Sulfur-containing acid phosphoric ester internal release agent

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an internal release agent, a method for molding a resin using the internal release agent and a molded article obtained therefrom.
2. Description of the Related Art
There are known various methods for molding resins such as casting molding, injection molding and the like. In each method, so-called release agents are used for improving releasability between a molded article and a mold.
In particular, urethane resin, epoxy resins and the like have a strong adhesion and therefore, it is essential to use a release agent.
Release agents are generally classified into two groups, that is, external release agents and internal release agents.
External release agents should be applied to the inner surface of a mold with each molding procedure. Therefore, there are various problems as shown below. The productivity of the molded articles is poor, an external release agent is transferred onto the surface of the resulting molded articles resulting in irregular portions on the surface of the molded article and causing defective coating and dyeing. Furthermore, a transparent resin molded article becomes turbid, and the like.
On the contrary, an internal release agent is added to a resin producing monomers in advance. It is not necessary to apply it to a mold with each molding. Therefore, an internal release agent favors improvement in productivity.
As internal release agents, there are known internal release agents for urethane resin molding, for example, fluorine type nonionic surface active agents, silicone type nonionic surface active agents, alkyl quaternary ammonium salts, acid phosphoric esters, liquid paraffin, waxes, higher fatty acids and metal salts thereof, higher fatty acid esters, higher aliphatic alcohols, bisamides, polysiloxanes, aliphatic amine ethylene oxide adducts and the like (Japanese Patent Application Laid-open No. Hei 1-295201).
Phosphoric acid esters having polyether substituents have been recently proposed (Japanese Patent Application Laid-open No. Hei 3-287641).
For reaction injection molding of urethane resins, zinc stearate is generally used, but zinc stearate is not so soluble in the starting materials that various compatibilizers have been proposed (Japanese Patent Application Laid-open No. Hei 3-273030 and Japanese Patent Publication No. Hei 3-27586).
In the molding of epoxy resins, there are known a method using zinc stearate as an internal release agent (Japanese Patent Application Laid-open No. Hei 1-213602), a method using fluorine type nonionic surface active agents, silicon type nonionic surface active agent, alkyl quaternary ammonium salts, acid phosphoric esters and the like as internal release agents (Japanese Patent Application Laid-open No. Hei 3-81320), and methods of using both an external release agent and an internal release agent (Japanese Patent Application Laid-open Nos. Sho 63-144302 and 63 - 144303).
Further, in the molding of polyolefin resins, there are used aliphatic alcohols, aliphatic esters, phthalic acid esters, triglycerides, fluorine type surface active agents, higher fatty acid metal salts and the like as internal release agents (Japanese Patent Application Laid-open Nos. Hei 2-84409 and 2-44301).
In the molding of polycarbonate resins, there are used higher fatty acid esters, waxes, liquid paraffin, silicone oil, alkyl glyceryl ethers and the like as internal release agents (Japanese Patent Application Laid-open Nos. Hei 1-315460 and 1-315459).
For molding acrylic resins, there are generally used molding methods where higher alcohols, higher fatty acid esters, higher fatty acids and the like are used as internal release agents (Japanese Patent Application Laid-open No. Hei 2-105844).
The known internal release agents as above are effective and improve productivity of the molded articles as compared with external release agents. However, the releasing function is not sufficient and thereby, the resins sometimes remain on the surface of molds and in the case of molds made of glass, glass sometimes peeled off. In addition, excess stress is applied due to the resistance upon releasing and thereby the molded article is liable to warp or to be strained.
When internal release agents are used in an amount sufficient to release satisfactorily, the molded articles are liable to become turbid.
Such drawbacks are fatal to molding optical products such as plastic lenses particularly requiring surface accuracy and transparency, light discs and the like, and deteriorate the commodity value to a great extent.
In view of the foregoing, development of a new internal release agent has been strongly demanded which has a sufficient releasing function and does not deteriorate transparency in the case of molding a transparent resin.
SUMMARY OF THE INVENTION
An object of the present invention is to provide an internal release agent capable of exhibiting at least partly a high releasability, suppression of occurrence of strain in a molded article upon releasing, prevention of the resin from dirtying the surface of a mold, and substantially no adverse influence on transparency when a transparent resin is molded.
Another object of the present invention is to provide a method for molding a resin with the internal release agent.
A further object of the present invention is to provide a molded resin article produced using the internal release agent.
According to one aspect of the present invention, there is provided an internal release agent which comprises at least one sulfur-containing acid phosphoric ester selected from the group consisting of thiophosphoric acid esters and dithiophosphoric acid esters of the formula, ##STR2## where X and Y are independently selected from the group consisting of an oxygen atom and a sulfur atom, at least one of X and Y is a sulfur atom, and R.sub.1 and R.sub.2 are independently alkyl groups.
According to another aspect of the present invention, there is provided a method for molding a resin comprising using the internal release agent as mentioned above.
According to a further aspect of the present invention, there is provided a resin molded article produced by the method for molding as mentioned above.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The thiophosphoric acid ester of the formula (1) as above has the following equilibrium of the formula (2) and is known to be present in the form of the mixture (Methoden der Organischen Chemie, Band XII/2, P. 604, 1964). ##STR3##
Conventional uses of sulfur-containing phosphoric acid esters are mainly starting materials for insecticides and germicide (U.S. Pat. No. 3,742,097) and thereby, concern the field of agricultural chemicals.
Therefore, it is not predictable at all from the conventional uses of the sulfur-containing phosphoric acid ester that such compound can be used as a useful internal release agent.
Exemplary suitable internal release agents of the present invention include:
dimethyl thiophosphate,
diethyl thiophosphate,
dipropyl thiophosphate,
diisopropyl thiophosphate,
dibutyl thiophosphate,
dioctyl thiophosphate,
didecyl thiophosphate,
didodecyl thiophosphate,
ditetradodecyl thiophosphate,
dihexadecyl thiophosphate,
and
dioctadecyl thiophosphate.
Exemplary suitable dithiophosphoric acid esters of the formula (1) include:
dimethyl dithiophosphate,
diethyl dithiophosphate,
dipropyl dithiophosphate,
diisopropyl dithiophosphate,
dibutyl dithiophosphate,
dihexyl dithiophosphate,
dioctyl dithiophosphate,
didecyl dithiophosphate,
didodecyl dithiophosphate,
ditetradecyl dithiophosphate,
dihexadecyl dithiophosphate,
and dioctadecyl dithiophosphate.
Resins to which the present invention is applied are not particularly critical.
As thermosetting resins, there are mentioned, for example,
urethane resins,
epoxy resins,
polyolefin resins,
polyene-polythiol resins,
unsaturated polyester resins,
phenolic resins,
furan resins,
xylene resins,
formaldehyde resins,
ketone resins,
urea resins,
melamine resins,
aniline resins,
sulfonamide resins,
alkyd resins,
and
composite resins thereof.
As thermoplastic resins, there are mentioned, for example,
polyolefin resins,
polycarbonate resins,
thermoplastic polyester resins,
polyether resins,
polyamide resins,
polyimide resins,
urethane resins,
polyvinylketone resins,
polyvinyl ether resins,
and
composite resins thereof.
Molding methods may be appropriately selected depending on the characteristics of resins.
In general, thermosetting resins, are molded by casting polymerization methods, compression molding methods and the like, and thermoplastic resins are molded by injection molding methods, extrusion molding methods and the like.
The present invention may be effected by any molding method.
In the case of casting polymerization, a sulfur-containing acid phosphoric ester may be added to monomer or monomer mixtures in advance, followed by polymerizing the resulting mixture in a mold.
According to other molding methods, resin powder or pellets may be molded by mixing resin powder with a sulfur-containing acid phosphoric ester, melted or plasticized, poured into a mold and then molded, or when producing resin powder or pellets, a sulfur-containing acid phosphoric ester may be added in advance and the resulting resin powder or pellets may be directly molded.
Or any other methods may be used.
The amount of the sulfur-containing acid phosphoric ester used is preferably 0.01-5% by weight based on the total amount of monomers in the case of casting polymerization of urethane resins or epoxy resins which are difficult to be released.
When the amount is less than 0.01% by weight, the releasing becomes poor. When it exceeds 5% by weight, various inherent physical properties of the resins may be adversely affected.
In the case of injection molding or the like of thermoplastic resins such as polyolefin resins, polycarbonate resins, acrylic resins and the like, releasing is relatively easy, and therefore, the amount of sulfur-containing acid phosphoric ester may be preferably as low as 0.01-1% by weight.
In the formula (1), the alkyl groups of R.sub.1 and R.sub.2 may be similar or dissimilar, and in general, the shorter the alkyl chain, the higher the releasing function. Therefore, sulfur-containing acid phosphoric esters having C.sub.1 -C.sub.8 alkyl groups are preferably used.
However, when a particularly high temperature is necessary, for example, in the case of injection molding, it is preferable to use sulfur-containing acid phosphoric esters of high boiling points, and in such a case, alkyl groups up to C.sub.18 are preferably used.
Sulfur-containing acid phosphoric esters having alkyl groups of more than C.sub.18 exhibit lower release function, and in the case of molding transparent resins, the molded articles are liable to be turbid.
As the material for the mold, there may be used stainless steels, copper, aluminum, alloys thereof, wood, ceramics and glass generally used as molds.
In the following, some of the representative resins which may be used in the present invention are explained in more detail.
As urethane resins, there may be mentioned resins prepared by polymerizing at least one iso(thio)cyanate compound selected from the group consisting of polyisocyanate compounds, polyisothiocyanate compounds and isothiocyanate compounds having an isocyanate group with at least one active hydrogen compound selected from the group consisting of polyol compounds, polythiol compounds and hydroxythiol compounds.
Upon polymerization molding, there may be added various additives such as known chain extender, crosslinking agent, photo-stabilizer, UV absorber, antioxidant, oil soluble dye, filler, polymerization catalyst and the like, depending on the purpose.
Exemplary suitable polyisocyanate compounds include:
aliphatic polyisocyanates such as
ethylene diisocyanate,
trimethylenediisocyanate,
tetramethylenediisocyanate,
hexamethylenediisocyanate,
octamethylenediisocyanate,
nonamethylenediisocyanate,
2,2'-dimethylpentanediisocyanate,
2,2,4-trimethylhexanediisocyanate,
decamethylenediisocyanate,
butenediisocyanate,
1,3-butadiene-1,4-diisocyanate,
2,4,4-trimethylhexamethylenediisocyanate,
1,6,11-undecanetriisocyanate,
1,3,6-hexamethylenetriisocyanate,
1,8-diisocyanato-4-isocyanatomethyloctane,
2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane,
bis(isocyanatoethyl)carbonate,
bis(isocyanatoethyl)ether,
1,4-butyleneglycoldipropylether-.alpha., .alpha.'-diisocyanate,
lysine diisocyanate methyl ester,
lysine triisocyanate,
2-isocyanatoethyl-2,6-diisocyanatohexanoate,
2-isocyanatopropyl-2,6-diisocyanatohexanoate,
xylylenediisocyanate,
bis(isocyanatoethyl)benzene,
bis(isocyanatopropyl)benzene, .alpha.,.alpha.,.alpha.', .alpha.'-tetramethylxylylenediisocyanate,
bis(isocyanatobutyl)benzene,
bis(isocyanatomethyl)naphthalene,
bis(isocyanatomethyl)diphenylether,
bis(isocyanatoethyl)phthalate,
mesitylylenetriisocyanate,
2,6-di(isocyanatomethyl)furan and the like;
alicyclic polyisocyanates such as
isophoronediisocyanate,
bis(isocyanatomethyl)cyclohexane,
dicyclohexylmethanediisocyanate,
cyclohexanediisocyanate,
methylcyclohexanediisocyanate,
dicyclohexyldimethylmethanediisocyanate,
2,2'-dimethyldicyclohexylmethanediisocyanate,
bis(4-isocyanato-n-butylidene)pentaerythritol,
dimer acid diisocyanate,
2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane,
2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane,
2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane,
2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane,
2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo-[2.2.1]-heptane,
2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo-[2.2.1]-heptane,
2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatomethyl)-bicyclo-[2.2.1]-heptane,
2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo-[2.2.1]-heptane,
2,5 (or 6)-bis(isocyanatomethyl)-bicyclo-[2.2.1]-heptane, and the like; and
aromatic polyisocyanates such as
phenylene diisocyanate,
tolylene diisocyanate,
ethylphenylene diisocyanate,
isopropylphenylene diisocyanate,
dimethylphenylene diisocyanate,
diethylphenylene diisocyanate,
diisopropylphenylene diisocyanate,
trimethylbenzene triisocyanate,
benzene triisocyanate,
naphthalene diisocyanate,
methylnaphthalene diisocyanate,
biphenyl diisocyanate,
tolidine diisocyanate,
4,4'-diphenylmethane diisocyanate,
3,3'-dimethyldiphenylmethane-4,4'-diisocyanate,
bibenzyl-4,4'-diisocyanate,
bis(isocyanatophenyl)ethylene,
3,3'-dimethoxybiphenyl-4,4'-diisocyanate,
triphenylmethane triisocyanate,
polymeric MDI,
naphthalene triisocyanate,
diphenylmethane-2,4,4'-triisocyanate,
3-methyldiphenylmethane-4,6,4'-triisocyanate,
4-methyl-diphenylmethane-3,5,2',4',6'-pentaisocyanate,
phenylisocyanatomethylisocyanate,
phenylisocyanatoethylisocyanate,
tetrahydronaphthalenediisocyanate,
hexahydrobenzenediisocyanate,
hexahydrodiphenylmethane-4,4'-diisocyanate,
diphenylether diisocyanate,
ethylene glycol diphenylether diisocyanate,
1,3-propyleneglycol diphenylether diisocyanate,
benzophenone diisocyanate,
diethylene glycol diphenylether diisocyanate,
dibenzofuran diisocyanate,
carbazole diisocyanate,
ethylcarbazole diisocyanate,
dichlorocarbazole diisocyanate, and the like.
