JPS6020949A - Vinyl chloride resin composition having excellent blocking resistance and agricultural vinyl sheet - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent blocking resistance without detriment to transparency, weather resistance and fish eye, containing a specified partially crosslinked vinyl chloride resin. CONSTITUTION:Vinyl chloride or a monomer mixture mainly composed of vinyl chloride and a bisphenol-modified di(meth)acrylate of formula I , II or III (wherein R1 is H, -CH3; R2 is H, a 1-4C alkyl; R3, R4 are each H, -CH3, -CH2CH3; -CH2CH2COOH; i, j are each 1-5; m, n are each 1-10; l is 0 or 1-20; X is Br, Cl, H) are copolymerized to obtain a partially crosslinked vinyl chloride resin having a gel fraction of 0.02-1.0%. A thermal stabilizer, an ultraviolet light absorber, a lubricant, etc. are blended with said vinyl chloride resin. The resulting compsn. is molded into a sheet to obtain an agricultural vinyl sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention prevents damage to the transparency, weather resistance, and fish eyes (hereinafter referred to as F and E) of vinyl chloride resin! l:
t, t < The present invention relates to a vinyl chloride resin composition and an agricultural vinyl sheet that can form molded products such as films and sheets with extremely improved bronking resistance. More specifically, it is a resin composition obtained by mixing a vinyl chloride resin for adjustment containing 0.02 to 1.0% (by weight, same hereinafter) of gel content, the ratio of gel content to the total amount of resin. Transparency, weather resistance, F of 0.02 to 1.0%
The present invention relates to a vine vinyl chloride resin composition and an agricultural vinyl sheet that provide molded products with extremely improved blocking resistance without impairing the properties of .

Vinyl chloride resin has various excellent properties and is used in a wide range of fields. Among these, it is used for molded products such as various transparent films and sheets in the packaging field, stationery, agriculture field, miscellaneous goods field, etc. When manufacturing hard, semi-hard, or soft transparent sheets or films, they are usually stored in rolls or in sheet-shaped caps. However, in the next step, when the film or sheet is peeled off from such a roll or sheet and used, the films may come together,
The sheets block each other and cannot be easily removed. This has caused major problems such as a significant drop in work efficiency.

In this industry, various attempts have been made to solve this problem, but so far no simple and effective method has been found, and each shrine and temple is making efforts to solve it using its own method. is the current situation. For example, there are methods to prevent blocking by applying organic substances such as starch to the entire surface of the film or sheet, and methods to knead imitation powder of inorganic substances such as calcium carbonate. This is a blocking prevention method.

However, in these methods, the process becomes complicated and workability deteriorates, and in order to obtain an effective anti-blocking effect, it is necessary to add a large amount of the powder. The above-mentioned method gave unsatisfactory results due to the loss of transparency. The same is true for molded products other than films and sheets; if they are stored in piles, blocking occurs, and when they are removed, the appearance of the peeled surface is impaired.

Furthermore, the use of crosslinked vinyl chloride resins has attracted attention in recent years, and various compositions containing partially crosslinked vinyl chloride resins have been studied. For example, a proposal was made to obtain a partially crosslinked vinyl chloride resin using a crosslinking agent such as diallyl phthalate, diallyl maleate, polyethylene glycol diacrylate, or polyethylene dimethacrylate, and to utilize a composition using this. 8 (Specification No. 1554,
J, such as Japanese Patent Application Laid-Open No. 56-5845. However, molded products obtained from compositions using conventional partially crosslinked vinyl chloride resins have extremely poor weather resistance and cannot be used for applications such as agricultural vinyl sheets.

