JPS63125542A - Molding - Google Patents

Abstract

PURPOSE:To obtain a molding of excellent yellowing resistance, comprising a polyolefin resin composition containing a specified reaction product and a phenolic stabilizer. CONSTITUTION:An at least trihydric polyalcohol mono- or diester of formula I [wherein R2 is a 11-22C (un)saturated alkyl, and R3 is H or a group of formula II] is reacted with boric acid (anhydride) at a molar tatio of 1:0.2-1 at 95-200 deg.C to obtain a reaction product of formula III or IV. A polyolefin resin composition formed by mixing a polyolefin resin (e.g., PE) with 0.01-5wt% phenolic stabilizer [e.g., n-octadecyl-3-(4'-hydroxy-3,5-di-t-butylphenyl)propionate] and 0.01-5wt% said reaction product is molded to obtain a molding used in applications where at is in contact with alkali metal ions.

Description

[Detailed Description of the Invention] The present invention relates to molded products such as containers, bags, and bags, and more specifically, it is intended to prevent four colors and problems such as yellowing over time. lζ, encased in polyolefin molded products used in applications that come into contact with alkali metal ions.

The polyolefin resin of Polyl Robylene Kasa has excellent moldability and chemical reaction resistance, so it can be used for various mulberry products. It is also widely used as a packaging material for chemical products.

However, in conventional polyolenoin packaging, depending on the type of the packaged item, the packaging material may gradually become discolored when stored for a long period of time.

For example, when the encapsulated product contains salts such as physiological saline, common salt, soap, etc., conventional polyolefin packaging materials may be used for long periods of time. There was a problem that it yellowed over time.

The present inventors believe that the yellowing of polyolefin packaging materials over time when storing articles containing alkali metal ions, such as sodium sulfur packaging bags, is due to the following:
I found out that the cause was that the phenolic stabilizer contained in polyolefin packaging (=r) is mixed with alkali metal ions, and then converted to quinones, and conducted a thorough study. As a result, it was found that 1'1''1 caused by such imefyl alcohol-based stabilizers was found to have a trivalent or higher valency in the polyolefin fruit tree resin.
I! The release can be effectively suppressed by adding an anti-one-core product of -[) or diester of alcohol and monotonic acid.
After discovering that it is possible to do this, we completed the present invention1.

Purpose of the Invention The present invention is an attempt to solve the above-mentioned problems associated with the prior art.
The object of the present invention is to provide a molded article made of a polyolefin-based (or fat) composition containing a phenol-based stabilizer.

(1) Outline of the present invention The molded article according to the present invention is made from a polyolefin resin composition containing a phenolic stabilizer and is used for applications in which it comes into contact with alkali metal ions. J
3, and the composition is further 3! 1lfi more than 7 songs) 7 Lecole's anti-1, self, (1 composition;'dt 15
i%.

DETAILED DESCRIPTION OF THE INVENTION Below, a molded article made of a polyolefin resin composition containing a phenolic stabilizer according to the present invention will be specifically described, including examples.

As the polyolefin resin as the main material i'il,
Highly crystalline components of conventionally known polyethylene, polypropylene, 4-methyltopentene homopolymers or copolymers, ethylene α-Δrefine J1 crystal trade or low-crystalline polymers, propylene 1-Li Amorphous or amorphous such as amorphous T1 or low crystal freight car combination. i℃crystal°l! Resins such as single components or block copolymers or blends thereof may be used.

