororesin is expensive and is subject to secondary processing such as welding. It has a drawback that it is difficult to use, and therefore has poor versatility. Therefore, it has been strongly desired that a chlorine-containing resin which does not have such a drawback is suitable for the above-mentioned use.

In addition, the resin molded product as described above may be desired to be non-translucent (semi-transparent to opaque, hereinafter collectively referred to as non-translucent) depending on the use. However, in general, metal oxides such as titanium oxide are mainly used as the non-transparency imparting agent. When used in the above-mentioned electronic parts, positive chemicals, food-related equipment, etc., this non-transparency imparting agent is used. There is a concern that metal elements such as titanium may elute from
It has never been possible to apply a conventional non-light-transmitting agent as it is. Therefore, there has been a strong demand for the development of non-translucent resin molded products for such applications.

The present invention has been made in view of the above, and aims at thermal stabilization of a chlorine-containing resin with an effective stabilizer not containing a metal element such as Pb or Sn, and furthermore, a non-light-transmitting agent containing no metal element. The purpose of the present invention is to provide a molded article that is extremely effective for the above-mentioned applications by containing the above.

(Means for Solving the Problems) The chlorine-containing resin molded product of the present invention for achieving the above object is substantially free of a metal element, is stabilized by an aminocarboxylic acid ester and an epoxy compound, and has a melamine content. -It is characterized in that a chlorine-containing resin containing a cyanuric acid adduct or a melamine / isocyanuric acid adduct is molded into a desired shape to make it white non-translucent having a total light transmittance of 20% or less.

Here, the chlorine-containing resin refers to a resin mainly composed of vinyl chloride, such as a chlorinated vinyl chloride resin, an ethyleneated vinyl chloride resin, and an alloy with another resin, in addition to the above-mentioned PVC resin. Although the degree of polymerization of such a chlorine-containing resin is variously selected,
When a low polymerization degree which can be processed at a low temperature and does not require much heat resistance, for example, one having an average polymerization degree of 600 to 800, is used, the processing range is widened and a high quality molded product is obtained.

The aminocarboxylic acid ester employed here is a general term for a compound having an amino group and a carboxylic acid group. Examples of the compound having an amino group include ammonia, urea, acrylonitrile, aminoacetanilide, aminoanthraquinone, aminoethanol, and aminoethanol. Ethylene, aminoethylbenzene, aminocresol, aminophenol, caprolactam, etc., while the compounds having a carboxylic acid group include butyric acid, caproic acid, lauric acid, palmitic acid, stearic acid, crotonic acid, oleic acid, linolenic acid , Benzoic acid, naphthalic acid, malonic acid,
Examples include succinic acid, adipic acid, maleic acid, phthalic acid and the like. Representative examples of the aminocarboxylic acid esters of these compounds include acetylglutamate, glycine, alanine, pyrrolidonecarboxylate, lysine, alkynine, tryptophan, anthranilate, benzoate, β
-Amino crotonic acid ester, α-amino acrylate, α-amino adipate, aminomalonate, acetylphenylalanine, acetylmethionine ester compound, further acetyl amino acid and pentaerythritol or dipentaerythritol ester compound and the like, Further, an ester compound of 2-pyrrolidone-5-carboxylic acid and pentaerythrol and the like can be mentioned. Of these aminocarboxylic acid esters, β-
Aminocrotonates have the general formula However, it is represented by n; 1 to 6 R; a residue of a mono- to hexa-valent alcohol. Specific examples of ROH) n constituting this ester include methanol, ethanol, propanol, isopropanol, butanol,
-Ethylhexanol, isooctanol, octanol, isononanol, decanol, lauryl alcohol, myristyl alcohol, palmityl 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, mannitol, xylitol,
Dipentaerythritol and the like. The ester of the present invention is obtained by condensation polymerization of these alcohols and β-aminocrotonic acid. Preferred examples of the ester include stearyl alcohol β-aminocrotonate, 1,4-butanediol diβ- Amino crotonic acid ester, thiodiethanol di-β-amino crotonic acid ester, trimethylolpropane tri β-amino crotonic acid ester, pentaerythritol tetra β-amino crotonic acid ester, dipentaerythritol hexa β-amino crotonic acid ester and the like. .

