JPH01170656A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having excellent discoloration resistance especially during processing, containing a polyphosphite compound prepared by reacting a mixed alcohol having a specific composition with triphenyl or phosphorus trichloride. CONSTITUTION:100 pts.wt. any of various resins is blended with 0.01-5 pts.wt., preferably 0.1-3 pts.wt. based on the resin of one or more polyphosphite compounds such as a compound shown by formula I (DPG is group shown by formula II and R is group shown by formula III) prepared by reacting (A) a mixed alcohol of a monohydric alcohol (e.g., nonyl alcohol) and dihydric or trihydric alcohol (e.g., ethylene glycol) in the molar ratio of the dihydric or trihydric alcohol to the monohydric alcohol of >=1 with (B) a stoichiometric amount of triphenyl phosphite or phosphorus trichloride and, if necessary, a metallic organic acid salt, organic phosphite compound and epoxy compound to give a resin compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a resin composition containing a specific polyphosphite compound, which is particularly excellent in preventing discoloration during processing.

[Prior Art] It is known that various resins become colored and deteriorated by the action of heat and light, making them unusable. Various additives have been used to prevent such deterioration.

In particular, phosphite compounds are widely used because they have the advantage of improving heat resistance and weather resistance and preventing discoloration during processing. However, the phosphite compounds that have been used so far have been found to be insufficient in terms of heat resistance, weather resistance, and coloration prevention.

[Purpose of the Invention] In view of the current situation, the present inventors conducted various studies and aimed to find a resin composition that exhibits excellent heat resistance, weather resistance, and coloration prevention effects.

[Constitution of the Invention In other words, the present invention consists of (1) a mixed alcohol in which the molar ratio of dihydric or trihydric alcohol to monohydric alcohol is 1 or more, and triphenyl phosphite in stoichiometric equivalent amounts; (2) A mixed alcohol in which the molar ratio of dihydric or trihydric alcohol to monohydric alcohol is 1 or more and trichloride. The gist of the invention is a resin composition containing at least one type of polyphosphite obtained by reacting phosphorus in stoichiometrically equivalent amounts.

Monohydric alcohols used in the reaction in the present invention include nonyl alcohol, 1-nonyl alcohol, decyl alcohol, isodecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, CI2-C, IS mixed alcohol, and cetyl alcohol. Alcohol, stearyl alcohol, oleyl alcohol, eicosyl alcohol, tocosyl alcohol, Crt 112
50 ” CII 20 CII20 CII 201
1. Ce Ill? 0CII 20CII 201
1. etc. can be mentioned.

Examples of divalent or trivalent alcohols include ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1.2-propanediol, 1.3-propanediol, 1.2-butanediol, 1.3-butanediol, 1.4-butanediol, neopentyl glycol, thiodiethylene glycol, 1.6-hexanediol, 1.10-decanediol, 1.4-cyclohexanediol, 1.4-cyclohegysandiol Examples include methanol, 1,4-phenyldimethanol, bisphenol A1 hydrogenated bisphenol A, glycerin, trimethylolmethane, trimethylolethane, trimethylolpropane, tris-(2-hydroxyethyl)isocyanurate, and the like.

Representative examples of the polyphosphite compounds used in the present invention are shown below.

DPG: -0C11zC11zCllz-0-CI
lzCIIaCIIaO-R: Cl2115-N o , 2 OR DPG: -0C11zCllzC11z-0-CI
lzCIhCIIaO-R: C+5llav- R: C+5llav R: C rumor 11zr NPG: -0CIh-C-CIIzO-R
: C*II*- G: C1h-0- Direct C1+ -0- C11a-0- R: C+5llav- Tr'G: -0CIIzCII, C11z-
0-CIIzC11zC112-0-C112CIIa
C1120-R: Cuffza-DEG: -0CllzCIIz -0-CI
laCIlzO-R: (,yllfF- R: C*IIat- 4pc-p-oR\oR NPG: -0Cllz-C-CIIaO-
CI+ R: Cl311*- The amount of these polyphosphite compounds used is
0.01-5 parts by weight, preferably 0.01-5 parts by weight.
1 to affi parts.

Furthermore, the resins used in the present invention include polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene,
Chlorinated polypropylene, polyethylene, polypropylene, polybutene-1, polypentene-11 poly(3-methylbutene-1), poly(4-methylpentene-1), polyoctene-1, ethylene-propylene copolymer, polystyrene, poly-α -Methyl styrene, styrene-butadiene copolymer, methyl methacrylate-butadiene-
Styrene copolymer, acrylonitrile-styrene copolymer, styrene-1 maleic anhydride copolymer, ADS resin, polyurethane, polycarbonate, acrylic resin, E
Examples include VA. 28 or more of these may be used in combination.

It goes without saying that a metal organic acid salt may also be used in combination with the composition of the present invention.

Examples of metal components in this case include Li, Na,
Mg S Ca, Ba, Zn, Sn
, Sr.

Examples of a-acid residues include carboxylic acid and phenol residues as shown below.

Examples of carboxylic acids include acetic acid, propionic acid, butyric acid,
Valeric acid, caproic acid, enanthic acid, caprylic acid, neodecanoic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxy Stearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, P-ter
t-Butylbenzoic acid, 3,5-di-tert-butyl-4
-Hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, alpha aromatic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid 1, N, N-dimethylbenzoic acid, acetoxybenzoic acid,
Monohydric carboxylic acids such as salicylic acid, P-tert-octylsalicylic acid, oleic acid, elaidic acid, linoleic acid, linoleic acid, mercaptopro-and-ionic acid, octylmercaptopropionic acid, oxalic acid, malonic acid, succinic acid, adipic acid, pimelic acid, glutaric acid, speric acid,
Azelaic acid, cepatine, phthalic acid, isophthalic acid,
Terephthalic acid, oxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid,
Monoesters or monoamide compounds of divalent carboxylic acids such as methaconic acid, itaconic acid, aconitic acid, and thiodipropionic acid; trivalent or tetravalent carboxylic acids such as hemimellitic acid, trimellitic acid, merophonic acid, and pyromellitic acid; Examples include di- or triester compounds.