Exemplary suitable polyisocyanate compounds containing sulfur atom include:
sulfur-containing aliphatic isocyanates such as
thiodiethyl diisocyanate,
thiodipropyl diisocyanate,
thiodihexyl diisocyanate,
dimethylsulfone diisocyanate,
dithiodimethyl diisocyanate,
dithiodiethyl diisocyanate,
dithiodipropyl diisocyanate,
and the like;
aromatic isocyanates containing sulfide bond such as
diphenylsulfide-2,4'-diisocyanate,
diphenylsulfide-4,4'-diisocyanate,
3,3'-dimethoxy-4,4'-diisocyanate dibenzylthioether,
bis(4-isocyanatomethylphenyl)sulfide,
4,4'-methoxyphenylthioethyleneglycol-3,3'-diisocyanate,
and the like;
aromatic isocyanates containing disulfide bond such as
diphenyldisulfide-4,4'-diisocyanate,
2,2'-dimethyldiphenyldisulfide-5,5'-diisocyanate,
3,3'-dimethyldiphenyldisulfide-5,5'-diisocyanate,
3,3'-dimethyldiphenyldisulfide-6,6'-diisocyanate,
4,4'-dimethyldiphenyldisulfide-5,5'-diisocyanate,
3,3'-dimethoxydiphenyldisulfide-4,4'-diisocyanate,
4,4'-dimethoxydiphenyldisulfide-3,3'-diisocyanate,
and the like;
aromatic isocyanates containing sulfone bond such as
diphenylsulfone-4,4'-diisocyanate,
diphenylsulfone-3,3'-diisocyanate,
benzidinesulfone-4,4'-diisocyanate,
diphenylmethanesulfone-4,4'-diisocyanate,
4-methyldiphenylsulfone-4,4'-diisocyanate,
4,4'-dimethoxyphenylsulfone-3,3'-diisocyanate,
3,3'-dimethoxy-4,4'-diisocyanatobenzyldisulfone,
4,4'-dimethyldiphenylsulfone-3,3'-diisocyanate,
4,4'-di-tert-butyldiphenylsulfone-3,3'-diisocyanate,
4,4'-methoxyphenylethylenesulfone-3,3'-diisocyanate,
4,4'-dicyclodiphenylsulfone-3,3'-diisocyanate,
and the like;
aromatic isocyanates containing sulfonic acid ester bond such as
4-methyl-3-isocyanatophenylsulfonyl-4'-isocyanatophenol ester,
4-methoxy-3-isocyanate phenylsulfonyl-4'-isocyanatophenol ester,
and the like;
aromatic isocyanates containing sulfonamide bond such as
4-methyl-3-isocyanatophenylsulfonylanilide-3'-methyl-4'isocyanate,
diphenylsulfonyl-ethylenediamine-4,4'-diisocyanate,
4,4'-methoxyphenylsulfonyl-ethylenediamine-3,3'-diisocyanate,
4-methyl-3-isocyanatophenylsulfonylanilide-4-methyl-3'isocyanate,
and the like;
sulfur-containing heterocyclic compounds such as thiophene-2,5-diisocyanate and the like;
and
1,4-dithiane-2,5-diisocyanate and the like.
Exemplary suitable polyisothiocyanate compound include:
aliphatic polyisothiocyanate such as
1,2-diisothiocyanatoethane,
1,3-diisothiocyanatopropane,
1,4-diisothiocyanatobutane,
1,6-diisothiocyanatohexane,
p-phenylenediisopropylidene diisothiocyanate,
and the like;
aliphatic isothiocyanate such as
cyclohexane diisothiocyanate and the like;
aromatic polyisothiocyanate such as
1,2-diisothiocyanatobenzene,
1,3-diisothiocyanatobenzene,
1,4-diisothiocyanatobenzene,
2,4-diisothiocyanatotoluene,
2,5-diisothiocyanato-m-xylene,
4,4-diisothiocyanato-1,1'-biphenyl,
1,1'-methylenebis(4-isothiocyanatobenzene),
1,1'-methylenebis(4-isothiocyanato-2-methylbenzene),
1,1'-methylenebis(4-isothiocyanato-3-methylbenzene),
1,1'-(1,2-ethanediyi)bis(4-isothiocyanatobenzene),
4,4'-diisothiocyanatobenzophenone,
4,4'-diisothiocyanato-3,3'-dimethylbenzophenone,
benzanilide-3,4'-diisothiocyanate,
diphenylether-4,4'-diisothiocyanate,
diphenylamine-4,4'-diisocyanate,
and the like;
heterocyclic ring-containing isothiocyanate such as
2,4,6-triisothiocyanato-3,5-triazine and the like;
and
carbonylisothiocyanate such as
hexanedioyldiisothiocyanate,
nonanedioyldiisothiocyanate,
carbonic diisothiocyanate,
1,3-benzenecarbonyldiisothiocyanate,
1,4-benzenecarbonyldiisothiocyanate,
(2,2'-bipyridine)-4,4'-dicarbonyldiisothiocyanate,
and the like.
Exemplary suitable polyisothiocyanates containing at least one sulfur atom other than isothiocyanato group include:
sulfur-containing aliphatic polyisothiocyanate such as
thiobis(3-isothiocyanatopropane),
thiobis(2-isothiocyanatoethane),
dithiobis(2-isothiocyanatoethane),
and the like;
sulfur-containing aromatic polyisothiocyanate such as
1-isothiocyanato-4-[(2-isocyanato)sulfonyl]benzene,
thiobis(4-isothiocyanatobenzene),
sulfonylbis(4-isothiocyanatobenzene),
sulfinylbis(4-isothiocyanatobenzene),
dithiobis(4-isothiocyanatobenzene),
4-isothiocyanato-1-[(4-isocyanatophenyl)sulfonyl]-2-methoxy-benzene,
4-methyl-3-isothiocyanatobenzenesulfonyl-4'-isocyanatophenyl ester,
4-methyl-3'isothiocyanatobenzenesulfonylanilide-3'-methyl-4'-isocyanate,
and the like;
and
sulfur-containing heterocyclic compound such as
thiophene-2,5-diisothiocyanate,
1,4-dithiane-2,5-diisothiocyanate,
and the like.
Exemplary suitable isothiocyanate compounds containing isocyanato group include:
aliphatic or alicyclic compound such as
1-isocyanato-3-isothiocyanatopropane,
1-isocyanato-5-isothiocyanatopentane,
1-isocyanato-6-isothiocyanatohexane,
isothiocyanatocarbonylisocyanate,
1-isocyanato-4-isothiocyanatocyclohexane
and the like;
aromatic compound such as
1-isocyanato-4-isothiocyanatobenzene,
4-methyl-3-isothiocyanato-1-isothiocyanatobenzene,
and the like;
heterocyclic compound such as
2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine,
and the like;
and
compounds containing sulfur atom other than isothiocyanato group such as
4-isothiocyanato-4'-isothiocyanatodiphenylsulfide,
2-isothiocyanato-2'-isothiocyanatodiethyldisulfide,
and the like.
In addition, there may be used halogen-substituted compounds derived from the above-mentioned iso(thio)cyanate compounds such as the chloro- or bromo-substituted compounds and the like,
products of a biuret forming reaction of the above-mentioned compounds,
products of the adduct reaction with trimethylolpropane,
and
the dimerized or trimerized reaction products.
These compounds may be used alone or in combination.
Exemplary suitable polyol compounds include:
aliphatic polyol such as
ethylene glycol,
diethylene glycol,
propylene glycol,
dipropylene glycol,
butylene glycol,
neopentyl glycol,
glycerine,
trimethylolethane,
trimethylolpropane,
butanetriol,
1,2-methylglucoside,
pentaerythritol,
dipentaerythritol,
tripentaerythritol,
sorbitol,
erythritol,
threitol,
ribitol,
arabinitol,
xylitol,
allitol
mannitol,
dulcitol
iditol
glycol,
inositol,
hexanetriol,
triglycerol,
diglycerol
triethylene glycol,
polyethylene glycol,
tris(2-hydroxyethyl)isocyanurate,
cyclobutanediol,
cyclopentanediol,
cyclohexanediol,
cycloheptanediol,
cyclooctanediol,
cyclohexanedimethanol,
hydroxypropylcyclohexanol,
tricyclo[5.2.1.0.sup.2.6 ]decane-dimethanol,
bicyclo[4.3.0]-nonanediol,
dicyclohexanediol,
tricyclo[5.3.1.1]dodecanediol,
bicyclo[4.3.0]nonane-dimethanol,
tricyclo[5.3.1.1]docedane-diethanol,
hydroxypropyltricyclo[5.3.1.1]dodecanol,
spiro[3,41octanediol,
butylcyclohexanediol,
1,1'-bicyclohexylidenediol,
cyclohexanetriol,
maltitol,
lactose
and the like;
aromatic polyol such as
dihydroxynaphthalene,
trihydroxynaphthalene,
tetrahydroxynaphthalene,
dihydroxybenzene,
benzene triol,
biphenyl tetraol,
pyrogallol,
(hydroxynaphthyl)pyrogallol,
trihydroxyphenanthrene,
bisphenol A,
bisphenol F,
xylyleneglycol,
di(2-hydroxyethoxy)benzene,
bisphenol A-bis(2-hydroxyethylether),
tetrabromobisphenol A,
tetrabromobisphenol A-bis(2-hydroxyethylether),
and the like;
halogenated polyol such as
dibromoneopentyl glycol,
and the like;
high polymer polyol such as
epoxy resins,
and the like;
and further,
condensation reaction products of the above-mentioned polyols with the following organic acids such as
oxalic acid,
glutamic acid,
adipic acid,
acetic acid,
propionic acid,
cyclohexane carboxylic acid,
.beta.-oxocyclohexane propionic acid,
dimer acid,
phthalic acid,
isophthalic acid,
salicylic acid,
3-bromopropionic acid,
2-bromoglycol,
dicarboxycyclohexane,
pyromellitic acid,
butanetetracarboxylic acid,
bromophthalic acid,
and the like;
addition reaction products of the above-mentioned polyols with alkylene oxide such as ethylene oxide, propylene oxide and the like;
addition reaction products of alkylene polyamine with alkylene oxide such as ethylene oxide, propylene oxide and the like; and
polyol containing sulfur atom such as
bis[4-(hydroxyethoxy)phenyl]sulfide,
bis[4-(2-hydroxypropoxy)phenyl]sulfide,
bis[4-(2,3-dihydroxypropoxy)phenyl]sulfide,
bis[4-(4-hydroxycyclohexyloxy)phenyl]sulfide,
bis[2-methyl-4-(hydroxyethoxy)-6-butylphenyl]sulfide,
compounds formed by adding average three molecules or less of ethylene oxide and/or propylene oxide per one hydroxyl group of the above-mentioned sulfides,
di-(2-hydroxyethyl)sulfide,
1,2-bis(2-hydroxyethylmercapto)ethane,
bis(2-hydroxyethyl)disulfide,
1,4-dithiane-2,5-diol,
bis(2,3-dihydroxypropyl)sulfide,
tetrakis (4-hydroxy-2-thiobutyl)methane,
bis(4-hydroxyphenyl)sulfone(Bisphenol S, trade name),
tetrabromobisphenol S,
tetramethylbisphenol S,
4,4'-thiobis(6-tert-butyl-3-methylphenol),
1,3-bis(2-hydroxyethylthioethyl)-cyclohexane,
and the like.
