JPH01275644A - Agricultural synthetic resin covering material - Google Patents

Abstract

PURPOSE:To obtain an agricultural synthetic resin covering material having resistance to weather and water, fog-preventing and nonhazing properties, by using a copolymer of a specified unsaturated alpha-fluoroester with a compound copolymerizable therewith. CONSTITUTION:The title agricultural synthetic resin covering material is produced by using a copolymer of a 4-20C fluoroalkyl-terminated unsaturated alpha-fluoroester (e.g., a compound of formula I or II) with a compound copolymerizable therewith [e.g., (meth)acrylic acid, methyl (meth)acrylate, styrene or vinyl chloride]. Owing to the alpha-fluorine atom, the above fluorinated copolymer can give a synthetic resin covering material having various excellent properties such as weathering resistance, heat resistance, water resistance, fog-preventing and nonhazing properties and transparency and forming no brown spots on the film after being left to stand for a long time and shows excellent retentivity of the nonhazing property.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to agricultural synthetic resin covering materials.

[Prior Art] It is known that properties of agricultural synthetic resin coating materials, such as weather resistance, fogproofing properties, and antifogging properties, can be improved by blending fluorine-containing compounds.

However, by using conventionally known fluorine-containing compounds, various properties required for synthetic resin coating materials can be satisfied to a certain extent, but they do not have sufficient weather resistance, fog resistance, and anti-fog properties. has not been obtained. In particular, when a synthetic resin coating material is used for a long period of time, brown spots become visible on the surface, which causes problems in weather resistance.

[Object of the Invention] An object of the present invention is to provide a synthetic resin covering material for agricultural use having various excellent properties, particularly excellent weather resistance, fog proofing properties, and heat proofing properties.

[Structure of the Invention] The gist of the present invention is to provide a fluorine-containing ester comprising at least one α-fluoro unsaturated ester containing a fluoroalkyl group having 4 to 20 carbon atoms at the terminal and at least ti of other copolymerizable compounds. An agricultural synthetic resin coating material characterized by containing a copolymer.

In the present invention, the α-fluorounsaturated ester preferably has the formula: Rf-A-C0CF=CI, (1) [wherein,
Rf is a C4-C1° fluoroalkyl group in which at least half of the hydrogens are substituted with fluorine, and A is a divalent organic group. ] It is a compound shown by.

In formula (1), the A group preferably has the formula ni (CH
,)Otori0-1-[(CHt)llO]n-(CsHsO)P(Cs)
(sO)q-1-[(CH*)10]n-(CsHs
O)p(CtHa O)Q-1OR'-[(CHJIO]n-CHt CHCHtO(CsH
sO)p(Csll*0)q-1OR' -[(CHt)sO]n-CHt CHCHtO(Cs
HsO)P(CJsO)Q-1■ -S O1N (CH*)Maro-1 -(CHt)s+-9-(CtH,0)ah- or -C
ON H(CH*)m- [wherein, R' is hydrogen or the acyl group of CI-04, R is hydrogen or the alkyl group of C, -C, 1 is the number of 1 to 4, n
is 0 or 1, p and q are numbers from θ to 20 (however, p + q
is 30 or less). ] is a group represented by

Specific examples of α-fluoro unsaturated esters are as follows: GFs(CF*)sCsH+OCOCF=C
HtCF a (CF *)7C* H40G OCF
= CH*(CFs)ICP(CFi)sc*H*0
cOcF=cHt(CFi)tcF(CFi)*C*H
aOCOCF=CH*CFs(CF*)tC
H* CH(OH) CH* OCOCF = CH*
(CF,), CP(CF,), C)1*cH(011
)C1,0COCF=CIIfiCFa(CFt)sc
H*cH(OCOCIIs)CHtOCOCF=CHx
CF*(CFi)t(CsH40)icOcF=CH*
(CF,), CF(CPfi)@CIH,O(C,H,
O), C0CP=C)i.

CPs(Crt)s(Ctl(io)t(CJsO)t
cOcF=cHtCPa(CFi)sC-H*0(CJ
,O)+(CJ-0)*C0CF=CH*(CF s
) ICP (CF*)a CHtCH(OH)CH
t0(CJ40) tocOcF=ctl t(CF
,) ICP(CF,),CI,CI(OH)CIl,
O(C,H,@C0CF=CHICFs(CFi),
cHtcll(OH)CHtO(CtH-0)s(Cs
HsO)+. C0CP=CIICPs (CP *)?
CH* CII (011)CH,0(C,11,0)
S (C, H, O), OC0CF=CI.