Examples of phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, 'ethylphenol, isopropylphenol, isooctylphenol, and 2-ethylhexylphenol. phenol, ter
t-nonylphenol, decylphenol, tert-
Examples include octylphenol, isohexylphenol, octadecylphenol, methylprophenol, methylisohexylphenol, and methyl-t-octylphenol.

The composition of the present invention may further contain conventionally known organic phosphite compounds and/or epoxy compounds.

Organic phosphite compounds that can be used in the present invention include:
Diphenyldecyl phosphite, triphenyl phosphite, tris-nonylphenyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, dilauryl acid phosphite, dibutyl acid phosphite, tris (dinonylphenyl) phosphite , trilauryl trithiophosphite, trilauryl phosphite, tribenzyl phosphite, dibenzyl phosphite, decakis(phenyl)hexakis dipropylene glycol octaphosphite, distearyl pentaerythritol diphosphite, diphenyl acid phosphite, tetratri Decyl-1,1,3-)lis(2'-methyl-5'-tert-butyl-4'oxyphenyl)butane diphosphite, tetra(C'+z -C
T! mixed alkyl) 4,4'-isobropylidene diphenyl diphosphite, tris(4-oxy-2,5-di-tert-butylphenyl) phosphite, tris(4-oxy-3,5-di-tert-butylphenyl) ) phosphite,
2-ethylhexyl diphenyl phosphite, tris(
Mono- and di-mixed nonylphenyl) phosphites, hydrogenated-
4,49-isopropylidene diphenol polyphosphite, and the like.

Epoxy compounds that can be used in the present invention include epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, evoquinated raw tallow oil, epoxidized polybutadiene, epoxy methyl stearate, -butyl, - 2-ethylhexyl, -stearyl, tris(epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized flower oil, epoxidized linseed oil fatty acid butyl, 3-(2-xenoxy)-1,2-epoxypropane, bisphenol-A di Examples include glycidyl ether, vinylcyclohexene dieboxide, dicyclopentadiene dieboxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate, and the like.

Phthalate plasticizers, other ester plasticizers, polyester plasticizers, phosphate plasticizers, chlorine plasticizers, and other plasticizers are used in the composition of the present invention as appropriate depending on the purpose. can.

Adding an antioxidant to the composition of the present invention can increase the oxidative deterioration prevention properties of the composition, so it can be used as appropriate depending on the purpose of use.

These antioxidants include phenolic antioxidants, sulfur-containing compounds, and the like.

If an ultraviolet absorber is added to the composition of the present invention, the photostability can be improved, so it is possible to select and use these as appropriate depending on the purpose of use. These include benzophenone, benzotriazole, salicylate, substituted acrylonitrile, various metal salts or metal chelates, especially nickel or chromium salts or chelates, triazine, piperine, and the like.

Others as necessary, such as crosslinking agents, pigments, fillers, foaming agents, antistatic agents, antifogging agents, plate-out inhibitors, lubricants, a-fuel agents, fluorescent agents, antifungal agents, bactericidal agents, and metal deactivators. ,
Photodegradants, processing aids, mold release agents, reinforcing agents, and the like can be included.

Next, the present invention will be explained with reference to examples, but the present invention is not limited to these examples.

Note that the =f values in Examples are as follows.

○: Excellent Δ: Fair: Slightly inferior Oven (180℃) heat resistance test, line 170
'C-70kg/ewe', coloring property ◆ transparency by 10 minute press test, and outdoor exposure test for 1 year. The yields are as shown in Table 1.

Examples 7 to 12 The agricultural and agricultural compositions shown in Table 2 were kneaded for 5 minutes with a roll at 180°C to form a sheet with a thickness of 0.4 mm. Performance tests were conducted using this sheet in the same manner as in Examples 1 to 6. The results are shown in Table 2.

Examples 13 to 18 The compositions shown in Table 3 were kneaded for 5 minutes using two rolls at 190°C to form sheets with a thickness of 0.6 mm. Performance tests were conducted using this sheet in the same manner as in Examples 1 to 6. The results are shown in Table 3.

Examples 19-24 The compositions shown in Table 4 were kneaded for 5 minutes using two rolls at 190'C to form a sheet with a thickness of 0.3 mm. Performance tests were conducted using this sheet in the same manner as in Examples 1 to 6. The results are shown in Table 4.

Examples 25 to 30 The compositions shown in Table 5 are kneaded for 5 minutes with two rolls at 200°C to form a sheet with a thickness of 0.5 mm. Performance tests were conducted using this sheet in the same manner as in Examples 1 to 6. The results are shown in Table 5.

Claims (2)

[Claims] (1) Polyphosphite obtained by transesterifying triphenyl phosphite in stoichiometrically equivalent amounts with a mixed alcohol in which the molar ratio of divalent or trivalent alcohol to monovalent alcohol is 1 or more. A resin composition containing at least one of the following. (2) At least one polyphosphite obtained by reacting a mixed alcohol in which the molar ratio of dihydric or trihydric alcohol to monohydric alcohol is 1 or more and phosphorus trichloride in stoichiometrically equivalent amounts. A resin composition containing one type of