JPH0576428B2 - - Google Patents

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to molded products made of chlorine-containing resin, and is particularly applicable to manufacturing equipment for semiconductors and other electronic components, packaging containers, equipment cases thereof, and biochemical, medical, pharmaceutical, and food-related applications. The present invention relates to a novel chlorine-containing resin molded product that can be suitably used. (Prior art) Vinyl chloride (hereinafter referred to as PVC) resin, which is a typical example of chlorine-containing resin, is widely used as synthetic resin molded products because it is inexpensive, tough, chemical resistant, and has excellent secondary processability. It is being Due to the characteristics of the PVC resin structure, H
and CI elements are liberated and dehydrochlorinated, causing yellowing or blackening of the molded product, so it is common to add a stabilizer for PVC resin to the resin raw material in advance.
As such stabilizers, stabilizers of Pb or Sn-based metal compounds are mainly used, and similar metal-based stabilizers have been used in other chlorine-containing resins other than PVC. (Problems to be Solved by the Invention) Incidentally, the recent development of electronic components based on semiconductors has been remarkable. It is well known that synthetic resin molded products have come to be used for related equipment such as cases. In the manufacturing process of electronic components using such manufacturing equipment, various treatments such as washing with water and pickling must be performed, and packaging containers, equipment cases, etc. must also be treated with pickling or washing with water. However, as mentioned above, chlorine-containing resins containing metal compounds such as Pb or Sn as stabilizers are not suitable for high-temperature resins, as these metal elements will be eluted during the above treatment and have an adverse effect on electronic components. It could not be used as a component for high-quality semiconductors, for example, 1 megabit semiconductors. In addition, metal elution 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 applications, but fluororesin is expensive and requires secondary processing such as welding. It has the disadvantage of being difficult to remove, so it lacks versatility. Therefore, there has been a strong desire for a chlorine-containing resin that does not have these drawbacks and is inexpensive, strong, and has excellent chemical resistance and is suitable for the above-mentioned uses. In addition, synthetic resin molded products generally have a high electrical resistivity (the above-mentioned chlorine-containing resin is no exception), easily become charged due to friction or peeling, and attract dirt and dust in the atmosphere, so they are not suitable for the above applications. If exposed, it will adversely affect the performance of electronic components, etc. The present invention was made in view of the above, and
By combining a chlorine-containing resin stabilized with a stabilizer that does not contain metal elements, such as antistatic or conductive material, metal elements do not elute, and there is no adhesion of dirt or dust. The present invention aims to provide a novel chlorine-containing resin molded product that is extremely effective and inexpensive for semiconductor-related applications. (Means for Solving the Problems) The structure of the chlorine-containing resin molded product of the present invention to achieve the above object will be explained based on the attached example drawings. Figure 1 shows an example of the molded product of the present invention. FIG. 2 is a partially enlarged perspective view showing an example of its application. That is, the chlorine-containing resin molded product of the present invention is a chlorine-containing resin stabilized with one or more nonmetallic stabilizers such as aminocarboxylic acids, hydrazides, epoxy compounds, and organic phosphite esters. The main feature is that an antistatic or conductive coating layer 2 is integrally laminated on at least one side of a base layer 1, and the entire body is formed into a desired shape. Here, the chlorine-containing resin that constitutes the base layer portion 1 is:
In addition to the above PVC resin, chlorinated vinyl chloride resin,
Refers to resins mainly composed of vinyl chloride, such as ethylene vinyl chloride resins and alloys with other resins. Various degrees of polymerization can be selected for such chlorine-containing resins, but if you use a low degree of polymerization that allows for low processing temperatures and does not require much heat resistance, for example, an average degree of polymerization of 700 to 800, the processing range will be expanded and high quality will be achieved. A molded product is obtained. This low degree of polymerization resin is preferably employed especially when obtaining transparent molded products. The chlorine-containing resin constituting the base layer portion 1 is stabilized with a non-metallic stabilizer such as those mentioned above. This is a general term for compounds that have this amino group, and examples of compounds that have this amino group include ammonia, urea, acrylonitrile, aminoacetanilide, aminoanthraquinone, aminoethanol, aminoethylene, aminoethylbenzene,
Examples include aminocresol, aminophenol, caprolactam, etc., while compounds having carboxylic acid groups include butyric acid, caproic acid, lauric acid, palmitic acid, stearic acid, crotonic acid,
Examples include oleic acid, linolenic acid, benzoic acid, naphthoric acid, malonic acid, 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-aminoacrylic acid, α-aminoadipic acid, aminomaloic acid, acetylphenylalanine, acetylmethionine, and ester compounds thereof, as well as esters of acetylamino acid and pentaerythritol or dipentaerythritol. compounds, ester compounds of 2-pyrrolidone-5-carboxylic acid and pentaerythritol, and the like. Among these aminocarboxylic acids, β-aminocrotonic acid ester has the general formula