CPs(CFi)tsO*NctH40cOcF=CH
tCsH? CFi (CFi)tctH*sc*H40cOcF=c
)ItH(CFffi),. C) [t OCOCF =
CHsH(CF m)@CH*O(CsHsO)sC
OCF = CHgI2(CFi)scHtOcH*c
■(OH)CH0COCP=CI.

Cl2(CFi)-tcH*0cOcP=CH*CFs
(CFi)scONHc*H40cOcF=CH*H(
CP m ) * CON HC * H-OCOCF
=CH*α-fluorounsaturated ester can be generally produced, for example, according to the following reaction formula.

Rr −A −H+ F COCF = CH*→
Rf-A-COCF=CI1+HF [In the above formula, R and A have the same meanings as above.] In this reaction, reaction conditions such as solvent, reaction temperature, and reaction time follow usual reaction conditions.

Other copolymerizable compounds include, for example, unsaturated carboxylic acids (e.g. acrylic acid, methacrylic acid), unsaturated carboxylic acid esters (e.g. methyl acrylate, acrylic acid 2-
Ethylhexyl, polyethylene glycol monoacrylate, polyethylene diacrylate, aminoethyl acrylate, polypropylene monoacrylate, polyethylene polypropylene monoacrylate, methyl methacrylate, hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, polyethylene monomethacrylate, polypropylene monomethacrylate, glycidyl methacrylate), Saturated carboxylic acid amides (e.g. acrylamide, methylolated acrylamide), styrene, alpha-methylstyrene, divinylbenzene, vinyl alcohol, vinyl ethers (e.g. methyl vinyl ether, ethyl vinyl ether), acrylonitrile, methacrylate trile, vinyl amines, vinyl chloride, other vinyl monomers It is.

Copolymerization of at least one α-fluoro unsaturated ester and at least one other copolymerizable compound can be carried out in a container by a method such as solution polymerization, emulsion polymerization, or bulk polymerization using known techniques. can. In the copolymer, α
- The molar ratio of the fully unsaturated ester and other copolymerizable compounds is usually 0.1:0.9 to 0.9:0.1.

The number average molecular weight of the fluorine-containing copolymer is usually 1°o
o-t, o o o, o o o, preferably 3.0
00~too, ooo.

The agricultural synthetic resin coating material of the present invention uses a synthetic resin material as a soil component, and contains a fluorine-containing copolymer. The amount of the fluorine-containing copolymer is usually 0.01 to 2.0 parts by weight, preferably 0.01 to 2.0 parts by weight, per 100 parts by weight of the synthetic resin material.
05 to 0.5 parts by weight.

The synthetic resin material is generally a film-forming conventional synthetic resin such as polyvinyl chloride, polyolefin, polyvinyl acetate, acrylic resin, polyester, polyamide, or a blend of such synthetic resins.

The synthetic resin coating material of the present invention may contain a drip-proofing agent, a plasticizer, a stabilizer, a lubricant, a filler, an ultraviolet absorber, an antistatic agent, an antioxidant, etc. as appropriate.

The fluorine-containing copolymer can be blended into a synthetic resin material, for example, by adding it directly to a solution of the synthetic resin material or by soaking it in the synthetic resin material in a molten state. Next, it can be formed into a form such as a film by a conventional method, and is used as a synthetic resin covering material.

[Effects of the Invention] In the present invention, the fluorine-containing copolymer has various properties excellent in synthetic resin coating materials, such as weather resistance, fog proofing property, anti-fogging property, and heat resistance, due to the fluorine atom at the α position. , provides water resistance and transparency. In particular, no brown spots are observed on the synthetic resin coating material even after being left for a long period of time.

It also has excellent anti-fog durability.

[Example] EXAMPLES The present invention will be specifically explained below with reference to Examples.

Production Example 1 (Production of Copolymer A) CF Co (Chapter CF) in a 3-hole flask with a reflux device? CtHaOCOCF=CHt5
09CaH1tOCOC(CHs)=CHs
I59HO(CsHaO)scOc(CHs)=CH
*359 and ethyl acetate 1009 were charged. Further, C++*H*sSH2,09 as a molecular weight regulator and 0.59% of azoisobutyronitrile as a polymerization initiator were added, and the reaction was carried out at 60°C for 10 hours. After the reaction, the solvent ethyl acetate was distilled off under reduced pressure to obtain the title copolymer A.