Epoxy compounds include epoxidized animal and vegetable oils,
Examples include epoxidized fatty acid esters, epoxidized alicyclic compounds, glycidyl ether or glycidyl ester compounds, epoxidized polymer compounds, and other epoxy compounds. Specifically, epoxidized animal and vegetable oils include epoxidized soybean oil, epoxidized linseed oil, epoxidized safflower oil, epoxidized sunflower oil, epoxidized cottonseed oil, and the like. Epoxidized fatty acid esters include epoxidized stearin oil. Methyl acrylate, epoxidized butyl stearate, epoxidized octyl stearate, epoxidized linseed oil fatty acid butyl, and the like. Epoxidized environmental compounds include epoxidized tetrahydrophthalic acid esters (alcohols such as butanol, octanol, and decanol). Glycidyl ether or glycidyl ester compounds include bisphenol A glycidyl ether, glycidyl methacrylate and polymers thereof, and epoxidized polybutadiene and epoxidized epoxy polymer compounds. Acrylonitrile-butadiene rubber.

As for the combination of the aminocarboxylic acid ester and the epoxy compound, the combination of β-aminocrotonate and glycidyl ether or glycidyl ester is excellent in thermal stability and is best.

The stabilizer is added in an amount of 0.5 to 5.0 parts by weight of the aminocarboxylic acid ester and 0.5 to 5.0 parts by weight of the epoxy compound with respect to 100 parts by weight of the chlorine-containing resin to stabilize the chlorine-containing resin. Is characterized by not containing any metal element such as Pb or Sn. The appropriate amount of the mixture to be added to the chlorine-containing resin is as described above, but when both of the above stabilizers are less than 0.5 parts by weight, sufficient thermal stability cannot be obtained. Although the stability is improved accordingly, it is economically disadvantageous, and preferably both are used in the range of 1.0 to 3.0 parts by weight.

In addition, a melamine / cyanuric acid adduct or a melamine / cyanuric acid adduct (hereinafter referred to as a melamine / (iso) cyanuric acid adduct) is imparted to the chlorine-containing resin stabilized by the stabilizer to impart non-light transmittance. It is contained as an agent, is colored white, and has non-light-transmitting properties with a total light transmittance of 20% or less. Among the non-light-transmitting agents, melamine / cyanuric acid adduct is a planar structure in which a melamine molecule having a 6-membered ring structure and a cyanuric acid molecule are strongly bonded by hydrogen bonds and arranged in a plane. The melamine and isocyanuric acid adducts are composed of melamine molecules and isocyanuric acid molecules bound in the same way, and have a cleavage property, while white has recently been developed as an organic solid lubricant. It is a fine powder. The melamine / (iso) cyanuric acid adduct is obtained from a precipitate obtained by mixing an aqueous melamine solution and an aqueous solution of cyanuric acid or isocyanuric acid, and further obtained by mixing the melamine / (iso) cyanuric acid adduct with cyanuric acid. Alternatively, a mixture with isocyanuric acid can be used. The adduct is a white powder having a particle size of 0.5 to 5 μm and shows a uniform particle size distribution. In addition, it does not contain a metal element as described above, and when dispersed in a chlorine-containing resin, presses or extrudes the chlorine-containing resin by coloring it white to impart non-light-transmitting properties and imparting lubricity to the resin. At the time of molding, etc., it also has a function as a lubricant to improve mold releasability from the mold and improve moldability, and 1 to 20 parts by weight based on 100 parts by weight of the resin.
It is added in parts by weight.

As described above, by combining the above stabilizers, the thermal stability of the chlorine-containing resin can be obtained, and by blending the melamine / (iso) cyanuric acid adduct, the resin molded article can have white non-light-transmitting properties. Furthermore, other metal-free stabilizing aids and additives can be freely added as long as the white non-light-transmitting property is not impaired. Examples of the stabilizing aid include organic phosphites, phenol derivatives, polyhydric alcohols,
Examples include nitrogen-containing compounds, sulfur-containing compounds, keto compounds, and the like. As additives, amine-based, phenol-based,
Antioxidants such as sulfur-based and phosphorus-based, light stabilizers such as ultraviolet absorbers, polyols, β-diketo compounds, auxiliaries such as nitrogen-containing compounds, phthalate esters, aromatic carboxylic acid esters,
Plasticizers such as aliphatic dibasic esters, reinforcing agents such as ABS and MBS, halogen-based, phosphate-based flame retardants, organic coatings,
An antifungal agent, a foaming agent, etc. are used to promote the stabilization of the chlorine-containing resin, improve the workability, improve the weather resistance, improve the mechanical properties, or plasticize or foam. Or you can let them.