[Chemical formula] However, n: 1-6 R: residue of mono- to hexavalent alcohol. Further, specific examples of R(-OH)n constituting this ester include methanol, ethanol, propanol, isopropanol, butanol, 2-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, etc. Can be mentioned.
The above esters are obtained by condensation polymerization of these alcohols and β-aminocrotonic acid. Preferred specific examples of the esters include stearyl alcohol β-aminocrotonic acid ester, 1,4
-butanediol diβ-aminocrotonic acid ester, thiodiethanol diβ-aminocrotonic acid ester, trimethylolpropane triβ-aminocrotonic acid ester, pentaerythritol tetraβ-aminocrotonic acid ester, dipentaerythritol hexaβ-aminocrotonic acid ester Examples include acid esters. In addition, hydrazide has the general formula, RCONHNH ₂ (R is an alkyl group or an aryl group)
Specific examples include acetohydrazide, butyric acid hydrazide, caproic acid hydrazide, lauric acid hydrazide, palmitic acid hydrazide,
Stearic acid hydrazide, crotonic acid hydrazide, oleic acid hydrazide, linolenic acid hydrazide, benzoic acid hydrazide, naphthoic acid hydrazide, malonic acid hydrazide, succinic acid hydrazide,
Glutamic acid hydrazide, adipic acid hydrazide, maleic acid hydrazide, phthalic acid hydrazide, etc. are used. Furthermore, examples of the epoxy compound include epoxidized animal and vegetable oils, epoxidized fatty acid esters, epoxidized alicyclic compounds, glycidyl ether or glycidyl ester compounds, and epoxidized polymer compounds. Specifically, epoxidized animal and vegetable oils include epoxidized soybean oil, epoxidized linseed oil, epoxidized safflower oil, epoxidized sunflower oil, and epoxidized cottonseed oil, and epoxidized fatty acid esters include epoxidized butyl stearate, epoxidized butyl stearate, and epoxidized fatty acid esters. epoxidized octyl stearate,
Epoxidized linseed oil fatty acid butyl etc. are used as epoxidized alicyclic compounds, epoxidized tetrahydrophthalate esters (alcohols include butanol, octanol, decanol, etc.), glycidyl ether or glycidyl ester compounds such as bisphenol A glycidyl ether, glycidyl methacrylate. Examples of the epoxidized polymer compound include epoxidized polybutadiene, epoxidized acrylonitrile-butadiene rubber, and the like. Examples of organic phosphorous esters include triphenyl phosphite and tris(p-phenyl phenyl).
Triaryl phosphorites such as phosphorite, tris(o-cyclohexylphenyl) phosphorite, tris(p-nonylphenyl) phosphorite, phenyl-p-nonylphenyl phosphorite, tris(2,4 di-t-butylphenyl) phosphorite, monoalkyl diphite Alkyl/aryl phosphite such as enyl phosphite and dialkylmonophenyl phosphite, oligophosphite oligomerized with glycol, polyol, bisphenol, trisphenol, etc., and acidophosphite such as diphel amide phosphite and dilauryl amide phosphite. Fuite etc. are used. As other nonmetallic stabilizers, phenol derivatives, polyhydric alcohols, nitrogen-containing compounds, sulfur-containing compounds, and keto compounds are used. As phenol derivatives, hindered phenol, hindered bisphenol, etc. are used, and as polyhydric alcohols, glycerin, mannitol, xylitol, trimethylolpropane, pentaerythritol, sorbitol, polyethylene glycol,
Sorbitan monolaurylate, glycerin monostearate and partially esterified products with carboxylic acids, nitrogen-containing polyhydric alcohols, sulfur-containing polyhydric alcohols, etc. are used, and as nitrogen-containing compounds, 2-
Phenyl indole, diphenylthiourea, triazine, etc. are used, sulfur-containing compounds include thiodipropionic acid ester, triazinethiol, thiol carboxylic acid anhydride, etc., and keto compounds include acetoacetic acid ester, dehydroacetic acid, β- Diketones and the like are used. These stabilizers are added in a total of 0.5 to 7.0 parts by weight per 100 parts by weight of chlorine-containing resin, and mainly stabilize the chlorine-containing resin, but these stabilizers also contain Pb.
It is characterized by the fact that it does not contain any metal elements such as or Sn. The appropriate amount of the stabilizer added to the chlorine-containing resin is as described above, but if it is less than 0.5 parts by weight, sufficient thermal stability will not be obtained;
If it exceeds 7.0 parts by weight, the thermal stability will improve accordingly, but it will be economically disadvantageous. Among these stabilizers, when aminocarboxylic acids, hydrazides, epoxy compounds, and organic phosphite aster are used alone or in combination, the amount is 0.5 to 5 parts by weight, preferably 1.0 parts by weight.
and 3.0 parts by weight, and also phenol derivatives,
