JPS6032809A - Highly weatherable delustered agricultural sheet - Google Patents

Abstract

PURPOSE:To obtain the titled sheet by forming a resin composition with specific gel content, comprising specific partially-crosslinked polyvinyl chloride resin or its blend with vinyl chloride resin. CONSTITUTION:The objective sheet can be obtained by forming a composition with a gel content 1.0-35wt%, comprising either a partially-crosslinked vinyl chloride resin prepared by the copolymerization of a mixture consisting of (A) vinyl chloride or a monomer mixture consisting mainly of vinyl chloride and (B) a bisphenol-modified di(meth)acrylate [e.g., a compound of formula (R1 is H or CH3; R2 is H or 1-4C alkyl; R3 and R4 are each H, CH3, CH2CH3 or C2H4COOH; m and n are each 1-10; X is Br, Cl, or H)], or its blend with vinyl chloride resin. USE:For green house for the purpose of moisture condensation prevention, frost- falling shield, heat insulatin, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a matte agricultural sheet which can be obtained by using a resin composition, and particularly relates to a matte agricultural sheet with excellent il (P property). A partially crosslinked vinyl chloride resin alone or a mixed resin with a vinyl chloride resin obtained by copolymerizing a monomer mixture A consisting of a main component and a monomer mixture B consisting of a bisphenol-modified diacrylate or a bisphenol-modified dimethacrylate, which is a total resin. The ratio of gel content in the ingredients is 1.
The present invention relates to a matte agricultural sheet with excellent weather resistance formed by molding a resin composition of 0 to 35% (weight %, hereinafter the same).

In recent years, so-called matte molded products that have lost the plastic luster have become popular in vinyl chloride resin molded products in various fields, and various matte technologies have been developed. The matte technology is attracting particular attention. In other words, is it a matte technique that uses partially cross-linked vinyl chloride resin? Ij has the following advantages: (1) it does not drastically reduce mechanical properties like matte technology that uses a large amount of filler, and (2) it does not involve increased costs like matte technology that uses acrylic paint. (3) This is because it has advantages such as not requiring special equipment unlike the matting technique using embossing.

Therefore, compositions containing various partially crosslinked vinyl chloride resins have recently been studied. For example, a proposal 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 it (JP-A No. 54-8035
Specification No. 4, Japanese Patent Application Publication No. 56-5843, Japanese Patent Application Publication No. 54152054, Japanese Patent Application Publication No. 56-9202
4 specification, etc.).

However, the use of these partially cross-linked vinyl chloride resins has the disadvantage that the weather resistance of the molded products deteriorates significantly, so if we try to apply them to the production of matte agricultural sheets that are usually used outdoors, a large amount of It is necessary to use UV absorbers, heat stabilizers, anti-aging agents, etc., resulting in high costs.
There was a drawback.

In view of the current situation, the present inventors have conducted extensive research to apply partially crosslinked vinyl chloride resin to the production of ML industrial sheets. Partially crosslinked vinyl chloride resin alone or a mixed resin with vinyl chloride resin obtained by copolymerizing monomer mixture B consisting of modified diacrylate or bisphenol-modified dimethacrylate, wherein the gel content in the total resin component is 1 It was discovered that a matte agricultural sheet produced by molding a resin composition having a concentration of .

Hereinafter, in the present invention, a value calculated from the dry weight of the extraction residue remaining on a 350 mesh filter after extraction with tetrahydrofuran for 22 hours using a Soxhlet extractor will be referred to as gel fraction.

In addition, the matte agricultural sheets referred to in this specification are sheets used in vinyl greenhouses, sheets used in outdoor cultivation, etc. used for purposes such as preventing dew condensation, preventing T6 precipitation, and protecting It is something.

Further, monomer mixture A as used herein refers to vinyl chloride or a mixture of monomers containing vinyl chloride as a main component, and monomer mixture B refers to monomer mixture A in which bisphenol-modified diacrylate or bisphenol-modified diacrylate is added as a crosslinking agent. It means a mixture of monomers mixed with diacrylate.