The present inventors have discovered that the transparency, weather resistance, and IP of vinyl chloride resin, ]11. As a result of intensive research aimed at improving blocking resistance without impairing the
A resin composition containing a partially crosslinked vinyl chloride resin obtained by copolymerizing vinyl chloride or a monomer mixture A containing vinyl chloride as a main component and a monomer mixture B consisting of a bisphenol-modified diacrylate or a bisphenol-modified dimethacrylate, , discovered that a vinyl chloride resin composition in which the ratio of gel content in the total resin components of the composition is 0.02 to 1.0% can achieve the above object, and in completing the present invention. Ta. That is, the present invention
As a crosslinking agent, bis7 ether-modified diacrylate or bisphenol-modified dimethacrylate, especially λ and the general formula -4 alkyl group'R3''4 is H- atom, -0H3 group, -0H20H3 group, -0H20H20
Atom or group selected from 00H group, 1, jl is 1 to 5
m Sn is an integer of 1 to 10, 1 is 0 or 1 to
2o integer, X is a Br atom, a 01 atom, or a hydrogen atom) A resin composition containing a partially crosslinked vinyl chloride resin obtained by using the compound represented by The gel content contained in the product is 0.02 to 1.
0% vinyl chloride resin composition.

The seven-mer mixture A referred to herein,! :G;t means a mixture consisting of vinyl chloride or a monomer mainly composed of vinyl chloride, and monomer mixture B is a monomer obtained by adding pisphenol-modified diacrylate or bisphenol-modified dimethacrylate to monomer mixture A. means a mixture of

Hereinafter, in this specification, a value calculated by extracting with tetrahydrofuran for 22 hours using a Soxhlet extractor and calculating the dry weight of the extraction residue remaining on a 650 mesh filter will be referred to as gel fraction.

In the present invention, it is preferable to use a partially crosslinked vinyl chloride resin having a gel fraction of 0.02 to 1.0%. In addition, by blending a partially crosslinked vinyl chloride resin with a gel fraction of 1.0 to 50% and a vinyl chloride resin for gel content adjustment described below, the gel fraction is 0.02 to 1.0 with respect to the total resin amount. % is also preferably used. When partially crosslinked vinyl chloride resin is used alone, if the gel fraction is 1.0% or more, F, 1! ! , and transparency is deteriorated, which is undesirable. Further, if the F content is 0.02% or more, the anti-blocking effect will be reduced, which is not preferable.

In addition, when the gel fraction of vinyl chloride resin and resin for gel fraction adjustment becomes 50% or more, even if the gel fraction relative to the total resin amount is subsequently adjusted to 1.0% or less, F.
Or transparency deteriorates, which is undesirable. Furthermore, if the gel fraction is less than 0.02% based on the total amount of resin, the anti-blocking effect will be reduced, which is not preferable.

The production of the partially cross-linked IfJi vinyl chloride resin used in the present invention is disclosed in Japanese Patent Application No. 56-82862.

In the present invention, when a partially crosslinked vinyl chloride resin having a gel fraction of 1.0 to 50% is used, the vinyl chloride resin for gel content adjustment used to adjust the gel fraction refers to vinyl chloride monomer alone. This refers to a polymer that does not contain a gel component and is obtained by polymerizing a monomer mixture mainly consisting of vinyl chloride monomer or vinyl chloride monomer. For example, polyvinyl chloride, 4
Vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-problene copolymer, copolymer of vinyl chloride and acrylic acid or its ester, copolymer of vinyl chloride and maleic acid or its ester polymer,
Examples include copolymers of vinyl chloride and fumaric acid or its esters.

The vinyl chloride resin composition of the present invention is used to produce transparent films, sheets, plates, and other molded products for outdoor use.

In particular, a resin composition containing a partially crosslinked vinyl chloride resin obtained by copolymerizing vinyl chloride or a monomer mixture A containing vinyl chloride as a main component and a monomer mixture B consisting of a bisphenol-modified diacrylate or a bisphenol-modified dimethacrylate. and the proportion of gel contained in the total resin components of the composition is 0.02 to 1.0%.
It has been discovered that an agricultural vinyl sheet molded from a vinyl chloride resin composition is useful.

In order to obtain such transparent molded products, heat stabilizers, ultraviolet absorbers, lubricants, antioxidants, processing aids, fillers, plasticizers, or other modifications can be added to the resin composition of the present invention. Add agents and other ingredients as necessary and process. The molding process may be carried out by a known method for molding ordinary vinyl chloride/l/resin.