When polyhydric alcohols, nitrogen-containing compounds, sulfur-containing compounds, and keto compounds are used alone or in combination with the above stabilizers, they are used in an amount of 2 to 7 parts by weight, preferably 3 to 5 parts by weight. These stabilizers can be used alone or in combination, but when used in combination, a combination of an aminocarboxylic acid and an epoxy compound, a combination of an aminocarboxylic acid, an epoxy compound and an organic phosphite, a hydrazide, an epoxy compound and an organic phosphite are used. Combinations of phosphoric acid esters, and combinations of epoxy compounds and organic phosphorous esters are preferably employed. In addition, the chlorine-containing resin mentioned above may contain higher fatty acids such as stearic acid to improve release from the mold during molding and to improve the finished appearance of the molded product (especially luster, luster, etc.). , an acrylic lubricant that does not lower the softening temperature is used. The above-mentioned stabilizers contribute as main stabilizers to the thermal stability of chlorine-containing resins, and lubricants provide lubricity to resins, but other metal-free additives,
For example, antioxidants such as amine, phenol, sulfur, and phosphorus, light stabilizers such as ultraviolet absorbers, plasticizers such as phthalate esters, aromatic carboxylic acid esters, aliphatic dibasic esters, and transparent of
Reinforcing agents such as ABS/MBS, pigments, auxiliary agents, antifungal agents,
Adding additives such as foaming agents to help stabilize chlorine-containing resins, improve processability, improve weather resistance, improve mechanical properties, or plasticize and foam. I can do it. Furthermore, the molded product of the present invention is supplied as a transparent, translucent, or opaque molded product depending on its use, and the molded product may be semitransparent or opaque (hereinafter collectively referred to as semitransparent). The chlorine-containing resin of the base layer 1 is coated with various non-metallic colorants, such as organic pigments, acrylic modification modifiers, ABS resin, MBS resin, AAS resin, AES resin, ACS resin, AS resin, EVA resin, and foam. Base resin, carbon black, etc. are added as appropriate. Additionally, the coating layer 2 is formed by applying or laminating an antistatic or conductive material. As an antistatic material, an appropriate amount of an antistatic or conductive filler such as an organic compound having antistatic performance, conductive carbon, graphite, carbon fiber, metal fiber, or metal powder is added to increase the electrical resistivity to 10 ¹¹ to 10. ³ Ω-cm
In particular, organic compounds containing no metal are preferably employed. This organic compound may be a graft copolymer obtained by graft polymerizing a vinyl monomer or a vinylidene monomer to a rubber backbone polymer having a low specific volume resistivity, or An antistatic resin composition obtained by dissolving a thermoplastic resin that is compatible with the antistatic resin composition is used. The rubber backbone polymer here is 4 to 500
Monomers with alkylene oxide groups 10~
It is a copolymer consisting of 50% by weight and 50 to 90% by weight of one or more monomers selected from conjugated dienes and acrylic esters, and this rubber backbone polymer phase is incorporated into the technical polymer phase during processing. They are dispersed in a bridge state, and have an antistatic effect as the charge mainly diffuses and attenuates through the rubber core polymer phase.Moreover, the polyalkylene oxide group has a chemical effect on the rubber core polymer. Since the antistatic property is bonded to the antistatic property of the antistatic property, it does not deteriorate even after severe washing with water, and thus maintains a permanent antistatic effect. The above graft copolymer can be used alone, but in order to improve the lamination properties with the base layer 1 and the surface hardness of the coating layer 2, it may be used in combination with a thermoplastic resin that is compatible with the graft copolymer. preferable. The thermoplastic resin is not particularly limited as long as it is compatible with the graft copolymer, but includes PVC resin, polyvinylidene chloride resin, nitrile resin, and surface hardness resin that has good lamination properties with respect to the chlorine-containing resin of the base layer 1. Polymethyl methacrylate resin and its copolymer, acrylic-styrene-butadiene resin, etc., which are excellent in
It is most preferably adopted because it does not contain metal, has good lamination properties, and has excellent chemical resistance.