Phenolic stabilizers contained in such polyolefin resins have been widely used as antioxidants in polyolefin resins. -Hydroxyphenyl)propionate comethane, rr-)rphtadecyl-3-(4°-hydroxy-3,5-di[-absifinyl)propionate, 2,6-sheet blue cresol, 2,4. 0-1~Lis(3',5-di-l-
Butyl-4゛-hydroxybenzylthi;, l)-1.3
．． 5-1 ~ riazine, 2.2-meblenebis(4-methyl-6-t-butylphenol), 4,4°-meblenebis(2.6-di-t-butylphenol), 2,
2°-medylenehis3e-(1-methylcyclohexyl)P-cresol], bis13,5-bis(4-hydroxy-3-dobupurphenyl)butyric acido]glycol ester, =1, 4°-l tylidene bis(6
-1-butyl-111-cresol), 1,1.3-
Tris(2-methyl-11-hydro-1-cy-5-[-butylphenyl)butane, 1'+J+5-tris(2.6
-Lame blue 3-hydroxy-4-(-butylhensyl)isocyanurate, 1, 3. 5- Tris (3.
5-di[-butyl-4-human(koxyhenzyl)-2
,,L6- 1-lame-1-ruben, 1,3.5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanu 1-,1,3,! rl” squirrel (3,
5-G [-DiBlue 4-Human LJ =% dinonyl)
Propionyl quaternary] isocyanurate, 2-7
1 qubru-f71-, 1,G-ci (4-human ul-ci 3.5-gi t-'7 bru)pheno-1-ci 1.3.
5-1" riazine, 4,4"-thiazine (6-t-ablu n1-cresol), etc. are used.

The ratio 1ω of such a phenolic stabilizer in a polyolefin resin is usually 0.01.about.5JΦ41%.

If the molded product is made of polyolefin resin that does not contain phenolic stabilizers, the problem of yellowing will not occur even if it is used in applications that come into contact with alkali metal ions, but phenolic stabilizers should not be added. The polyolefin resin composition has poor heat resistance and I'i (inferior) when producing molded products from this resin composition by QJ molding. Q) A problem arises. Therefore, the present invention includes +1: (J, phenolic stabilizer is included, and l: polyolefin type).
The fact that the 1-fat composition can be used as a molded article is surprising.

According to the 111 study of Hon. (The main cause of the yellow ☆ phenomenon observed in the J3 case used in this study is determined as follows.

1J (Nanel), Puppy 11, Blank 4i Yellow ☆Currently, polyolefin type 1 or 1 containing phenol type 11
Molded products made from fat and compounds containing alkaline total ions and ions! The second example is physiological saline, which contains alkali metals (on or in contact for a long time), due to phenolic stabilizers or Iy2 elements in the air: 1. Compound lI: Which yellow substance is exposed to acid, which makes it think that it is a cow and a lion.
It is said that phosphorus-based stabilizers are effective in suppressing the phenomenon of residual particles in polyolefin resin (for example,
(Public cable No. 129033/1983). However, this phenomenon is different from the known yellowing phenomenon that the present invention aims to solve.

According to the present invention, J5 prevents or suppresses excessive yellowing when the polyolefin resin containing the phenolic stabilizer as described above comes into contact with alkali metal ions. Glycerinya) Pentaerythri 1~-ru or Tsuru and 1・-ru etc. 31+TIi or more 1i11
The method is characterized in that a reaction product of a mono- or diester of alcohol and boric acid is added to a polyolefin resin composition. An example of such a reaction product is fatty acid Shichinoguri L! There are reaction products of boric acid and di- or diglycerides or mixtures thereof.

Fatty acid/E diglyceride or diglyleride is represented by the following general formula (more specifically, stearic acid monoglyceride, lauric acid monoglyceride, myristic acid diglyceride, palmitic acid monoglyceride, l<henic acid heptanoglyceride, stearic acid diglyceride, lauric acid diglyceride) , myristate diglyceride, palimitin diglyceride, or a mixture thereof.

Examples of the boric acid include known commercially available products such as boric acid and boric anhydride.

In the lifting platform for reacting fatty acid glyceride and boric acid, the ratio is preferably fatty acid glyceride diboric acid-1=0.2 to 1, and the reaction temperature is preferably 95 to 200'C. The reaction product is easily converted to 17 by esterification under these steps.