Examplary suitable polythiol compounds include:
aliphatic polythiol such as
methanedithiol,
1,2-ethanedithiol,
1,1-propanedithiol,
1,2-propanedithiol,
1,3-propanedithiol,
2,2-propanedithiol,
1,6-hexanedithiol,
1,2,3-propanetrithiol,
1,1-cyclohexanedithiol,
1,2-cyclohexanedithiol,
2,2-dimethylpropane-1,3-dithiol,
3,4-dimethoxybutane-1,2-dithiol,
2-methylcyclohexane-2,3-dithiol,
bicyclo[2.2.1]hepta-exo-cis-2,3-dithiol,
1,1-bis(mercaptomethyl)cyclohexane,
thiomalic acid bis(2-mercaptoethylester),
2,3-dimercaptosuccinic acid (2-mercaptoethylester),
2,3-dimercapto-1-propanol(2-mercaptoacetate),
2,3-dimercapto-1-propanol(3-mercaptoacetate),
diethylene glycol bis(2-mercaptoacetate),
diethylene glycol bis(3-mercaptopropionate),
1,2-dimercaptopropyl methyl ether,
2,3-dimercaptopropyl methyl ether,
2,2-bis(mercaptomethyl)-1,3-propanedithiol,
bis(2-mercaptoethyl) ether,
ethylene glycol bis(2-mercaptoacetate),
ethylene glycol bis(3-mercaptopropionate),
trimethylolpropane tris(2-mercaptoacetate),
trimethylolpropane tris(3-mercaptopropionate),
pentaerythritol tetrakis(2-mercaptoacetate),
pentaerythritol tetrakis(3-mercaptopropionate),
1,2-bis(2-mercaptoethylthio)-3-mercaptopropane,
and the like;
aromatic polythiol such as
1,2-dimercaptobenzene,
1,3-dimercaptobenzene,
1,4-dimercaptobenzene,
1,2-bis(mercaptomethyl)benzene,
1,3-bis(mercaptomethyl)benzene,
1,4-bis(mercaptomethyl)benzene,
1,2-bis(mercaptoethyl)benzene,
1,3-bis(mercaptoethyl)benzene,
1,4-bis(mercaptoethyl)benzene,
1,2-bis(mercaptomethyleneoxy)benzene,
1,3-bis(mercaptomethyleneoxy)benzene,
1,4-bis(mercaptomethyleneoxy)benzene,
1,2-bis(mercaptoethyleneoxy)benzene,
1,3-bis(mercaptoethyleneoxy)benzene,
1,4-bis(mercaptoethyleneoxy)benzene,
1,2,3-trimercaptobenzene,
1,2,4-trimercaptobenzene,
1,3,5-trimercaptobenzene,
1,2,3-tris(mercaptomethyl)benzene,
1,2,4-tris(mercaptomethyl)benzene,
1,3,5-tris(mercaptomethyl)benzene,
1,2,3-tris(mercaptoethyl)benzene,
1,2,4-tris(mercaptoethyl)benzene,
1,3,5-tris(mercaptoethyl)benzene,
1,2,3-tris(mercaptomethyleneoxy)benzene,
1,2,4-tris(mercaptomethyleneoxy)benzene,
1,3,5-tris(mercaptomethyleneoxy)benzene,
1,2,3-tris(mercaptoethyleneoxy)benzene,
1,2,4-tris(mercaptoethyleneoxy)benzene,
1,3,5-tris(mercaptoethyleneoxy)benzene,
1,2,3,4-tetramercaptobenzene,
1,2,3,5-tetramercaptobenzene,
1,2,4,5-tetramercaptobenzene,
1,2,3,4-tetrakis(mercaptomethyl)benzene,
1,2,3,5-tetrakis(mercaptomethyl)benzene,
1,2,4,5-tetrakis(mercaptomethyl)benzene,
1,2,3,4-tetrakis(mercaptoethyl)benzene,
1,2,3,5-tetrakis(mercaptoethyl)benzene,
1,2,4,5-tetrakis(mercaptoethyl)benzene,
1,2,3,4-tetrakis(mercaptomethyleneoxy)benzene,
1,2,3,5-tetrakis(mercaptomethyleneoxy)benzene,
1,2,4,5-tetrakis(mercaptomethyleneoxy)benzene,
1,2,3,4-tetrakis(mercaptoethyleneoxy)benzene,
1,2,3,5-tetrakis(mercaptoethyleneoxy)benzene,
1,2,4,5-tetrakis(mercaptoethyleneoxy)benzene,
2,2'-dimercaptobiphenyl,
4,4'-dimercaptobiphenyl,
4,4'-dimercaptobibenzyl,
2,5-toluenedithiol,
3,4-toluenedithiol,
1,4-naphthalenedithiol,
1,5-naphthalenedithiol,
2,6-naphthalenedithiol,
2,7-naphthalenedithiol,
2,4-dimethylbenzene-1,3-dithiol,
4,5-dimethylbenzene-1,3-dithiol,
9,10-anthracenedimethanethiol,
1,3-di(p-methoxyphenyl)propane-2,2-dithiol,
1,3-diphenylpropane-2,2-dithiol,
phenylmethane-1,1-dithiol,
2,4-di(p-mercaptophenyl)pentane, and the like;
halogen-substituted (e.g. chloro-or bromo-substituted)
aromatic polythiol such as
2,5-dichlorobenzene-1,3-dithiol,
1,3-di(p-chlorophenyl)propane-2,2-dithiol,
3,4,5-tribromo-1,2-dimercaptobenzene,
2,3,4,6-tetrachloro-1,5-bis(mercaptomethyl)benzene,
and the like;
polythiol containing heterocyclic ring such as
2-methylamino-4,6-dithiol-sym-triazine,
2-ethylamino-4,6-dithiol-sym-triazine,
2-amino-4,6-dithiol-sym-triazine,
2-morpholino-4,6-dithiol-sym-triazine,
2-cyclohexylamino-4,6-dithiol-sym-triazine,
2-methoxy-4,6-dithiol-sym-triazine,
2-phenoxy-4,6-dithiol-sym-triazine,
2-thiobenzeneoxy-4,6-dithiol-sym-triazine,
2-thiobutyloxy-4,6-dithiol-sym-triazine,
and the like;
aromatic polythiol containing sulfur atom other than mercapto group such as
1,2-bis(mercaptomethylthio)benzene,
1,3-bis(mercaptomethylthio)benzene,
1,4-bis(mercaptomethylthio)benzene,
1,2-bis(mercaptoethylthio)benzene,
1,3-bis(mercaptoethylthio)benzene,
1,4-bis(mercaptoethylthio)benzene,
1,2,3-tris(mercaptomethylthio)benzene,
1,2,4-tris(mercaptomethylthio)benzene,
1,3,5-tris(mercaptomethylthio)benzene,
1,2,3-tris(mercaptoethylthio)benzene,
1,2,4-tris(mercaptoethylthio)benzene,
1,3,5-tris(mercaptoethylthio)benzene,
1,2,3,4-tetrakis(mercaptomethylthio)benzene,
1,2,3,5-tetrakis(mercaptomethylthio)benzene,
1,2,4,5-tetrakis(mercaptomethylthio)benzene,
1,2,3,4-tetrakis(mercaptoethylthio)benzene,
1,2,3,5-tetrakis(mercaptoethylthio)benzene,
1,2,4,5-tetrakis(mercaptoethylthio)benzene,
and the above-mentioned compounds with nuclear alkyl substituent(s),
and the like;
aliphatic polythiol containing sulfur atom other than mercapto group such as
bis(mercaptomethyl)sulfide,
bis(mercaptoethyl)sulfide,
bis(mercaptopropyl)sulfide,
bis(mercaptomethylthio)methane,
bis(2-mercaptoethylthio)methane,
bis(3-mercaptopropylthio)methane,
1,2-bis(mercaptomethylthio)ethane,
1,2-(2-mercaptoethylthio)ethane,
1,2-(3-mercaptopropylthio)ethane,
1,3-bis(mercaptomethylthio)propane,
1,3-bis(2-mercaptoethylthio)propane,
1,3-bis(3-mercaptopropylthio)propane,
1,2,3-tris(mercaptomethylthio)propane,
1,2,3-tris(2-mercaptoethylthio)propane,
1,2,3-tris(3-mercaptopropylthio)propane,
tetrakis(mercaptomethylthiomethyl)methane,
tetrakis(2-mercaptoethylthiomethyl)methane,
tetrakis(3-mercaptopropylthiomethyl)methane,
bis(2,3-dimercaptopropyl)sulfide,
2,5-dimercapto-1,4-dithiane,
2,5-bis(mercaptomethyl)-1,4-dithiane,
bis(mercaptomethyl)disulfide,
bis(mercaptoethyl)disulfide,
bis(mercaptopropyl)disulfide, and the like,
and thioglycolic acid or mercaptopropionic acid esters of the above-mentioned compounds,
hydroxymethylsulfide bis(2-mercaptoacetate),
hydroxymethylsulfide bis(3-mercaptopropionate),
hydroxyethylsulfide bis(2-mercaptoacetate),
hydroxyethylsulfide bis(3-mercaptopropionate),
hydroxypropylsulfide bis(2-mercaptoacetate),
hydroxypropylsulfide bis(3-mercaptopropionate),
hydroxymethyldisulfide bis(2-mercaptoacetate),
hydroxymethyldisulfide bis(3-mercaptopropionate),
hydroxyethyldisulfide bis(2-mercaptoacetate),
hydroxyethyldisulfide bis(3-mercaptopropionate),
hydroxypropyldisulfide bis(2-mercaptoacetate),
hydroxypropyldisulfide bis(3-mercaptopropionate),
2-mercaptoethylether bis(2-mercaptoacetate),
2-mercaptoethylether bis(3-mercaptopropionate),
1,4-dithiane-2,5-diol bis(2-mercaptoacetate),
1,4-dithiane-2,5-diol bis(3-mercaptopropionate),
thioglycolic acid bis(2-mercaptoethylester),
thiodipropionic acid bis(2-mercaptoethylester),
4,4-thiodibutyric acid bis(2-mercaptoethylester),
dithiodiglycolic acid bis(2-mercaptoethylester),
dithiodipropionic acid bis(2-mercaptoethylester),
4,4-dithiodibutyric acid bis(2-mercaptoethylester),
thiodiglycolic acid bis(2,3-dimercaptopropylester),
thiodipropionic acid bis(2,3-dimercaptopropylester),
dithioglycolic acid bis(2,3-dimercaptopropylester),
dithiodipropionic acid (2,3-dimercaptopropylester),
and the like; and
heterocyclic compounds containing sulfur atom other than mercapto group such as
3,4-thiophenedithiol,
2,5 -dimercapto-1,3,4-thiadiazole,
and the like.
Exemplary suitable hydroxythiol compounds include:
2-mercaptoethanol,
3-mercapto-1,2-propanediol,
glycerine di(mercaptoacetate),
1-hydroxy-4-mercaptocyclohexane,
2,4-dimercaptophenol,
2-mercaptohydroquinone,
4-mercaptophenol,
3,4-dimercapto-2-propanol,
1,3-dimercapto-2-propanol,
2,3-dimercapto-1-propanol,
1,2-dimercapto-1,3-butanediol,
pentaerythritol tris(3-mercaptopropionate),
pentaerythritol mono(3-mercaptopropionate),
pentaerythritol bis(3-mercaptopropionate),
pentaerythritol tris(thioglycolate),
pentaerythritol pentakis(3-mercaptopropionate),
hydroxymethyl-tris(mercaptoethylthiomethyl)methane,
1-hydroxyethylthio-3-mercaptoethylthiobenzene,
4-hydroxy-4'-mercaptodiphenylsulfone,
2-(2-mercaptoethylthio)ethanol,
dihydroxyethylsulfide mono(3-mercaptopropionate),
dimercaptoethane mono(salicylate),
hydroxyethylthiomethyl-tris(mercaptoethylthio)methane,
and the like.