The number average molecular weight of the copolymer was 6,000.

Production Example 2 (Production of Copolymer B) Monomer (CFs)mCF(CFs)sCH*CH(OH)CH
s-0COCF='CHt 409 and HO(Cs H
*0) *-(C*HaO)sCOC(CHs
)=CH* The same procedure as in Production Example 1 was repeated except that 609 was used to obtain the title copolymer B. The number average molecular weight of the copolymer was 7,000.

Production Example 3 (Production of Copolymer C) H(CFs)acH*0cOcF=cH* 509H as a monomer
O(CfiH,0)scOc(CH3)=CH1309
HO(CsH*0)*C0C(CHs)=CH*20
The title copolymer C was obtained by repeating the same procedure as in Production Example 1 except that Copolymer 9 was used. The number average molecular weight of the copolymer is t
It was o, o o o.

Example 1 Polyvinyl chloride (average degree of polymerization 1300) 100 parts by weight Dioctyl phthalate 45 parts by weight Tricresyl phosphate 5 parts by weight Epoxy resin
2 parts by weight Ba-Zn liquid stabilizer
2 parts by weight Ba-Zn powder stabilizer 1 part by weight benzophenone ultraviolet absorber o, 1 part by weight sorbitan monopalmitate 2 parts by weight are the basic composition, and a production example is added to this! 0.1 part by weight of the copolymer A obtained above was blended to prepare a film having a thickness of 0.1 gl.

Example 2 A film was prepared by repeating Example 1 except that 80.1 parts by weight of copolymer was used in place of copolymer A.

Example 3 A film was prepared by repeating Example 1 except that 1 part by weight of copolymer C00 was used in place of copolymer A.

Comparative Example 1 C* Ht s CHt CH(O
H) -CH*0 (C*H*0)+4CHs 0,
A film was prepared by repeating Example 1 except that 1 part by weight was used.

Comparative Example 2 A film was prepared by repeating Example 1, except that 0.3 parts by weight of copolymer A was used.

Comparative Example 3 CFs(CFs)tc*I(40GOCF=CH*5
CFs (CFs), c*HaOcOcH=
Repeat Production Example 1 except for using cH*50g,
A copolymer having a number average molecular weight of 5,000 was obtained. Copolymer A
A film was made by repeating Example I except using this copolymer instead of .

Test Examples Examples 1 to 3 and Comparative Examples 1 to 3 were placed in a tunnel-shaped greenhouse (house) with a width of 4881, a height of 4.8 m, and a depth of 25 m.
The film obtained in step 1 was stretched and evaluated for weather resistance, anti-fog properties, and anti-fog properties. The results are shown in Table 1. In addition, weather resistance,
Evaluation of anti-fogging properties and anti-fogging properties was carried out as follows.

(1) Weather resistance was evaluated by visual observation. The evaluation criteria are as follows: 1: No change observed in appearance 2: Only a few brown spots observed 3: Brown spots observed here and there 4: Many brown spots observed 5: Full surface (2) Fog resistance was evaluated by visual observation every hour 12 times per day from 7 a.m. to 6 p.m. The evaluation criteria are as follows:! = There is no fog at all inside the house, or there is a slight amount of fog forming only near the inner surface of the film 2: There is fog throughout the house, but the back of the house 25M away can be clearly identified.・3 : The fog is somewhat thick throughout the house, and the back of the house beyond 2511 cannot be clearly discerned. 4 : The fog is thick throughout the house, and the back of the 7X house at the tip of the 25th leg cannot be discerned at all (3) With the naked eye. The antifogging properties were evaluated by observation. The evaluation criteria are as follows: 1: Water adheres in the form of a thin film and no water droplets are observed 2:
Water is attached to a thin film, but slightly large water droplets are observed 3: Water is attached to a thin film, but large water droplets are observed to be partially attached 4: Fine water droplets are partially observed 5: Fine water droplets are observed on the entire inner surface of the film.

Claims (1)

[Scope of Claims] 1. Fluorine-containing copolymerization of at least one α-fluoro unsaturated ester containing a fluoroalkyl group having 4 to 20 carbon atoms at the terminal and at least one other copolymerizable compound A synthetic resin covering material for agricultural use that is characterized by containing a compound. 2. α-fluoro unsaturated ester with 4 to 4 carbon atoms at the end
The coating material according to claim 1, which is an α-fluoroacrylate containing 20 fluoroalkyl groups.