(Action) As described above, the chlorine-containing resin containing an aminocarboxylic acid ester as a stabilizer and an epoxy-based stabilizer can be used to form a plate, sheet, pipe, or the like by a usual molding method, that is, a calender roll, a press, an extrusion or an injection method. , Angles, welding rods, pipe joints or valves and other industrial materials. During the molding, the temperature of the chlorine-containing resin becomes 150-200 ° C. Therefore, if the stabilizer is not contained in the resin, the hydrogen element and the chlorine element in the resin structure are liberated and dehydrochlorinated, and the resin turns yellow or black. However, in the molded article of the chlorine-containing resin of the present invention, the action of the stabilizer comprising the aminocarboxylic acid ester and the epoxy compound, that is, the action of preventing the release of chlorine element by the epoxy group and the action of preventing the double bond formation by the amino group are synergistic. Since heat stability has been imparted by preventing polyol formation,
It does not discolor even when the temperature rises during molding.

In addition, the chlorine-containing resin stabilized as described above contains a melamine / (iso) cyanuric acid adduct that imparts non-light-transmitting properties and also serves as a lubricant. In addition to being light-emitting, the moldability during press or extrusion molding is improved, and a very glossy and excellent appearance is exhibited.

A molded product obtained by molding a chlorine-containing resin stabilized by an aminocarboxylic acid ester and an epoxy compound containing no metal element as described above contains substantially no metal, and the semiconductor-related manufacturing equipment (particularly cleaning) Device)
There is no concern that harmful metal elements such as Sn and Sn will elute, and the inexpensive, tough properties and chemical resistance of the chlorine-containing resin will be maintained, so medical, pharmaceutical, biochemical, If applied to manufacturing equipment for food and the like, related equipment, etc., a great benefit is brought economically. Here, the expression that substantially no metal is used is used when a chlorine-containing resin, a stabilizer, a lubricant, a coloring agent, or the like is produced in an unintentional and inevitable range when a trace amount of metal is used. This is because metal may not be completely absent in the final molded product, and each metal may be contained in several ppm.

Also, chlorine-containing resin is extremely easy to perform secondary processing such as cutting, cutting, welding, welding, hot bending, etc., so it is more versatile than conventional fluororesin molded products, and it can be used in various applications related to the above applications. Promised.

Further, as described above, the melamine / (iso) cyanuric acid adduct that imparts non-light-transmitting properties makes the molded product itself white non-light-transmitting and has a total light transmittance of 20% or less. Does not contain a metal element as described above, the characteristics of the chemical resistance (with respect to treatments such as pickling and washing) are maintained, and therefore, it is not desirable to see through the inside of the electronic component. It is also very suitable for a manufacturing facility or a manufacturing apparatus for medical, pharmaceutical, biochemical, food-related substances, etc., which easily cause photochemical reactions.

(Example) Next, an example is described.

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

In addition, (1) to (3) in the column of sample No. in Table 1 show the No. of the embodiment. As the melamine / cyanuric acid adduct, MCA manufactured by Yuka Melamine Co., Ltd. was used.

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

The ratios (1) to (4) in Table 2 show comparative examples.
Also, the acrylic modified modifier is disclosed in Japanese Unexamined Patent Publication No.
It is equivalent to the colorant used in 48643.

(Ii) Measurement of thermal stability For each of the above samples, a calender roll (160 ° C x
5 minutes), after the sheet is made, the pressing time is changed to 3 minutes and 10 minutes with a press (160 ° C), and each is heated and molded to a thickness of 5 mm.
The thermal stability was measured by the change in hue due to the difference in press time of the molded product. Table 3 shows the results.

As understood from Table 3, in Examples (1) and (2), when the press time was long, the color changed from white to milky and opaque. However, from the viewpoint of Comparative Example (2), sufficient heat stability was obtained. Is evaluated. In Example (3), no discoloration was observed. However, it is considered that the discoloration was suppressed because the addition amount of the melamine / cyanuric acid adduct was large and the whiteness was strong. Furthermore, comparing the appearances of the 3-minute pressed samples of Examples (1) to (3) and Comparative Example (4), Examples (1) to (3) have higher whiteness and gloss than Comparative Example (4). And was extremely excellent.

(Iii) Measurement of General Physical Properties The general physical properties of the press-molded products of the above Examples and Comparative Examples were measured. The results are shown in Table 4.

In Table 4, "Actual" and "Ratio" indicate the examples and comparative examples, respectively. As understood from Table 4, Examples (1), (2) and (3) have almost the same physical property values as Comparative Example (1) and can be used in the same manner as the conventional PVC plate. I understand. In addition, it is understood that the thermal deformation temperatures of Examples (1), (2), and (3) are higher than those of Comparative Example (1), and are suitable for use at relatively high temperatures.