Further, there may be used halo-substituted active hydrogen compounds as mentioned above, such as the chloro-substituted or bromo-substituted compounds and the like.
The above-mentioned compounds may be used alone or in combination.
The ratio of the iso(thio)cyanate compound to the active hydrogen compound may be such that the functional group molar ratio,(NCO+NCS)/(OH+SH), is usually 0.5-3.0, preferably 0.5-1.5.
Methods for molding urethane resins are usually casting polymerization method and reaction injection molding method.
The casting polymerization method may be carried out, for example, by dissolving at least one sulfur-containing acid phosphoric ester in a mixture of at least one polyisocyanate compound and at least one active hydrogen compound, if necessary, defoaming the resulting mixture, then pouring the mixture into a mold, and polymerizing the poured mixture by raising the temperature gradually in the range of from -20.degree. to 200.degree. C., preferably from room temperature to 150.degree. C., more preferably from 50.degree. to 120.degree. C. for 0.5-72 hours.
The reaction injection molding method may be carried out, for example, such that an active hydrogen compound and a polyisocyanate compound in which a sulfur-containing acid phosphoric ester is dissolved are separately fed into tanks for a high pressure mixing machine, mixed in the high pressure mixing machine under heating, and then injected into a mold to effect molding.
Epoxy are resins which may be produced by polymerizing a material containing a monomer having an epoxy group. Epoxy resins used in the present invention are not particularly critical.
Exemplary suitable monomers having an epoxy group include:
(1) Amine type epoxy compounds
Epoxy compounds having the group of the following formula, ##STR4## The epoxy compounds may be prepared, for example, by reacting a compound having an amino or amido group with an epihalohydrin such as epichlorohydrin, methylepichlorohydrin, epibromohydrin and the like.
Examples of the epoxy compounds include N,N,N',N'-tetraglycidylaminodiphenylmethane, meta-N,N-diglycidylaminophenylglycidyl ether, N,N,N',N'-tetraglycidyl terephthalamide and the like.
Exemplary suitable compounds having an amino group include:
diaminodiphenylmethane,
m-xylylenediamine,
p-xylylenediamine,
m-aminobenzylamine,
p-aminobenzylamine,
1,3-bisaminomethylcyclohexane,
1,4-bisaminomethylcyclohexane,
1,3-diaminocyclohexane,
1,4-diaminocyclohexane,
m-phenylenediamine,
p-phenylenediamine,
benzylamine,
diaminodiphenylsulfone,
diaminodiphenylether,
diaminodiphenylsulfide,
diaminodiphenylketone,
naphthalenediamine,
aniline,
toluidine,
m-aminophenol,
p-aminophenol,
aminonaphthol,
and the like.
Exemplary suitable compounds having amido group include:
phthalamide,
isophthalamide,
terephthalamide,
benzamide,
toluamide,
p-hydroxybenzamide,
m-hydroxybenzamide,
and the like.
In the case of the compounds having amino group or amido group, when said compounds have hydroxyl, carboxyl, mercapto group or the like capable of reacting with an epihalohydrin other than the amino or amido group, a part or all of the group(s) capable of reacting with an epihalohydrin may react with a epihalohydrin and as a result, the compounds may have an epoxy substituent.
(2) Phenol type epoxy compounds
This type of compounds may be prepared from a phenol type compound and an epihalohydrin.
Examples of this type of compounds are bisphenol A diglycidyl ether and Epitohto YDCN-220 (trade name, supplied by Tohto Kasei).
Exemplary suitable phenol type compounds include:
hydroquinone,
catechol,
resorcin,
bisphenol A,
bisphenol F,
bisphenol sulfone,
brominated bisphenol A,
novolac,
cresol novolac,
tetraphenylethane,
triphenylethane,
and the like.
(3) Alcohol type epoxy compounds
The compounds may be prepared from an alcohol type compound and an epihalohydrin and include
trimethylolpropane triglycidyl ether,
neopentylglycol diglycidyl ether,
and the like.
Exemplary suitable alcohol type compounds include:
polyhydric alcohol such as
ethylene glycol,
diethylene glycol,
triethylene glycol,
polyethylene glycol,
propylene glycol,
dipropylene glycol,
polypropylene glycol,
1,4-butanediol,
1,6-hexanediol,
neopentyl glycol,
dibromoneopentyl glycol,
trimethylotpropane,
glycerin,
pentaerythritol,
polycaprolactone,
polytetramethylene ether glycol,
polybutadiene glycol,
hydrogenated bisphenol A,
cyclohexanedimethanol,
bisphenol A-ethylene oxide adducts,
bisphenol A-propylene oxide adducts,
and the like,
and polyester polyols producible from the polyhydric alcohols and polybasic carboxylic acids.
(4) Epoxidized unsaturated compounds
There may be mentioned epoxidized unsaturated compounds such as
cyclopentadiene epoxide,
epoxidized soybean oil,
epoxidized polybutadiene,
vinylcyclohexene epoxide,
ERL - 4221, ERL - 4234 and ERL - 4299 (trade name, supplied by Union Carbide Co.),
and the like.
(5) Glycidyl ester type epoxy compounds
The compounds may be produced from a carboxylic acid and a epihalohydrin.
Examples thereof are tetrahydrophthalic acid diglycidyl ester and the like.
Exemplary suitable carboxylic acids include:
polybasic carboxylic acid such as
adipic acid,
sebacic acid,
dodecane dicarboxylic acid,
dimer acid,
phthalic acid,
isophthalic acid,
terephthalic acid,
tetrahydrophthalic acid,
methyltetrahydrophthalic acid,
hexahydrophthalic acid,
fatty acid,
nadic acid,
maleic acid,
fumaric acid,
trimellitic acid,
benzene tetracarboxylic acid,
butane tetracarboxylic acid
benzophenone tetracarboxylic acid,
5-(2,5-dioxotetrahydrofuryl)-3-methyl-cyclohexene-1,2dicarboxylic acid,
and the like.
(6) Urethane type epoxy compounds
The compounds may be prepared from polyhydric alcohols as enumerated in (3) above and diisocyanates, glycidols, or 3-hydroxypropylenesulfides.
Exemplary suitable diisocyanates include:
tolylene diisocyanate,
diphenylmethane-4,4'-diisocyanate,
hexamethylene diisocyanate,
isophorone diisocyanate,
xylylene diisocyanate,
naphthalene diisocyanate,
and the like.
(7) Alicyclic epoxy compounds
Examples of the alicyclic epoxy compounds include:
3,4-epoxycyclohexyl-3,4-epoxycyclohexane carboxylate,
vinylcyclohexene dioxide,
2-(3,4-epoxycyclohexyl)-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane,
bis(3,4-epoxycyclohexyl)adipate,
and the like.
(8) Epoxy Compounds having unsaturated double bond
Examples of the compounds include:
glycidyl methacrylate,
glycidyl acrylate,
allylglycidyl ether,
methacrylglycidyl ether,
4-(glycidyloxy)styrene,
.alpha.-methyl-4-(glycidyloxy)styrene,
4-vinylbenzoic acid glycidyl ester,
4-isopropenylbenzoic acid glycidyl ester,
2,2'-divinylbisphenol A glycidyl ether,
2,2'-dipropenylbisphenol A glycidyl ether,.
bis(2-vinylbenzoic acid glycidyl ester)methane,
bis(2-propenylbenzoic acid glycidylester)methane,
epoxysuccinic acid diallyl ester,
3,4-epoxymethacryloyloxytricyclo[5.2.1.0.sup.2.6 ] decane,
and the like.
These epoxy compounds may have a halogen substituent such as chlorine, bromine and the like, and may have episulfide group in place of the epoxy group.
Further, these epoxy compounds may be polymerized alone or in combination.
Furthermore, the epoxy compounds may be polymerized together with known compounds which are generally classified into epoxy resin curing agents, such as alcohols, phenols, thiols, carboxylic acids, carboxylic acid anhydrides, amines, amides, sulfonic acids, isocyanates and the like.
Exemplary suitable curing agents include:
alcohols such as
ethylene glycol,
trimethylolpropane,
and the like;
phenols such as
bisphenol A,
tetrabromobisphenol A,
bis(hydroxyethyl)sulfide,
bis[4-(hydroxyethoxy)phenyl]sulfide,
and the like;
thiols such as
ethanedithiol,
trithioglycerine,
pentaerythritol tetrakis(thioglycolate),
bis(mercaptoethyl)sulfide,
and the like;
carboxylic acids such as
maleic acid,
succinic acid,
thiodiglycolic acid,
3,3'-thiodipropionic acid,
phthalic acid,
p-phenylenedithiodiglycolic acid,
and the like;
carboxylic acid anhydrides such as phthalic anhydride,
hexahydrophthalic anhydride,
trimellitic anhydride,
dodecylsuccinic anhydride,
tetrabromophthalic anhydride,
adduct of methylcyclopentadiene and maleic anhydride,
and the like;
amines such as
diethylene triamine,
triethylene tetramine,
m-phenylene diamine,
diaminodiphenylamine,
diaminodiphenylsulfone,
and the like;
polyamides such as
condensates of an aliphatic acid such as fatty acids, dimer acid, trimer acid and the like with an aliphatic polyamine, and the like;
sulfonic acids such as
m-benzenedisulfonic acid,
bis(4-sulfobenzene)disulfide,
and the like;
isocyanates such as
toluene diisocyanate,
diphenylmethane diisocyanate,
xylylenediisocyanate,
hexamethylene diisocyanate,
isophorone diisocyanate,
and the like;
and curing agents having two or more functional groups such as
2-mercaptoethanol,
thiogylcolic acid,
glycolic acid,
3-(hydroxysulfoxy) propionic acid,
4-aminobenzenesulfonic acid,
4-mercaptobenzenesulfonic acid,
4-aminobenzenethiophenol,
2-mercaptoethylamine,
and the like.
In addition, there may be mentioned complex of boron trifluoride and ethylamine, and salts such as diazonium salts, iodonium salts, bromonium salts, sulfinium salts and the like of boron tetrafluoride,phosphorus hexafluoride and the like.
These epoxy resin curing agents may be used alone or in combination.
When epoxy compounds having an unsaturated double bond are used, there may be effected a copolymerization with vinyl monomers such as acrylic ester, styrene, diallyl phthalate, diethylene glycol methacrylate, diethylene glycol bisallyl carbonate and the like.
When an epoxy resin curing agent is used, the functional group molar ratio, i.e. (reactive group of the curing agent)/(epoxy group of the epoxy compound), is preferably in the range of 0.1-2.0.
Epoxy resin molding is usually carried out by casting polymerization. As the method for polymerization, there may be heat polymerization and photo-polymerization and the method is appropriately selected depending on the epoxy resin to be used.
A general heat polymerization may be carried out by adding a sulfur-containing acid phosphoric ester internal release agent and a polymerization catalyst to an epoxy monomer mixture, pouring the resulting mixture into a mold composed of a resin gasket and metal or glass mold members and heating at 10.degree.-150.degree. C. for 2-30 hours.
A polymerization catalyst for heat polymerization may be appropriately selected from known polymerization catalysts such as tertiary amines, salts thereof, quaternary ammonium salts, imidazoles, tin compounds, peroxides, carboxylic acid metal salts, phosphines, tetraphenyl boron salts depending on the type of the epoxy resin to be used.
Photo-polymerization may be carried out by adding a sulfur-containing acid phosphoric ester internal release agent, a known polymerization catalyst such as peroxides, onium salts of Lewis acid anions, silanol derivative aluminum chelates and the like, if necessary, known additives such as a photo-polymerization initiating auxiliary, sensitizer and the like to an epoxy monomer mixture, pouring the resulting mixture to a mold composed of a resin gasket and glass mold members, and irradiating the poured mixture with a light of b 180-700 nm for 0.5-15 min.
In such casting polymerization, if necessary, there may be added known additives such as ultraviolet light absorber, antioxidant, dye, fillers and the like.
Polyolefin resins are resins producible by radical polymerization of monomers having an unsaturated double bond.