Since the purpose of the present invention is to coat transparent molded products such as transparent films or sheets, the use of lead-based stabilizers, fillers, pigments, modifiers, or processing aids should be kept to a small amount. is preferred. Therefore, particularly preferred thermal stabilizers include O'a-Ba stabilizers and Qa-I stabilizers.
There are Zn-based stabilizers, Sn-based stabilizers, Ba-Zn-based stabilizers, and the like. Particularly preferred lubricants include stearic acid, polyethylene wax, and montan acid wax. Furthermore, the plasticizer is used for the purpose of softening or improving processability, and conventionally known plasticizers can be freely used as required. Examples include phthalate ester plasticizers, arabic ester plasticizers, sebacate ester plasticizers, phosphate ester plasticizers, trimellitic ester plasticizers, and polyester plasticizers. Moreover, you may use 2 or more types of them together.

Hereinafter, embodiments of the present invention will be explained in more detail with reference to examples, but the present invention is limited only to these examples and is not numbered. Manufacturing) 5
01 stainless steel polymerization machine, 200 parts of ion-exchanged water (parts by weight, same hereinafter), 2 g of partially saponified polyvinyl acetate, 0.0 g of di-2-ethylhexyloxydicarbonate.
The resulting monomer mixture B was polymerized at 55°O for 15 hours, and the slurry was dehydrated and dried to obtain a white powder.

The gel fraction of the obtained resin was 28%, and the degree of soluble polymerization was 1020. Reference Example 2 (Production of partially crosslinked vinyl chloride resin (2)) Tetraethylene glycol diacrylate was prepared in the same manner as white. I got the powder. The resin had a gel fraction of 0.80% and a soluble polymerization degree of 1010.

Reference Example 3 (Manufacture of partially crosslinked vinyl chloride resin (3)) The procedure was exactly the same as Reference Example 2 except that 0.3 parts of tetraethylene glycol diacrylate was changed to 5.0 parts of polyoxyethylated bisphenol A diacrylate H3. A white powder was obtained. The resin had a gel fraction of 52% and a soluble polymerization degree of 1010.

Reference Example 4 (Production of partially crosslinked vinyl chloride resin (4)) Polyoxyethylated bisphenol A diacrylate 5
．． A white powder was obtained in exactly the same manner as in Reference Example 3 except that 0 part was changed to 0.1 part. The gel fraction of the resin is 0601%
The soluble polymerization degree was 1090.

Reference Example 5 (Production of partially crosslinked vinyl chloride resin (5)) Polyoxyethylated bisphenol A diacrylate 0.
A white powder was obtained in exactly the same manner as in Reference Example 4 except that 1 part was changed to 0.6 part. The gel fraction of the resin was 0.81%, and the soluble polymerization degree was 1080.

Reference Example 6 (Production of partially crosslinked vinyl chloride resin (6)) Polyoxyethylenated bisphenol A diacrylate 0.
A white powder was obtained in exactly the same manner as in Reference Example 5 except that 6 parts was changed to 1.0 parts. The resin had a gel fraction of 18.0% and a soluble polymerization degree of 1080.

Examples 1 to 4 and Comparative Examples 1 to 7 Tin laurate stabilizer (Oa-Zn stabilizer), stearic acid, dioctyl phthalate (DOP) and epoxidized soybean oil were added to the resin components shown in Table 1, respectively. 1. Blend the amounts shown in Table 1, put it into an 8-inch roll heated to 160°C, knead for 8 minutes, and make a 0.2 m
A film with a thickness of m was produced.

In Table 1, Kanevinyl S-1001 (trade name) is polyvinyl chloride with a degree of polymerization of 1050 manufactured by Kanebuchi Chemical Industry ■, and Kanevinyl M-1008 (trade name) is a polyvinyl chloride with a degree of polymerization of 800 manufactured by Kanebuchi Chemical Industry ■. It is a vinyl chloride-vinyl acetate copolymer.