In the present invention, the gel fraction obtained by copolymerizing vinyl chloride or monomer mixture A containing vinyl chloride as a main component and monomer mixture B consisting of bisphenol-modified diacrylate or bisphenol-modified dimethacrylate is 160 to 35%. Preferably, a partially crosslinked vinyl chloride resin is used. Alternatively, a mixed resin mixed with vinyl chloride resin may be used so that the gel fraction is 1.0 to 35%.

In the present invention, bisphenol-modified diacrylate or bisphenol-modified dimethacrylate as the crosslinking agent has general formula (I); general formula (■): (II) or general formula (2): (wherein, R is H atom or 10H3 group, R2 is H atom or alkyl group having 1 to 4 carbon atoms, R3, R, is H atom, -0H3 group, -0H20H3 group, -0H20H200
Atom or group selected from 0H group, 1 and j are integers of 1 to 5, m and n are integers of 1 to 10, l is 0 or 1 to 20
and X is an aZ atom, a Br atom, or a hydrogen atom) is preferably used.

The amount to be copolymerized with monomer mixture A is
The amount of the crosslinking agent is preferably 0.35 to 8 parts by weight per 100 parts by weight. The production of the partially crosslinked vinyl chloride resin used in the present invention is disclosed in Japanese Patent Application No. 56-82862.

Although partially crosslinked vinyl chloride resin can be used alone in the present invention, the matting agent is usually polyvinyl chloride resin, vinyl chloride-ethylene copolymer resin, vinyl chloride-propylene JH [polymer resin, vinyl chloride- Vinyl acetate copolymer resin, copolymer resin of vinyl chloride and acrylic acid or its derivatives, etc. have a gel fraction of 1.0 to 1.0 in the total resin component.
35%, heat stabilizers, lubricants, antioxidants, rubbers, ultraviolet absorbers, processing aids, pigments, plasticizers, etc. are blended as necessary and molded. Produces hard or soft matte agricultural sheets.

In the present invention, if the gel fraction in the total resin component exceeds 35%, the weather resistance will be insufficient, while if it is less than 1.0%, the matting effect will not be significant, which is not preferable.

As the heat stabilizer added when manufacturing the matte agricultural sheet of the present invention, known heat stabilizers used for vinyl chloride resins can be used.

tin-based stabilizers such as octyltin maleate,
Lead-based stabilizers such as tribasic lead sulfate, metal soaps, 0a-
Zn-based stabilizers, Ba-based stabilizers, etc. may be used alone or in combination. Further, as the lubricant, known lubricants such as polyethylene wax-based lubricants, stearic acid-based lubricants, and alcohol-based lubricants may be used alone or in combination. Further, thermoplastic resins that can be used in combination include acrylic rubber, KVA
and so on. As the plasticizer used for further softening, known plasticizers such as 7-thalic acid plasticizers such as dioctyl phthalate, polyester plasticizers, phosphate ester plasticizers, and epoxy plasticizers can be used alone. Or it can be used in combination.

Further, as the molding method used for producing the matte agricultural sheet of the present invention, conventional methods such as calendar molding and extrusion molding can be used. Moreover, the molding conditions can be the same as those for ordinary vinyl chloride resin.

Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.

Reference Examples 1 to 3 (For production of partially crosslinked vinyl chloride resins (1) to (3), 200 ml of ion-exchanged water was placed in a stainless steel polymerization vessel with an internal volume of 3,001 ml.
0 parts (parts by weight, same hereinafter), partially saponified polyvinyl acetate 0
．． 2 parts, 0.06 part of diisopropyl peroxide, 0.06 part of lauroyl peroxide, and 0.5 part of bisphenol-modified diacrylate shown in Table 1,
After degassing, 100 parts of vinyl chloride monomer was charged, and polymerization was carried out at a polymerization temperature of 680a for 15 hours. The resulting slurry was dehydrated and dried in a hot air dryer at 55°0 for 24 hours to obtain a white powder. Table 1 shows the gel fraction of the powder obtained.

Reference Examples 4 to 8 (Production of partially cross-linked vinyl chloride resins (4) to (8)) 2Ion-exchanged water, partially saponified polyvinyl acetate, diisopropyl 1.0 part of peroxide, lauroyl peroxide, and the crosslinking agent shown in Table 1 were charged, and after degassing, the in-situ vinyl monomer was charged, and polymerization was carried out at a polymerization temperature of 68° 0 for 15 hours. A white powder was obtained during the operation.