Exemplary suitable monomers having an unsaturated double bond include:
aliphatic olefin compound such as
ethylene,
propylene,
vinyl chloride,
and the like;
aromatic vinyl compounds such as
styrene,
.alpha.-methylstyrene,
p-methylthiostyrene,
m-divinylbenzene,
3,3'-divinylbiphenyl,
2-(4-vinylbenzylthio)ethanol,
isopropenylnaphthalene,
1,4-bis(4-vinylbenzylthio)benzene,
1,2-bis(4-vinylbenzylthio)ethane,
2-(p-vinylphenylthio)benzothiazole,
cinnamic acid p-vinylbenzyl ester,
and the like;
acrylic acid ester compounds such as
methyl acrylate,
methyl methacrylate,
benzyl methacrylate,
cyclohexyl methacrylate,
triphenylmethyl methacrylate,
tribromophenyl methacrylate,
isonorbornyl methacrylate,
2-methacryloyloxymethylthiophene,
2-bicyclo[2.2.1]heptane methacrylate,
ethylene glycol dimethacrylate,
2,2-bis(4-methacryloxyphenyl)propane,
1,1,1-trimethylolpropane triacrylate,
N,N',N"-isocyanurtriacrylate,
bis(2-methacryloylthioethyl)sulfide,
2,5-di(methacryloyloxy)-1,4-dithione,
bis(acryloxymethyl)tricyclo[5.2.1.0.sup.2,6 ]decane,
S-methylthiomethacrylate,
1,2-bis(methacryloylthio)ethane,
bis(methacryloylthioethyl)sulfide,
4,4'-dimercaptodiphenylsulfide dimethacrylate,
and the like;
unsaturated nitrile compounds such as
acrylonitrile,
methacrylonitrile,
cinnamonitrile,
and the like;
acrylamide compounds such as
acrylamide,
methacrylamide,
and the like;
allyl ester compounds such as
diallyl phthalate,
diallyl maleate,
diallyl fumarate,
allyl cinnamate,
allyl benzoate,
and the like;
allyl ether compounds such as
diallyl ether,
bis(allyloxy)ethane,
2,2-bis(4-allyloxyphenyl)propane,
2,2-bis(4-allyloxyethoxyphenyl)propane,
1,4-bis(allylthio)benzene,
diallylidene pentaerythritol,
and the like;
allyl carbonate compounds such as diethylene glycol bisallyl carbonate, .beta.-thiodiglycol bisallyl carbonate, 2,2-bis[4-(2-allyloxycarbonyloxy)ethoxy-3,5-dibromophenyl]propane,
and the like; and
maleimide compounds such as
cyclohexylmaleimide,
n-octylmaleimide,
phenylmaleimide,
chlorophenylmaleimide,
N,N'-(4,4'-diphenylmethane)bismaleimide,
and the like.
These compounds having an unsaturated double bond may be polymerized alone or in combination.
In usual, thermoplastic polyolefin resins are molded by injection molding, and thermosetting polyolefin resins are molded by casting polymerization.
Conditions of casting polymerization are optionally selected depending on the monomers to be used. Usually, a sulfur-containing acid phosphoric ester and a radical polymerization initiator are added to the monomers, and if necessary, a defoaming treatment is effected under reduced pressure, and then the mixture is poured into a mold. Then, a radical polymerization is carried out by means of heat, microwaves, infrared ray, ultraviolet ray or the like.
Exemplary suitable radical polymerization initiators usable for polymerization by means of heat, microwave or infrared rays include:
azo compounds such as
2,2'-azobisisobutyronitrile,
2,2'-azobisisovaleronitrile,
2,2'-azobis(2,4-dimethylvaleronitrile)
and the like;
ketone peroxides such as
methyl ethyl ketone peroxide,
methyl isobutyl ketone peroxide,
cyclohexanone peroxide,
acetylacetone peroxide,
and the like;
diacyl peroxides such as
isobutyryl peroxide,
2,4-dichlorobenzoyl peroxide,
o-methylbenzoyl peroxide,
lauroyl peroxide,
p-chlorobenzoyl peroxide,
and the like;
hydroperoxides such as
2,4,4-trimethylpentyl-2-hydroperoxide,
diisopropylbenzene peroxide
cumene hydroperoxide,
t-butylperoxide,
and the like;
dialkyl peroxides such as
dicumyl peroxide,
t-butylcumyl peroxide,
di-t-butyl peroxide,
tris(t-butyl peroxide)triazine,
and the like;
peroxyketals such as
1,1-di-t-butylperoxycyclohexane,
2,2-di-(t-butylperoxy)butane,
and the like;
alkyl peresters such as
t-butylperoxypivalate,
t-butylperoxy-2-ethylhexanoate,
t-butylperoxyisobutyrate,
di-t-butylperoxyhexahydroterephthalate,
di-t-butylperoxyazelate,
t-butylperoxy-3,5,5-trimethylhexanoate,
t-butylperoxyacetate,
t-butylperoxybenzoate,
di-t-butylperoxytrimethyladipate,
and the like; and
percarbonates such as
diisopropyl peroxydicarbonate,
di-sec-butyl peroxydicarbonate,
t-butyl peroxyisopropylcarbonate,
and the like.
Exemplary suitable radical polymerization initiators for polymerization by means of ultraviolet rays include:
carbonyl compounds such as
acetophene,
2,2-dimethoxy-2-phenylacetophenone,
2,2-diethoxyacetophenone,
4'-isopropyl-2-hydroxy-2-methylpropiophenone,
2-hydroxy-2-methylpropiophenone,
4,4'-bis(diethylamino)benzophenone,
benzophenone,
methyl(o-benzoyl)benzoate,
1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime,
1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime,
benzoin,
benzoin methyl ether,
benzoin ethyl ether,
benzoin isopropyl ether,
benzoin butyl ether,
benzoin octyl ether,
benzil,
benzil dimethylketal,
benzil diethylketal,
diacetyl,
and the like;
anthraquinone or thioxanthone derivatives such as
methylanthraquinone,
chloroanthraquinone,
chlorothioxanthone,
2-methylthioxanthone,
2-isopropylthioxanthone,
and the like; and
sulfur compounds such as
diphenyl disulfide,
dithiocarbamate,
and the like.
The amount of the radical polymerization initiator may be optionally selected depending on the type of radical polymerization initiator, type of monomers to be used, and the like. It is usually 0.001-10 mol %, preferably 0.1-3 mol % based on the monomer to be used.
When the amount of the radical polymerization initiator is less than 0.001 mol %, the polymerization does not substantially proceed. When the amount exceeds10 mol %, such large amount is not economical, and moreover, sometimes foaming occurs during polymerization or the molecular weight of the resulting cured product is markedly small.
In the case of casting polymerization, the monomer composition may be directly polymerized and cured, or may be polymerized and cured after preliminary polymerization, so as to adjust the viscosity or decrease shrinkage upon polymerization, depending on the purpose.
When transparency of the molded product is not particularly required, various fillers may be compounded, if necessary.
As the fillers, there may be mentioned glass fibers, alumina fibers, carbon fibers, aramid fibers and the like, and powder-like fillers such as silica, alumina, barium sulfate, titanium oxide and the like. In addition, there may be used flame retardants, dyes, pigments and the like.
Polymerization temperature and polymerization time for casting polymerization can not be unanimously determined since these factors vary depending on the types of radical polymerization initiators used and amounts thereof, but the polymerization temperature is usually 0.degree.-150.degree. C., preferably 20.degree.-120.degree. C.
In the case of heat polymerization, the polymerization temperature is gradually raised usually over 10-30 hours, and in the case of polymerization using ultraviolet rays, the irradiation is effected for 0.5-10 min. to complete the polymerization.
Among polyolefin resins, as an example of the resins which can be injection-molded, thermoplastic acrylic resins can be shown, and the acrylic resins may be homopolymers of an acrylic monomer, copolymers of acrylic monomers, or copolymers of an acrylic monomer and other olefin monomers.
Examples of acrylic monomers may be acrylic acid compounds and methacrylic acid compounds.
Exemplary suitable acrylic acid compounds include:
acrylic acid alkyl esters such as
methyl acrylate,
ethyl acrylate,
butyl acrylate,
2-ethylhexyl acrylate,
and the like;
acrylic acid cycloalkyl esters such as
cyclohexyl acrylate,
bornyl acrylate,
menthyl acrylate,
adamantyl acrylate,
tricyclodecyl acrylate,
and the like;
acrylic acid aromatic esters such as
phenyl acrylate,
benzyl acrylate,
naphthyl acrylate,
and the like;
acrylic acid halo-substituted aromatic esters such as
fluorophenyl acrylate,
chlorophenyl acrylate,
and the like;
acrylic acid halogenated alkyl esters such as
fluoromethyl acrylate,
chloroethyl acrylate,
bromoethyl acrylate,
and the like;
acrylic acid hydroxyalkyl esters; and
thioacrylic acid S-alkyl esters such as
S-methyl thioacrylate and the like.
Exemplary suitable methacrylic acid compounds include:
methacrylic acid alkyl esters such as
methyl methacrylate,
ethyl methacrylate,
butyl methacrylate,
2-ethylhexyl methacrylate,
and the like;
methacrylic acid cycloalkyl esters such as
cyclohexyl methacrylate,
bornyl methacrylate,
menthyl methacrylate,
adamantyl methacrylate,
tricyclodecyl methacrylate,
and the like;
methacrylic acid aromatic esters such as
phenyl methacrylate,
benzyl methacrylate,
naphthyl methacrylate,
and the like;
methacrylic acid halo-substituted aromatic esters such as
fluorophenyl methacrylate,
chlorophenyl methacrylate,
and the like;
methacrylic acid halogenated alkyl esters such as
fluoromethyl methacrylate,
chloroethyl methacrylate,
bromoethyl methacrylate,
and the like;
hydroxyalkyl methacrylates;
and
thiomethacrylic acid S-alkyl esters such as
S-methyl thiomethacrylate
and the like.
As other olefin monomers there may be mentioned the following compounds.
As vinyl compounds, there may be mentioned: aromatic vinyl compounds such as
styrene,
.alpha.-methylstyrene,
.alpha.-ethylstyrene,
fluorostyrene,
chlorostyrene,
bromostyrene,
methylstyrene,
methylthiostyrene,
and the like; and
cyanated vinyl compounds such as acrylonitrile, methacrylonitrile and the like.
As unsaturated dibasic acids and derivatives thereof, of, there may be mentioned N-substituted maleimide such as
N-methylmaleimide,
N-ethylmaleimide,
N-propylmaleimide,
N-octylmaleimide,
N-cyclohexylmaleimide,
N-phenylmaleimide,
and the like,
dipropyl maleate,
dibutyl maleate,
dipropyl fumarate,
dibutyl fumarate,
maleic anhydride,
and the like.
As unsaturated fatty acids and derivatives thereof, there may be mentioned acrylamide,
N,N-dimethylacrylamide, and the like.
Injection molding conditions may be optionally selected depending on the type of the resin used. In general, a mixture of an acrylic resin and a sulfur-containing acid phosphoric ester is melted at a resin temperature of 220.degree.-320.degree. C. and injected into a mold at 50.degree.-150.degree. C. with an extruder, and after completion of the molding, the molded product is released.
Further, according to the present invention, known additives such as antioxidant, ultraviolet ray absorber, photo-stabilizer, colorant, fillers and the like may be used depending on the purpose.
Polyene-polythiol resins are resins producible by addition polymerization of a polyene compound having at least two unsaturated double bonds in a molecule and a polythiol compound having at least two mercapto groups in a molecule.
Exemplary suitable polyene compounds for the polyene-polythiol resins include:
aromatic vinyl compounds such as m-divinylbenzene,
3,3'-divinylbiphenyl,
1,4-bis(4-vinylbenzylthio)benzene,
1,2-bis(4-vinylbenzylthio)ethane,
and the like;
acrylic acid ester compounds such as
ethylene glycol dimethacrylate,
ethylene glycol diacrylate,
2,2-bis(4-methacryloxyphenyl)propane,
bis(2-methacryloylthioethyl)sulfide,
2,5-di(methacryloyloxy)-1,4-dithiane,
1,2-bis(acryloylthio)ethane,
bis(4-methacryloylthiophenyl)sulfide,
and the like;
allyl ester compounds such as diallyl phthalate,
diallyl maleate,
diallyl fumarate,
allyl cinnamate,
and the like;
allyl ether compounds such as
diallyl ether,
diallyl sulfide,
bis(allyloxy)ethane,
2,2-bis(4-allyloxyphenyl)propane,
2,2-bis(4-allyloxyethoxyphenyl)propane,
1,4-bis(allylthio)benzene,
diallylidene pentaerythritol,
diallylidene-2,2,6,6-tetramethylol cyclohexane,
and the like; and
allyl carbonate compounds such as
diethylene glycol bis(allyl carbonate),
.beta.-thiodiglycol bisallyl carbonate,
2,2-bis[4-(allyloxycarbonyloxy)phenyl]propane,
and the like.