(Iv) Measurement of optical characteristics Examples (1) to (3) and Comparative Examples (1) to (4)
The light transmittance (total light, diffusion, parallel light transmittance) of the press-molded product (thickness, 3 mm) of the sample was measured. The results are shown in Table 5.

As understood from Table 5, the total light transmittances of Examples (1) to (3) were extremely lower than those of Comparative Examples (1) and (2).
In addition, it is understood that the amount of diffused light is large and the light is not translucent. Moreover, the non-light-transmitting property is larger than that of Comparative Example (4) using the acrylic modification modifier. Therefore, it is sufficiently applicable to the above-mentioned applications requiring non-light-transmitting properties.

(V) Measurement of color difference The three-minute press samples of Examples (2) and (3) and Comparative Examples (3) and (4) were measured for their color difference with a Suga Test Co., Ltd. SM color computer, model color SM-3-CH. It was measured. Table 6 shows the results.

However, st in the table means standard.

From Table 6, it is understood that the sample of the example of the present invention is almost pure white and has particularly excellent whiteness as compared with the comparative example (4).

(Vi) Apart from the above, Example (2) and Comparative Example (1)
For the test piece of (3), trace metal elements contained were determined by atomic absorption spectroscopy (Sn, Pb) and ICP emission spectroscopy (Ca, Z
n, Ti, Mg). Table 7 shows the results.

As understood from Table 7, in Example (2), metal elements such as Pb and Sn were hardly detected, and in Comparative Example (1), a large amount of Sn contained in the main stabilizer was detected. In ()), a large amount of Ti contained in the non-light-transmitting agent was detected.

(Vii) Dissolution test Example (2), Comparative Example (1) and Pb prepared separately
A sample of a PVC resin [Comparative Example (5)] with as a main stabilizer was prepared based on JIS K6743 in 100 ml of pure water with a surface area of 1
An 8 cm ² sample was immersed for 24 hours, and the eluted trace metals were analyzed by atomic absorption spectrometry and ICP emission spectrometry. Table 8 shows the results.

As understood from Table 8, no metal was eluted from Example (2). Further, Sn or Pb contained in the stabilizer was eluted from Comparative Examples (1) and (5).

In addition, the same test as described above was carried out for PVC resins using aminocarboxylic acid esters and epoxy compounds other than the above examples, and substantially the same results were obtained. In addition, when the appearance of the molded product obtained by injection, extrusion, or the like was observed, all were extremely excellent, and good moldability was confirmed. Further, when a chlorinated vinyl chloride resin is used instead of the PVC resin, the heat deformation temperature is improved to approximately 100 ° C., and when an alloy is used, the secondary workability is improved.

(Effects of the Invention) As described above, the chlorine-containing resin molded product of the present invention does not contain a metal compound such as Pb or Sn as a stabilizer unlike conventional chlorine-containing resins of this type, and therefore, semiconductors, biochemistry, Medical,
There is no concern that metal elements will be eluted when supplied to manufacturing facilities for pharmaceuticals, foods, etc. In addition, the inherently inexpensive and tough properties inherent in chlorine-containing resins and excellent properties in chemical resistance and secondary processing are added to this. Therefore, it is very suitably used for the above applications.
In addition, since the aminocarboxylic acid ester and the epoxy compound impart thermal stability, the original appearance is maintained without yellowing or blackening even when the temperature rises during molding. In addition, melamine containing no metallic elements
Since the (iso) cyanuric acid adduct is added as a non-light-transmitting substance that also functions as a lubricant, the molded product itself is made white non-light-transmitting while maintaining the property that metal is not eluted, and is transparent. It is very suitable for the above-mentioned use where no optical effect is required or when it is desired to eliminate optical effects. In particular, since the specified non-light-transmitting substance has a low total organic carbon (TOC), bacteria may propagate in the processing liquid even when the molded article of the present invention is used in a semiconductor-related processing apparatus or the like. Therefore, it can be said that, in this sense, it is extremely suitable for high-quality semiconductor manufacturing equipment and the like. In addition, the moldability is improved by the lubricating function, and an extremely excellent appearance is obtained.

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

Claims (1)

(57) [Claims] 1. A melamine / cyanuric acid adduct or a melamine / cyanuric acid adduct, substantially free of a metal element, stabilized by an aminocarboxylic acid ester and an epoxy compound.
A chlorine-containing resin molded product which is made of a chlorine-containing resin containing an isocyanuric acid adduct into a desired shape and has a white non-light-transmitting property with a total light transmittance of 20% or less.