Table 1 shows the gel fraction of the powder obtained.

Reference Examples 9 to 10 (Preparation of partially crosslinked vinyl chloride resins (9) to 00) Exactly the same as Reference Examples 1 to 3 except that the crosslinking agent used in the production of partially crosslinked vinyl chloride resin (2) was changed to 8 parts. A partially crosslinked vinyl chloride resin (9) was obtained using the same method as in Reference Examples 1 to 3, except that the amount of crosslinking agent was changed to 0.3 parts, and a partially crosslinked vinyl chloride resin uO) was obtained. The gel fractions were 38% and 0.8%, respectively.

Examples 1 to 8 Compounds obtained by blending partially crosslinked vinyl chloride resins (1) to (3) and (9) in a super mixer at 130° 0 for 5 minutes based on the formulation shown in Table 2. Mix for 15 minutes with a mixing roll controlled to 16580! L. Further, the obtained sheet was gradually put into an inverted calender to obtain a calender sheet with a thickness of 0.3 mm. Various properties of the obtained calendar sheet were measured and evaluated by the methods shown below. The results are shown in Table 2, and the sheet of the present invention has excellent matte properties;
It can also be seen that the weather resistance is significantly improved.

Matting property: Visually observe the surface condition of Q, 3mm thick sheet obtained by calendar molding as shown in the above example: ◎ Very good, ○ Good, △ Slightly glossy and × Evaluation was made on a four-level scale including gloss.

Weather resistance: The same sheet as above was deteriorated for 200 hours using a sunshine weather meter, and then the elongation rate was measured. Incidentally, the elongation rate was measured in accordance with J Engineering SK-6724. Further, the sunshine conditions were such that it rained at 6300 for 18 minutes every 2 hours, and the front and back sides of the test samples were changed every 20 hours.

Comparative Examples 1 to 8 Using partially crosslinked vinyl chloride resins (4) to Go+, the second
Based on the formulation shown in the table, in the same manner as in Examples 1 to 8,
A calender sheet with a thickness of 3.3 mm was obtained.

Various properties of the obtained calender sheets were measured and evaluated in the same manner as in Examples 1 to 8.

The results are shown in Table 2, and the sheets obtained in Comparative Examples 1 to 8 have poor weather resistance when they have good matte properties, and conversely, when they have good weather resistance, they have insufficient matte properties. I understand that.

In addition, Kanevinyl S-1001 and Kaneace PA-20 in Table 2 are each trade names manufactured by Kanebuchi Chemical Co., Ltd. f41J, and the gel fraction in the total resin component is the gel fraction of the partially crosslinked vinyl chloride resin. This is the value calculated from the original.

Claims (1)

[Scope of Claims] 1 A partially crosslinked vinyl chloride resin alone obtained by co-combining 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. Or a mixed resin with vinyl chloride resin, in which the gel content in the whole village #i7 component is 1.0 to 35 wt q%'
A matte agricultural sheet with excellent surface J weather resistance formed by molding a resin composition. 2 Bisphenol-modified diacrylate or bisphenol-modified dimethacrylate has the general formula (I): atom,
-OH group, -01 (20H3 group, 43 -0H20H3OOOH group, an atom or group,
The matte n industrial sheet according to claim 1, which is a compound represented by the following formula: m and n are integers of 1 to 10, and X is a Br atom, a C4 atom, or a H atom. 3 Bisphenol-modified diacrylate or bisphenol-modified dimethacrylate is represented by the general formula (ID: (1) (wherein, R, R3, R4, and X are the same as above, and l is 0 or an integer from 1 to 20) A sheet for consumption and agriculture, which is a compound described in claim 1. 4 Bisphenol-modified diacrylate or bisphenol-modified dimethacrylate is a compound of the general formula (3): The matte Q industrial sheet according to claim 1, which is a compound represented by R3, R4, l, and x are the same as above, and 1 and j are integers of 1 to 5.