These polyene compounds may be used alone or in combination.
Examples of polythiol compounds used for polyene-polythiol resins may be as mentioned below.
aliphatic polythiol such as
methanedithiol,
1,2-ethanedithiol,
1,1-propanedithiol,
1,2-propanedithiol,
1,3-propanedithiol,
2,2-propanedithiol,
1,6-hexanedithiol,
1,2,3-propanetrithiol,
1,1-cyclohexanedithiol,
1,2-cyclohexanedithiol,
2,2-dimethylpropane-1,3-dithiol,
3,4-dimethoxybutane-1,2-dithiol,
2-methylcyclohexane-2,3-dithiol,
bicyclo[2.2.1]hepta-exo-cis-2,3-dithiol,
1,1-bis(mercaptomethyl)cyclohexane,
thiomalic acid bis(2-mercaptoethylester),
2,3-dimercaptosuccinic acid (2-mercaptoethylester),
2,3-dimercapto-1-propanol(2-mercaptoacetate),
2,3-dimercapto-1-propanol(3-mercaptoacetate)
diethylene glycol bis(2-mercaptoacetate),
diethylene glycol bis(3-mercaptopropionate),
1,2-dimercaptopropyl methyl ether,
2,3-dimercaptopropyl methyl ether,
2,2-bis(mercaptomethyl)-1,3-propanedithiol,
bis(2-mercaptoethyl) ether,
ethylene glycol bis(2-mercaptoacetate),
ethylene glycol bis(3-mercaptopropionate),
trimethylolpropane bis(2-mercaptopropionate)
trimethylolpropane bis(3-mercaptopropionate),
pentaerythritol tetrakis(2-mercaptoacetate),
pentaerythritol tetrakis(3-mercaptopropionate),
bis(mercaptomethyl)sulfide,
bis(mercaptoethyl)sulfide,
bis(mercaptopropyl)sulfide,
bis(mercaptomethylthio)methane,
bis(2-mercaptoethylthio)methane,
bis(3-mercaptopropylthio)methane,
1,2-bis(mercaptomethylthio)ethane,
1,2-bis(mercaptoethylthio)ethane,
1,2-bis(mercaptopropylthio)ethane,
1,3-bis(mercaptomethylthio)propane,
1,3-bis(2-mercaptoethylthio)propane,
1,3-bis(3-mercaptopropylthio)propane,
1,2,3-tris(mercaptomethylthio)propane,
1,2,3-tris(2-mercaptoethylthio)propane,
1,2,3-tris(3-mercaptopropylthio)propane,
tetrakis(mercaptomethylthiomethyl)methane,
tetrakis(2-mercaptoethylthiomethyl)methane,
tetrakis(3-mercaptopropylthiomethyl)methane,
bis(2,3-dimercaptopropyl)sulfide,
2,5-dimercapto-1,4-dithiane,
2,5-bis(mercaptomethyl)-1,4-dithiane,
bis(mercaptomethyl)disulfide,
bis(mercaptoethyl)disulfide,
bis(mercaptopropyl)disulfide, and the like,
and thioglycolic acid or mercaptopropionic acid esters of the above-mentioned compounds,
hydroxymethylsulfide bis(2-mercaptoacetate),
hydroxymethylsulfide bis(3-mercaptopropionate),
hydroxyethylsulfide bis(2-mercaptoacetate),
hydroxyethylsulfide bis(3-mercaptopropionate),
hydroxypropylsulfide bis(2-mercaptoacetate),
hydroxypropylsulfide bis(3-mercaptopropionate),
hydroxymethyldisulfide bis(2-mercaptoacetate),
hydroxymethyldisulfide bis(3-mercaptopropionate),
hydroxyethyldisulfide bis(2-mercaptoacetate),
hydroxyethyldisulfide bis(3-mercaptopropionate),
hydroxypropyldisulfide bis(2-mercaptoacetate),
hydroxypropyldisulfide bis(3-mercaptopropionate),
2-mercaptoethylether bis(2-mercaptoacetate),
2-mercaptoethylether bis(3-mercaptopropionate),
1,4-dithiane-2,5-diol bis(2-mercaptoacetate),
1,4-dithiane-2,5-diol bis(3-mercaptopropionate),
thioglycolic acid bis(2-mercaptoethylester),
thiodipropionic acid bis(2-mercaptoethylester),
4,4-thiodibutyric acid bis(2-mercaptoethylester),
dithiodiglycolic acid bis(2-mercaptoethylester),
dithiodipropionic acid bis(2-mercaptoethylester),
4,4-dithiodibutyric acid bis(2-mercaptoethylester),
thiodiglycolic acid bis(2,3-dimercaptopropylester),
thiodipropionic acid bis(2,3-dimercaptopropylester),
dithioglycolic acid bis(2,3-dimercaptopropylester),
dithiodipropionic acid bis(2,3-dimercaptopropylester),
and the like;
aromatic polythiol such as
1,2-dimercaptobenzene,
1,3-dimercaptobenzene,
1,4-dimercaptobenzene,
1,2-bis(mercaptomethyl)benzene,
1,3-bis(mercaptomethyl)benzene,
1,4-bis(mercaptomethyl)benzene,
1,2-bis(mercaptoethyl)benzene,
1,3-bis(mercaptoethyl)benzene,
1,4-bis(mercaptoethyl)benzene,
1,2-bis(mercaptomethyleneoxy)benzene,
1,3-bis(mercaptomethyleneoxy)benzene,
1,4-bis(mercaptomethyleneoxy)benzene,
1,2-bis(mercaptoethyleneoxy)benzene,
1,3-bis(mercaptoethyleneoxy)benzene,
1,4-bis(mercaptoethyleneoxy)benzene,
1,2,3-trimercaptobenzene,
1,2,4-trimercaptobenzene,
1,3,5-trimercaptobenzene,
1,2,3-tris(mercaptomethyl)benzene,
1,2,4-tris(mercaptomethyl)benzene,
1,3,5-tris(mercaptomethyl)benzene,
1,2,3-tris(mercaptoethyl)benzene,
1,2,4-tris(mercaptoethyl)benzene,
1,3,5-tris(mercaptoethyl)benzene,
1,2,3-tris(mercaptomethyleneoxy)benzene,
1,2,4-tris(mercaptomethyleneoxy)benzene,
1,3,5-tris(mercaptomethyleneoxy)benzene,
1,2,3-tris(mercaptoethyleneoxy)benzene,
1,2,4-tris(mercaptoethyleneoxy)benzene,
1,3,5-tris(mercaptoethyleneoxy)benzene,
1,2,3,4-tetramercaptobenzene,
1,2,3,5-tetramercaptobenzene,
1,2,4,5-tetramercaptobenzene,
1,2,3,4-tetrakis(mercaptomethyl)benzene,
1,2,3,5-tetrakis(mercaptomethyl)benzene,
1,2,4,5-tetrakis(mercaptomethyl)benzene,
1,2,3,4-tetrakis(mercaptoethyl)benzene,
1,2,3,5-tetrakis(mercaptoethyl)benzene,
1,2,4,5-tetrakis(mercaptoethyl)benzene,
1,2,3,4-tetrakis(mercaptomethyleneoxy)benzene,
1,2,3,5-tetrakis(mercaptomethyleneoxy)benzene,
1,2,4,5-tetrakis(mercaptomethyleneoxy)benzene,
1,2,3,4-tetrakis(mercaptoethyleneoxy)benzene,
1,2,3,5-tetrakis(mercaptoethyleneoxy)benzene,
1,2,4,5-tetrakis(mercaptoethyleneoxy)benzene,
2,2'-dimercaptobiphenyl,
4,4'-dimercaptobiphenyl,
4,4'-dimercaptobibenzyl,
2,5-toluenedithiol,
3,4-toluenedithiol,
1,4-naphthalenedithiol,
1,5-naphthalenedithiol,
2,6-naphthalenedithiol,
2,7-naphthalenedithiol,
2,4-dimethylbenzene-1,3-dithiol,
4,5-dimethylbenzene-1,3-dithiol,
9,10-anthracenedimethanethiol,
1,3-di(p-methoxyphenyl)propane-2,2-dithiol,
1,3-diphenylpropane-2,2-dithiol,
phenylmethane-1,1-dithiol,
2,4-di(p-mercaptophenyl)pentane,
1,2-bis(mercaptomethylthio)benzene,
1,3-bis(mercaptomethylthio)benzene,
1,4-bis(mercaptomethylthio)benzene,
1,2-bis(mercaptoethylthio)benzene,
1,3-bis(mercaptoethylthio)benzene,
1,4-bis(mercaptoethylthio)benzene,
1,2,3-tris(mercaptomethylthio)benzene,
1,2,4-tris(mercaptomethylthio)benzene,
1,3,5-tris(mercaptomethylthio)benzene,
1,2,3-tris(mercaptoethylthio)benzene,
1,2,4-tris(mercaptoethylthio)benzene,
1,3,5-tris(mercaptoethylthio)benzene,
1,2,3,4-tetrakis(mercaptomethylthio)benzene,
1,2,3,5-tetrakis(mercaptomethylthio)benzene,
1,2,4,5-tetrakis(mercaptomethylthio)benzene,
1,2,3,4-tetrakis(mercaptoethylthio)benzene,
1,2,3,5-tetrakis(mercaptoethylthio)benzene,
1,2,4,5-tetrakis(mercaptoethylthio)benzene,
and the like,
and the above-mentioned compounds which are nuclear-alkylated;
and
heterocyclic polythiol compounds such as
2-methylamino-4,6-dithiol-sym-triazine,
2-ethylamino-4,6-dithiol-sym-triazine,
2-amino-4,6-dithiol-sym-triazine,
2-morpholino-4,6-dithiol-sym-triazine,
2-cyclohexylamino-4,6-dithiol-sym-triazine,
2-methoxy-4,6-dithiol-sym-triazine,
2-phenoxy-4,6-dithiol-sym-triazine,
2-thiobenzeneoxy-4,6-dithiol-sym-triazine,
3,4-thiophenedithiol,
Bismuthiol,
2,5-dimercapto-1,3,4-thiadiazole and the like.
Further, these polythiol compounds may have substituents, for example, halogen such as chloro, bromo, and the like, hydroxyl, amino and the like.
These polythiol compounds may be used alone or in combination.
The mixing ratio of the polythiol compound to the polyene compound is such that the functional group molar ratio, (mercapto group/double bond), is preferably 0.001-1.2, more preferably 0.01-1.0.
When the ratio is larger than 1.2, the hardness of the resulting resin is not sufficient. When the ratio is smaller than 0.001, various good physical properties such as high refractive index, low water absorption and the like can not be sufficiently exhibited.
For purposes of controlling the crosslinking density, monoolefin compounds such as methyl acrylate, styrene and the like or monothiol compounds such as octyl mercaptan, dodecyl mercaptan and the like may be added to a mixture of polyene compounds and polythiol compounds.
Casting polymerization conditions may be optionally selected depending on the monomers to be used. Usually, a sulfur-containing acid phosphoric ester and a radical polymerization initiator are added to a monomer to be used, if necessary, the resulting mixture is defoamed under reduced pressure, and poured into a mold. Then, a radical polymerization is carried out by means of heat, microwave, infrared rays, ultraviolet rays or the like.