A chlorine-containing resin molded product containing no metal can be obtained. The appropriate blending ratio of the thermoplastic resin and the graft copolymer is 90 to 1 part by weight of the thermoplastic resin to 10 to 99 parts by weight of the graft copolymer. It is important to blend the rubber backbone polymer in an amount of 5 to 80% by weight, preferably 8 to 60% by weight, based on the total amount of the rubber base polymer. Further, a conductive material can be used as the coating layer 2, and examples of the conductive material include PVC resin, polyvinylidene chloride resin, nitrile resin, polymethyl methacrylate resin and its copolymer, acrylic-styrene-butadiene resin, etc. The synthetic resin is blended with conductive fillers such as conductive carbon, graphite, carbon fiber, metal fiber, and metal powder, either alone or in appropriate combinations, to improve the electrical resistivity.
10 ² Ω-cm or less, and a chlorine-containing resin stabilized with a non-metallic stabilizer as described above is used as a synthetic resin to be blended with conductive carbon, graphite, and carbon fiber. When used, a molded product in which both the base layer portion 1 and the coating layer 2 do not contain metal can be obtained, and is particularly preferably employed. The materials prepared for the base layer portion 1 and the covering layer 2 as described above are laminated and integrated during molding and molded into a desired shape. Here, the desired shape is a plate-like body as shown in FIG. 1, or a box-shaped case as shown in FIG.
It also includes all shapes of members used for the above purpose, such as angle and block shapes.
Although FIGS. 1 and 2 show an example in which the covering layer 2 is integrally laminated on only one side of the base layer portion 1, it is not excluded that the covering layer 2 may be formed on both sides.
In this case, although it depends on the application, at least the side that comes into contact with the chemical solution or food, etc. has the thermoplastic resin used in the antistatic material and the stable non-metallic resin used as the blended resin of the conductive material. It is necessary to use a chlorine-containing resin stabilized with an agent and to use a non-metallic filler as an antistatic or conductive filler. The molding method is to fuse and integrate sheets or plate-shaped bodies of the above two types of materials using a heat press or calendar roll, or to extrude both materials at the same time and integrate them as they solidify. Furthermore, conventional synthetic resin lamination techniques such as an injection molding method in which the two are injected into the same mold from separate injection nozzles to integrate the two can be used as is. (Function) The molded product of the present invention obtained as described above has a temperature of 150-200°C of the chlorine-containing resin during molding.
If a stabilizer is not included in the resin, the H of the resin structure
and CI are liberated and dechlorinated, causing the resin to turn yellow or black. However, since the chlorine-containing resin constituting the base layer 1 of the molded product of the present invention is given thermal stability by the above-mentioned stabilizers, it will not change color even when the temperature rises during molding. The chlorine-containing resin that makes up the base layer 1 includes:
Since it does not substantially contain metal elements, when used for the above-mentioned purpose, if it is used in such a way that the base layer 1 comes into contact with chemical solutions or foods, harmful metals such as Pb and Sn will be removed from these chemical solutions or foods. Elements do not elute, and there are no concerns about various adverse effects caused by this. The expression "substantially free of metal" is used here because it is unintentional but unavoidable when manufacturing chlorine-containing resins, stabilizers, lubricants, colorants, etc., and during the above molding. This is because trace amounts of metal may be mixed in within a certain range, so it cannot be said that there is no metal in the final molded product. In addition, since the coating layer 2 is made of an antistatic or conductive material, it has an antistatic function, and there is no concern that it will attract dirt or dust in the atmosphere. Together, they are extremely suitable for applications such as those related to semiconductors. In particular, when the above-mentioned graft copolymer is used as an antistatic material, the antistatic function will not be permanently impaired even when used under harsh conditions such as washing with water. When used in combination, the rubber backbone polymer becomes embedded in the thermoplastic resin, and the antistatic function becomes more permanent. (Example) Next, an example will be described. (i) Preparation of test piece (-1) A chlorine-containing resin for the base layer was prepared according to the formulation shown in Table 1.