The structure of the reaction product produced in 17 is said to be shown by et al.8, but it has not yet been determined.

Of course, in addition to the above, polyhydric alcohols other than glycerin are used in Honzasoake! It seems that the R2 part of Koshinoya was substituted with polyoxyethylene (1 Shinode(bJ:i).

In this way, the amount of soil sprue added to the polyolenoin system (4+ fat is about 0.01 to 5% by weight, and furthermore, about 0.05 to 2% by weight of Q-Hoj and 43L).

In addition to the components listed in 1- above, the molded product tcJ)i according to the present invention may contain ordinary polyolefins such as other antioxidants, ultraviolet absorbers, lubricants, antistatic agents, fillers, etc. Ingredients added to! :9 is included.

The specific shapes of the molded products according to the present invention include saline U, water bottles, saline packaging bags, stone counter containers, and parts that come into contact with sweat, such as the inner lining of a helmet. Examples include the parts used.

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Examples Main + 0-octadecyl-3-(4°-
Polypropylene containing 0.05 sD♀% of hydro21-3,5-di-t-butyl)1-propionate (polypropylene prepared by adding the additives shown in Table 1 below)
Samples were prepared from the zero pyrene oil composition, and a yellowing test was conducted on each sample.

(Test equipment and test method) Cylindrical flat bottom separable flask with a capacity of 1.0 (100 ah
300 tnll of physiological saline (0
, 9%\a (:, I) (to a depth of about 40#l#1), each sample was made into a press sheet of 65 x 65 x 2 mm, and about half of the press sheet was immersed in the liquid.
In addition, the flask was placed in the lLj::ia Ifw without contacting each other. 80°C1
Can I just keep it for one week? , L,, /: Nora,
The yellowing state of each sample was checked.

(Evaluation of yolk strength) J method) The anti-q4 spectrum of each sample using 11 spectroscopic words JjJ,
We measured the l, a, and b hani, which are the indicator systems of hunters. The evaluation of cardiac change is Δb (
This was done using i1'B. This Δb is small, indicating that yellowing development is occurring at 4'. J5 and spectroscopy were measured using LJV 365 Color Back System Model 16 manufactured by Shimadzu Corporation (monochromatic proof method-C).

The measurement results are shown in Table 1 below.

- Methane Spring 2: Sude) Norin fl'2 Calcium 13 Varnish j Tunolinic Acid IIi Nail) Ke 4: De I-Ra V S (2,4-sheet t-tilnoenyl) - 11,4'-biphenylenedismall sulfonite 5: Reaction product of fatty ribs/lx dino & digurire 1 and boric acid (No.
3! ')) -f=314 From the test results, Example '1 according to the present invention
So, 44' containing the conventional 71-nol stabilizer? It can be seen that yellowing is significantly suppressed compared to Comparison 19111-3.

Effect of the invention Song Dynasty Examples and comparative examples as above f, lLj Song Dynasty to Otsu I11'! As can be understood, the molded article used in applications that come into contact with alkali metal ions according to the present invention contains poly(11ff1) of 311+ or more in the polyA reflex + i4 resin composition.
Contains reaction products such as alcohol or diester and boric acid, so it prevents color problems such as yellowing caused by the phenolic stabilizer added to the composition. It can be effectively prevented by covering.

Claims (3)

[Claims] (1) In a molded article made of a polyolefin resin composition containing a phenolic stabilizer and used for applications in which it comes into contact with alkali metal ions, the polyolefin resin composition further includes a mono- or diester of a polyhydric alcohol having a valence of 3 or more. A molded product with excellent yellowing resistance, characterized by containing a reaction product of and boric acid. (2) The molded article according to claim 1, wherein the mono- or diester of trihydric or higher polyhydric alcohol is a fatty acid mono- or diglyceride. (3) The molded article according to claim 1 or 2, wherein the molded article is a saline bottle or a sodium chloride packaging bag.