Exemplary suitable radical polymerization initiators usable for polymerization by means of heat, microwave or infrared rays include:
azo compounds such as
2,2'-azobisisobutyronitrile,
2,2'-azobisisovaleronitrile,
2,2'-azobis(2,4-dimethylvaleronitrile) and the like;
ketone peroxides such as
methyl ethyl ketone peroxide,
methyl isobutyl ketone peroxide,
cyclohexanone, peroxide,
acetylacetone peroxide,
and the like;
diacyl peroxides such as
isobutyryl peroxide,
2,4-dichlorobenzoyl peroxide,
o-methylbenzoyl peroxide,
lauroyl peroxide,
p-chlorobenzoyl peroxide,
and the like;
hydroperoxides such as
2,4,4-trimethylpentyl-2-hydroperoxide,
diisopropylbenzene peroxide
cumene hydroperoxide,
t-butylperoxide,
and the like;
dialkyl peroxides such as
dicumyl peroxide,
t-butylcumyl peroxide,
di-t-butyl peroxide,
tris(t-butyl peroxide)triazine,
and the like;
peroxyketals such as
1,1-di-t-butylperoxycyclohexane,
2,2-di-(t-butylperoxy)butane,
and the like;
alkyl peresters such ss
t-butylperoxypivalate,
t-butylperoxy-2-ethylhexanoate,
t-butylperoxyisobutyrate,
di-t-butylperoxyhexahydroterephthalate,
di-t-butylperoxyazelate,
t-butylperoxy-3,5,5-trimethylhexanoate,
t-butylperoxyacetate,
t-butylperoxybenzoate,
di-t-butylperoxytrimethyladipate,
and the like; and
percarbonates such as
diisopropyl peroxydicarbonate,
di-sec-butyl peroxydicarbonate,
t-butyl peroxyisopropylcarbonate,
and the like.
Exemplary, suitable radical polymerization initiators for polymerization by means of ultraviolet rays include:
carbonyl compounds such as
acetophene,
2,2-dimethoxy-2-phenylacetophenone,
2,2-diethoxyacetophenone,
4'-isopropyl-2-hydroxy-2-methylpropiophenone,
2-hydroxy-2-methylpropiophenone,
4,4'-bis(diethylamino)benzophenone,
benzophenone,
methyl(o-benzoyl)benzoate,
1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime,
1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime,
benzoin,
benzoin methyl ether,
benzoin ethyl ether,
benzoin isopropyl ether,
benzoin butyl ether,
benzoin octyl ether,
benzil,
benzil dimethylketal,
benzil diethylketal,
diacetyl,
and the like;
anthraquinone or thioxanthone derivatives such as
methylanthraquinone,
chloroanthraquinone,
chlorothioxanthone,
2-methylthioxanthone,
2-isopropylthioxanthone,
and the like; and
sulfur compounds such as
diphenyl disulfide,
dithiocarbamate,
and the like.
The amount of the radical polymerization initiator may be optionally selected depending on the type of radical polymerization initiator, type of monomers to be used, and the like. It is usually 0.001-10 mol %, preferably 0.1-3 mol % based on the monomer to be used.
When the amount of the radical polymerization initiator is less than 0.001 mol %, the polymerization does not substantially proceed. When the amount exceeds 10 mol %, such large amount is not economical, and moreover, sometimes foaming occurs during polymerization or the molecular weight of the resulting cured product is markedly small.
In the case of casting polymerization, the monomer composition may be directly polymerized and cured, or may be polymerized and cured after preliminary polymerization, so as to adjust the viscosity or decrease shrinkage upon polymerization, depending on the purpose.
When transparency of the molded product is not particularly required, various fillers may be compounded, if necessary.
As the fillers, there may be mentioned glass fibers, alumina fibers, carbon fibers, aramid fibers and the like, and powder-like fillers such as silica, alumina, barium sulfate, titanium oxide and the like. In addition, there may be used flame retardants, dyes, pigments and the like.
Polymerization temperature and polymerization time for casting polymerization can not be unanimously determined since these factors vary depending on the types of radical polymerization initiators used and amounts thereof, but the polymerization temperature is usually 0.degree.-150.degree. C., preferably 20.degree.-120.degree. C.
In the case of heat polymerization, the polymerization temperature is gradually raised usually Over 10-30 hours, and in the case of polymerization using ultraviolet rays, the irradiation is effected for 0.5-10 min. to complete the polymerization.
As polycarbonate resins, there may be mentioned homopolymers or copolymers producible by the reaction of dihydric phenols with carbonylation agents such as phosgene, diphenylcarbonate and the like. The polymers may be branched or have long chain alkyl groups at the ends. The average molecular weight may be about 12,000-30,000.
Further, the following modified polycarbonate resins may be used:
modified polycarbonate resins (produced by using a comonomer, a bisphenol having a carbon-carbon unsaturated double bond or vinylphenol as an end terminator) grafted with styrene,
polycarbonate resins having partly ester bonds prepared by using terephthalic acid chloride or isophthalic acid chloride as a part of phosgene, and
modified polystyrene graft-polymerized with polycarbonate resins (phenolic hydroxyl groups or the like have been introduced into the polystyrene as comonomers).
The present invention may be effectively used for reinforced resin compositions composed of polycarbonate resins reinforced with glass fibers, carbon fibers or the like, and resin compositions composed of polycarbonate resin and ABS resin, polyester resin such as polyethylene terephthalate, PMMA resin or the like.
As divalent phenols, there may be mentioned:
2,2-bis(4-hydroxyphenyl)propane,
bis(4-hydrophenyl)methane,
1,2-bis(4-hydroxyphenyl)ethane,
2,2-bis(4-hydroxyphenyl)butane,
1,1-bis(4-hydroxyphenyl)-1-phenylmethane,
1,1-bis(4-hydroxyphenyl-1,1-diphenyl)methane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
bis(4-hydroxyphenyl)ether,
bis(4-hydroxyphenyl)sulfide,
bis(4-hydroxyphenyl)sulfone,
and the like.
The phenyl groups may have lower alkyl group or halogen atom as a substituent.
According to the present invention, there may be added known antioxidant, ultraviolet ray absorber, colorant, fillers or the like, depending on the purposes.
As polyester resins, there may be mentioned thermosetting polyester resins such as alkyd resins, unsaturated polyester resins and the like, and thermoplastic polyester resins such as polyethylene terephthalate and the like.
Polyester resins are producible by condensing polybasic acids with polyols.
Exemplary suitable polybasic acids include:
phthalic anhydride,
isophthalic acid,
maleic acid,
fumaric acid,
sebacic acid,
adipic acid,
citric acid,
tartaric acid,
malic acid,
diphenic acid,
1,8-naphthalic acid,
terephthalic acid,
and the like.
Exemplary suitable polyols include:
glycerine,
pentaerythritol,
ethylene glycol,
diethylene glycol,
trimethylolpropane,
and the like.
Depending on the purposes, there may be added known antioxidant, ultraviolet ray absorber, colorant, fillers and the like.
According to the present invention, the internal release agent, i.e. the particular sulfur-containing acid phosphoric ester, can improve releasability of molded products in resin molding procedures and in addition, sufficiently satisfy the transparency of the molded product when a transparent resin is molded.
The particular sulfur-containing acid phosphoric ester has a good compatibility with various resins or monomers, and therefore, is easily used as an internal release agent.
The present invention is particularly useful for molding optical products such as plastic lens and the like which require surface accuracy and transparency.
The method for molding resins using the particular sulfur-containing acid phosphoric ester as an internal release agent according to the present invention can improve the releasability between a molded resin product and a mold, and the resulting molded product is substantially free from strains caused by stress upon releasing, and the resin does not dirty the surface of the mold. In addition, in the case of molding a transparent resin, substantially the transparency is not adversely affected.
The present invention is now more particularly described with reference to the following examples which are for the purpose of illustration only and are intended to imply no limitation thereon.
In Examples 1-38 and Comparative Examples 1-76, the urethane resins were molded into a flat plate of 70 mm in diameter and 9 mm in thickness.
Evaluation of releasability was made by inserting a Teflon wedge between the molded product and the mold, and when released easily, it was designated as ".circle.", when released though there was some resistance, it was designated as ".DELTA." and when not released, it was designated as "X".
The turbidity was determined by measuring the haze value of a flat plate of urethane resin of 9 mm thick by using Digital Haze Computer HGM-2DP manufactured by Suga Shikenki K.K. according to JIS K 7105, 6.4.

EXAMPLES 1-38
A mixture of a polyisocyanate compound, an active hydrogen compound, and a sulfur-containing acid phosphoric ester as shown in Table 1 was poured into a glass mold and the temperature was gradually raised from 25.degree. C. to 120.degree. C. over 48 hours to carry out a casting molding.
Table1 shows releasability and haze value of the urethane resin flat plate after polymerization. In each example, releasing was easily effected and the urethane flat plate had a small haze and was good.
COMPARATIVE EXAMPLES 1-76
Each of the procedures of Examples 1-38 was repeated except that a known internal release agent was used, or no release agent was used in place of using the sulfur-containing acid phosphoric ester, and the result was shown in Table 1.
As compared with the sulfur-containing acid phosphoric esters of the present invention, when known internal release agents were used, the releasing was not easy, and the haze values of urethane flat plates were high. When a release agent was not used, releasing was not possible and therefore, the haze value could not be measured.