[Table] However, the numbers in the table represent parts by weight.
(-2) Materials for the coating layer were prepared according to the formulations shown in Table 2.

[Table] The blended resins of (-3) and (-1) were made into a 0.5 mm sheet using a calendar roll (160℃ x 5 minutes), and 18 sheets were stacked on top of each other, and the material of (-2) was placed on both sides. 0.5mm thick sheets obtained by calender roll treatment (160℃ x 5 minutes) were stacked one by one and heated and pressure molded using a press (160℃ x 5 minutes) to form a 10mm thickness test. pieces, and each of these (−
Examples (1-A), (1-B), (1-C) to Example (7-A) correspond to (A), (B), and (C) of 1) to (-2). , (7-b), and (7-c). (-4), the blended resin in Table 3 was made into a 0.5 mm sheet using a calendar roll (160°C x 5 minutes), 20 of these sheets were stacked, and this was heated and heated in the same way as in (-3). A test piece with a thickness of 10 mm was obtained by pressure molding, and this was used as Comparative Example (1).

[Table] (ii) Measurement of thermal stability The test pieces obtained by heat molding in (-3) and (-4) above were observed for changes in hue on their outer surfaces. The results are shown in Table 4.

【table】

[Table] As understood from this Table 4, Examples (1-
a) (1-b) (2-a) (2-b) (3-c) (3
In -c) and (5-i) to (7-b), no change in hue was observed due to hot pressure molding, and they showed the same thermal stability as Comparative Example (1). Examples (3-i), (3-b), (4-i), and (4-b) were slightly inferior in thermal stability to comparative example (1), but the change was not significant enough to cause a practical problem. In addition, all test pieces had excellent moldability. (iii) Measurement of general physical properties Table 5 shows the results of measuring the general physical properties of the test pieces of Examples (6-a), (6-b), and (6-c) and Comparative Example (1). However, for (6-c), only the surface resistivity was measured.