Various physical properties of the 11 types of films thus obtained were measured and evaluated as follows. 'Anti-blocking property: Two films of 1 [] cm x 10 cm and 0.2 mm thick were stacked, a load of 10 nm was applied to this, and the two films were left at room temperature for 24 hours. Then, the ease of peeling of the two films was measured. Evaluated qualitatively, it is extremely easy to peel off (
◎), easy to peel off (○), slightly hard to peel off (Δ), and hard to peel off (x). Transparency: 1
60 sheets of 0 part m x 10 cm, 0.2 mm thick were stacked together and heat pressed under the conditions of 17 x 10 minutes x 50/cm2 to produce a 5 mm thick plate. The weight ratio (4) was measured for each. F.1. :
Prepare 5 pieces of 10cm x 10cm thick 0.2rIn film, measure the number of spots present in each film, and calculate the average value of the 5 pieces.III! iI/10cm
Displayed in units of x10 cm. Weather resistance = 10cm
10cm, thickness 0.21! II! The elongation rate ((6)) of each of the films of I was deteriorated for 200 hours using a sunshine weatherometer and measured. The elongation rate was measured in accordance with rxsK-6724.

Further, under the sunshine condition, the temperature was 66°C and the temperature was lowered every 2 hours for 18 minutes. In addition, the front and back sides of the test samples were changed every 20 hours. The measurement results are shown in Table 1. In Table 1, the gel fraction in all resin components is a value calculated from the gel fraction of the partially crosslinked vinyl chloride resin used.

As can be seen from the results in Table 1, Comparative Examples 1 and 2 had no anti-blocking properties at all, and Comparative Examples 6 and 5 using partially crosslinked vinyl chloride resins (1) and (2), respectively, Weather resistance is greatly reduced,
If the gel fraction is set to 0.01% as in Comparative Example 4, the anti-blocking properties will not be good, and if a partially crosslinked vinyl chloride resin (3) with a gel fraction of 52% is used as in Comparative Example 6. Even if adjusted to 0.052%, F! If, as in Comparative Example 7, the amount of partially crosslinked vinyl chloride resin (6) is increased to make the gel fraction in the total fat-saving content 6.0%, the transparency will decrease. I also don't like it.

On the other hand, in Examples 1.2.6 and 4, the transparency, y, and E were equivalent to those of Stray HPVA alone, and the weather resistance and anti-blocking properties were equivalent or better. It can be seen that this shows that

Claims (1)

[Claims] 1 Contains a partially crosslinked vinyl chloride resin obtained by copolymerizing vinyl chloride or a monomer mixture A containing vinyl chloride as a main component and a monomer mixture B consisting of a bisphenol-modified diacrylate or a bisphenol-modified dimethacrylate. A resin composition having a gel content of 0.02 to 1.0% by weight in the total resin components of the composition.
A vinyl chloride resin composition. 2 Bisphenol-modified diacrylate or bisphenol-modified dimethacrylate has the general formula (I): (wherein, R is a H atom or a 10H3 group, R2 is a H atom or an alkyl group having 1 to 4 carbon atoms, R3, R. H atom, -0H3 group, -0H20H3 group, -0H20
Atoms or groups selected from H2000 groups, ll14n
is an integer from 1 to 10, X is a Br atom, a 01 atom or)■
The vinyl chloride resin composition according to claim 1, which is a compound represented by (atom). 6 Compounds in which bisphenol-modified diacrylate or bisphenol-modified dimethacrylate is represented by the general formula (■): (wherein R, R3, R4, and X are the same as above, and 1 is 0 or an integer from 1 to 20) The vinyl chloride resin composition according to claim 1. 4 Bisphenol-modified diacrylate or bisphenol-modified dimethacrylate General formula (l[): (wherein, R, R2, R3, R4, 1, and X are the same as above, and 1 and j are 1 to 5. The vinyl chloride resin composition according to claim 1, which is a compound represented by: 5. A resin composition containing a partially crosslinked vinyl chloride resin obtained by copolymerizing vinyl chloride or a monomer mixture B consisting of a monomer a containing vinyl chloride as a main component and a monomer mixture B consisting of a compound t" and a bisphenol-modified diacrylate or a bisphenol-modified dimethacrylate. A vinyl sheet for industrial use, which is molded from a vinyl chloride resin composition in which the proportion of gel content in the total resin components of the composition is 0.02 to 1.0% by weight.