[Table] In this Table 5, "actual" and "ratio" represent Examples and Comparative Examples, respectively. As can be seen from Table 5 above, all of the Examples showed substantially the same physical property values as Comparative Example (1), and it can be seen that they can be used in the same way as conventional PVC boards.
In addition, the surface resistivities of Examples (6-a) and (6-b) are all 10 ¹¹ Ωcm, and have an antistatic function to the extent that they do not attract dirt or dust. Furthermore, the surface resistivity of Example (6-c) was 10 ² Ω-cm, indicating that it had a conductive function. (v) Dissolution test Above examples (6-a), (6-b), (6-c),
Samples of Comparative Example (1) and PVC resin containing Pb as the main stabilizer were separately prepared in the same manner as Comparative Example (1) [referred to as Comparative Example (2)], and immersed in pure water based on JISK6743 for elution. trace metals were analyzed using atomic absorption spectroscopy and
Analyzed by ICP emission spectrometry. The results are shown in Table 6.

[Table] As understood from this Table 6, Example (6-
No metal was eluted from a), (6-b), and (6-c). In addition, Sn or Pb contained in the stabilizer was eluted from Comparative Examples (1) and (2). Further, the surface resistivity of the samples of Examples (1-a) and (1-b) which had been subjected to the elution test was measured again, but there was no change. Incidentally, when PVC resins using stabilizers other than those in the above examples were also tested in the same manner as above, substantially the same results were obtained. (Effect of the invention) As mentioned above, the chlorine-containing resin molded product of the present invention has
It consists of a base layer of chlorine-containing resin that does not contain metal compounds such as Pb or Sn as a stabilizer, and an antistatic or conductive coating layer that is integrally laminated on at least one side of the base layer. medical care,
When used for pharmaceutical, food, etc.-related equipment, if the base layer or metal-free coating layer is used on the side that comes into contact with acid or pure water, that is, on the side that is treated with acid or pure water, these treatments can be avoided. There is no concern that metal elements will be leached into liquids, etc. Furthermore, since the inherent properties of chlorine-containing resins, such as being inexpensive and strong, as well as having excellent chemical resistance and secondary processability, are maintained, it is extremely suitable for use in equipment related to the above-mentioned applications. Furthermore, the antistatic function of the coating layer prevents the adsorption of dirt and dust in the atmosphere, further increasing suitability for the above-mentioned uses. The chlorine-containing resin molded product of the present invention having such excellent performance is extremely useful.

[Brief explanation of the drawing]

FIG. 1 is a partially cutaway vertical sectional view showing an embodiment of the molded product of the present invention, and FIG. 2 is a partially enlarged perspective view showing an example of its application. (Explanation of symbols), 1...base layer part, 2...surface layer part.

Claims (1)

[Scope of Claims] 1. At least the base layer portion of a chlorine-containing resin stabilized with one or more non-metallic stabilizers such as aminocarboxylic acids, hydrazides, epoxy compounds, and organic phosphite esters. A chlorine-containing resin molded product having an antistatic or conductive coating layer integrally laminated on one side and molded into a desired shape as a whole. 2. The above-mentioned antistatic coating layer is made of a graft copolymer obtained by graft polymerizing a vinyl monomer or a vinylidene monomer to a rubber base polymer having a small specific volume resistivity. Molded products described in scope 1. 3. The antistatic coating layer comprises an antistatic resin composition comprising the graft copolymer and a thermoplastic resin compatible with the copolymer. Molded product described in Section 2. 4. The above-mentioned thermoplastic resin is a chlorine-containing resin stabilized with one or more non-metallic stabilizers such as aminocarboxylic acids, hydrazides, epoxy compounds, and organic phosphites. Molded products described in scope 3. 5. The molded product according to claim 1, wherein the conductive coating layer is made of a synthetic resin blended with a conductive filler.