TABLE 1 Polyisocyanate Active hydrogen compound Internal release agent Releasabi lity Haze value (%) Example 1ComparativeExample 1ComparativeExample 2 OCN(CH.sub.2).s ub.6 NCO0.3 mol. ##STR5## Dimethyl thiophosphate0.01 wt %Unidain DS-401 .RTM.(fluorine type,manuf. by DaikinKogyo) 0.01 wt %None .largecircle..D ELTA.X 0.11.5 Example 2ComparativeExample 3ComparativeExample 4 ##STR6## ##STR7## Diethyl thiophosphate0.05 wt % Q2 .multidot. 120A .RTM. (silicontype, manuf. byDow Chemical)0.05 wt %None .largecircle..DELTA.X 0.1 3.2 Example 3ComparativeExample 5ComparativeExample 6 ##STR8## ##STR9## Dioctyl thiophosphate1.0 wt %Zinc stearte1.0 wt %None .largecircle..DELT A.X 0.228.1 Example 4ComparativeExample 7Comparative Example 8 (SCH.sub.2 CH.sub.2 NCO).sub.20.3 mol. ##STR10## Dimethyl dithiophosphate0.2 wt %Dioctyl phosphate0.2 wt %None .largecirc le..DELTA.X 0.1 1.5 Example 5 (SCH.sub.2 CH.sub.2 NCO).sub.2 HO(CH.sub.2).sub.2 S(CH.sub.2).sub.2 OH Diisopropyl dithiophosphate .largecircle. 0.1 0.3 mol. 0.3 mol. 0.8 wt % Comparative Trimethyl octyl .DELTA. 10.1 Example 9 ammonium chloride 0.8 wt % Comparative None X Example 10 Example 6ComparativeExample 11ComparativeExample 12 ##STR11## HO(CH.sub.2).sub.2 S(CH.sub.2).sub.2 SH0.3 mol. Dioctyl dithiophosphate5.0 wt %Dimethyl phosphate5.0 wt %None .largecircle..DELTA.X 0.32.7 Example 7ComparativeExample 13ComparativeExample 14 ##STR12## ##STR13## Dimethyl thiophosphate0.05 wt %Dimethyl polysiloxane0.05 wt %None .largecircle..DELTA.X 0.12.1 Example 8ComparativeExample 15ComparativeExample 16 ##STR14## ##STR15## Dipropyl thiophosphate0.5 wt %Stearyl glycerolether 0.5 wt %None .largecircle..DELTA.X 0.11.8 Example 9ComparativeExample 17ComparativeExample 18 ##STR16## ##STR17## Dibutyl thiophosphate2.0 wt %Dibutyl phosphate2.0 wt %None .largecircle. .DELTA.X 0.21.2 Example 10ComparativeExample 19ComparativeExample 20 ##STR18## ##STR19## Dimethyl dithiophosphate0.1 wt %Gafac RD-510 .RTM.(Phosphoric acid ester,manuf. by TohoKagaku Kogyo)None .largecircle..DELTA.X 0.11.0 Example 11ComparativeExample 21ComparativeExample 22 ##STR20## C(CH.sub.2 SCH.sub.2 CH.sub.2 0 SH).sub.40.15 mol. Diethyl dithiophosphate.05 wt %Dioctyl sodiumphosphat e0.05 wt %None .largecircle..DELTA.X 0.17.3 Example 12ComparativeExample 23ComparativeExample 24 ##STR21## HO(CH.sub.2).sub.4 OH0.3 mol. Dibutyl dithiophosphate1.0 wt %Trimethyl cetylammonium chloride1.0 wt%None .largecircle..DELTA.X 0.211.4 Example 13ComparativeExample 25ComparativeExample 26 ##STR22## ##STR23## Dimethyl thiophosphate0.05 wt %Diethyl thiophosphate0.05 wt %Dioctyl phosphate0.1 wt %None .largecircle..DELTA.X 0.11.1 Example 14ComparativeExample 27ComparativeExample 28 ##STR24## ##STR25## Diethyl thiophosphate0.05 wt%Diethyl dithiophosphate0.05 wt %Diethyl phophate0.8 wt %None .largecircle..DELTA.X 0.10.9 Example 15 SCN(CH.sub.2).sub.4 NCS C(CH.sub.2 SCH.sub.2 CH.sub.2 OH).sub.4 Dimethyl thiophosphate .largecircle. 0.1 0.4 mol. 0.2 mol. 0.01 wt % Comparative Unidain DS-401 .RTM. .DELTA. 1.2 Example 29 (fluorine type, manuf. by Daikin Kogyo) 0.01 wt % Comparative None X Example 30 Example 16ComparativeExample 31ComparativeExample 32 SCN(CH.sub.2).sub.2 S(CH.sub.2).sub.2 NCS0.4 mol. ##STR26## Diethyl thiophosphate0.03 wt %Q2 .multidot. 120A .RTM. (silicontype, manuf. byDow Chemical)0.05 wt %None .largecircle..DELTA.X 0.12.6 Example 17 SCN(CH.sub.2).sub.2 SS(CH.sub.2).sub.2 NCS C(CH.sub.2 SH).sub.4 Dioctyl thiophosphate .largecircle. 0.2 0.3 mol. 0.3 mol. 1.0 wt % Comparative Trimethyl octyl .DELTA. 12.7 Example 33 ammonium chloride 1.0 wt % Comparative None X Example 34 Example C 18omparativeExample 35 ComparativeExample 36 ##STR27## ##STR28## Dimethyl dithiophosphate0.5 wt %Dimethyl phosphate1.0 wt %None .largecir cle..DELTA.X 0.10.8 Example 19ComparativeExample 37ComparativeExample 38 SCN(CH.sub.2).sub.4 NCS0.3 mol.OCN(CH.sub.2).sub.4 NCS0.1 mol. ##STR29## Dibutyl dithiophosphate0.5 wt %Dibutyl thiophosphate0.5 wt %Zinc stearate1.0 wt %None .largecircle..DELTA.X 0.220. 9 Example 20ComparativeExample 39ComparativeExample 40 ##STR30## ##STR31## Dioctyl dithiophosphate5.0 wt %Stearyl glycerolether 5.0 wt %None .largecircle..DELTA.X 0.43.9 E Example 21ComparativeExample 41Comparativexample 42 ##STR32## ##STR33## Dimethyl thiophosphate0.01 wt%Q2 .multidot. 120A .RTM. (silicontype, manuf. byDow Chemical)0.01 wt %None .largecircle..DELTA.X 0.11.9 Example 22ComparativeExample 43ComparativeExample 44 ##STR34## C(CH.sub.2 SCH.sub.2 CH.sub.2 SH).sub.40.2 mol. Dibutyl thiophosphate1.0 wt %Diethyl thiophosphate0.5 wt %Trimethyl cetylammonium chloride1.0 wt %None .largecircle..DELTA.X 0.28.8 Example 23ComparativeExample 45ComparativeExample 46 ##STR35## ##STR36## Dioctyl thiophosphate2.0 wt %Octyl phosphate0.5 wt %None .largecircle..D ELTA.X 0.32.7 Example 24ComparativeExample 47ComparativeExample 48 ##STR37## ##STR38## Dimethyl dithiophosphate0.1 wt %Unidain DS-401 .RTM.(fluorine type,manuf. by DaikinKogyo) 0.05 wt %None .largecircle..D ELTA.X 0.13.2 Example 25 ComparativeExample 49ComparativeExample 50 ##STR39## HO(CH.sub.2).sub.2 SH0.3 mol. Diisopropyl dithiophosphate5.0 wt %Gafac RD-51- .RTM.(Phosphoric acidester, Toho KagakuKogyo 0.1 wt %None .largecircle..DELTA.X 0.21.0 E Example 26ComparativeExample 51Comparativexample 52 ##STR40## ##STR41## Dioctyl dithiophosphate4.0 wt %Stearyl glycerolether 4.0 wt %None .largecircle..DELTA.X 0.41.5 E Example 27ComparativeExample 53Comparativexample 54 ##STR42## ##STR43## Dimethyl thiophosphate0.02 wt %Dimethyl phosphate2.0 wt %None .largecirc le..DELTA.X 0.10.9 Example 28ComparativeExample 55ComparativeExample 56 OCN(CH.sub.2).sub.3 NCS0.4 mol. ##STR44## Diehtyl thiophosphate0.01 wt %Diethyl phosphate1.0 wt %None .largecircle ..DELTA.X 0.10.8 Example 29ComparativeExample 57ComparativeExample 58 O CN(CH.sub.2).sub.2 SS(CH.sub.2).sub.2 NCS0.3 mol. ##STR45## Dioctyl thiophosphate2.0 wt %Dioctyl dithiophosphate2.0 wt %Unidan DS-401 .RTM.(fluroine type,mauf. by DaikinKogyo) 0.03 wt%None .largecircle..DEL TA.X 0.53.0 Example 30ComparativeExample 59ComparativeExample 60 ##STR46## ##STR47## Dimethyl dithiophosphate0.3 wt %Dimethyl polysiloxane0.05 wt %None .largecircle..DELTA.X 0.24.1 E Example 31ComparativeExample 61Comparativexample 62 ##STR48## ##STR49## Dioctyl dithiophosphate2.0 wt %Zinc stearate1.0 wt %None .largecircle..D ELTA.X 0.229.7 Example 32ComparativeExample 63ComparativeExample 64 ##STR50## ##STR51## Dibutyl thiophosphate5.0 wt %Dibutyl phosphate2.0 wt %None .largecircle. .DELTA.X 0.40.8 Example 33ComparativeExample 65ComparativeExample 66 ##STR52## ##STR53## Dimethyl thiophosphate0.01 wt %Trimethyl octylammonium chloride0.5 wt %None .largecircle..DELTA.X 0.17.2 Example 34ComparativeExample 67ComparativeExample 68 ##STR54## HO(CH.sub.2).sub.2 S(CH.sub.2).sub.2 0 OH0.3 mol. Dimethyl dithiophosphate.05 wt %Dioctyl dithiophosphate0.1 wt %Gafac RD-510 .RTM.(phosphoric acidester, Toho KagakuKogyo) 0.1 wt %None .largecircle..DELTA.X 0.10.8 Example 35ComparativeExample 69ComparativeExample 70 ##STR55## ##STR56## Dioctyl thiophosphate1.0 wt %Dioctyl phosphate0.1 wt %None .largecircle. .DELTA.X 0.23.7 Example 36ComparativeExample 71ComparativeExample 72 ##STR57## ##STR58## Dioctyl dithiophosphate5.0 wt %Stearyl glycerylether 5.0 wt %None .largecircle..DELTA.X 0.55.3 E Example 37ComparativeExample 73Comparativexample 74 ##STR59## ##STR60## Diethyl thiophosphate0.05 wt %Q2 .multidot. 120A .RTM. (silicontype, manfu. byDow Chemical)0.05 wt %None .largecircle..DELTA.X 0.21.6 Example 38ComparativeExample 75ComparativeExample 76 ##STR61## ##STR62## Dibutyl thiophosphate0.5 wt %Dibutyl sodiumphsophate 0.5 wt %None .largecircle..DELTA.X 0.218.0
EXAMPLE 39
100 Parts by weight of branched polyoxyalkylene ether polyol (OHV 28) was mixed with 0.1 part by weight of triethylene diamine and 0.1 part by weight of dibutyltin dilaurate as a polymerization catalyst, and 5 parts by weight of diethyl thiophosphate as an internal release agent was added thereto to form a uniform solution.
To the resulting solution was added a urethane modified diphenyl methane diisocyanate (the isocyanate content being 23%) in an amount which made the isocyanate index 107 and molded into a flat plate of 70 mm in diameter and 9 mm in thickness in an aluminum mold by a reaction injection molding method.
Releasing was easy and the haze value of the resulting flat plate was as good as 0.4%.
COMPARATIVE EXAMPLE 77
The procedure of Example 39 was repeated except that 2 parts by weight of zinc stearate and 3 parts by weight of N,N,N'-tris(2-hydroxypropyl) ethylenediamine as internal release agents were heated to 90.degree.-100.degree. C. to make a uniform solution and used.
The releasing was easy, but the haze value of the resulting flat plate was as poor as 23.7%.
EXAMPLES 40-51
Epoxy compounds and various additives were combined as shown in Table 2, and the sulfur-containing acid phosphoric esters were mixed therewith as internal release agents, and then each of the resulting mixtures were poured into a mold constituted of a resin gasket and glass mold members, followed by heat polymerization or photo-polymerization to form a flat plate of resin of 70 mm in diameter and 9 mm in thickness.
Evaluation of releasability was made by inserting a Teflon wedge between the molded product and the mold, and when released easily it was designated as ".circle." when released though there was some resistance, it was designated as ".DELTA." and when not released, it was designated as "X".
The turbidity was determined by measuring the haze value of a flat plate of urethane resin of 9 mm thick by using Degital Haze Computer HGM-2DP manufactured by Suga Shikenki K.K. according to JIS K 7105, 6.4 to one place of decimals. The results are shown in Table 2.
COMPARATIVE EXAMPLES 78-101
In the combinations of monomers in the above-mentioned Examples, known internal release agents were used or no release agent was used in place of the sulfur-containing acid phosphoric esters and the procedures of the Examples were repeated, and there were measured the releasability and haze values of the resulting molded products. The results are shown in Table 2.
As compared with the sulfur-containing acid phosphoric esters of the present invention, when known internal release agents were used, the releasing was not easy and the haze value of the resin was high, and when no release agent was used, releasing was not possible and therefore, the haze value could not be measured.
TABLE 2__________________________________________________________________________ Polymeriza- Haze Internal tion condi- Releas- value Monomer agent tion ability (%)__________________________________________________________________________Example 40 Diepoxydicyclopentadiene Dimethyl thio- Metal .largecircle. 0.1 100 parts phosphate 0.01 wt % halide lampComparative 4-phenylthiophenyldiphenyl- Q2.120A .RTM. (silicon 80 w/cm Dis-Example 78 sulfonium hexafluoroantimo- type, manuf. by tance 20 cm .DELTA. 0.8 nate 1 part Dow Chemical 1 min. 0.01 wt %Comparative None XExample 79Example 41 3,4-Epoxycyclohexylmethyl- Diethyl thio- 80-120.degree. C. .largecircle. 0.1 3,4-epoxycyclohexane carbo- phosphate 0.05 wt % 22 hrComparative xylate 30 parts Diethyl phosphate .DELTA. 0.7Example 80 Tetrabromophthalic an- 0.5 wt %Comparative hydride 70 parts None XExample 81 Tin octylate 3 partsExample 42 Vinylcyclohexene diepoxide Dioctyl thio- 50-120.degree. C. .largecircle. 0.1 28 parts phosphate 2.0 wt % 20 hr.Comparative 2,2'-Diaminodiphenyldis- Unidain DS-403 .RTM. .DELTA. 1.0Example 82 sulfide 25 parts (fluorine type, Triethylamine 0.06 part manuf. by Daikin Kogyo) 0.015 wt %Comparative None XExample 83Example 43 1,4-Butanediglycidyl ether Dimethyldithiophosphate 50-120.degree. C. .largecircle. 0.0 20 parts 0.1 wt % 20 hr.Comparative Thiodiglycolic acid 15 parts Dibutyl phosphate .DELTA. 0.8Example 84 Triethylamine 0.06 part 0.1 wt %Comparative None XExample 85Example 44 Phthalic acid diglycidyl Diethyl dithio- 140.degree. C. .largecircle. 0.1 ether 20 parts phosphate 0.5 wt % 20 hr.Comparative Pentaerythritol tetrakis Trimethyl octyl .DELTA. 2.1Example 86 (thioglycolate) 15.5 parts ammonium chloride Tin octylate 0.15 parts 0.5 wt %Comparative None XExample 87Example 45 Diglycidyl 2,4-toluene di- Dibutyl dithio- 50-120.degree. C. .largecircle. 0.1 carbamate 50 parts phosphate 1.0 wt % 20 hr.Comparative Ethylene glycol 10 parts Dibutyl phosphate .DELTA. 0.5Example 88 Stannous chloride 0.1 part 1.0 wt %Comparative None XExample 89Example 46 N,N,N',N'-Tetraglycidyl Diethylthiophos- 50-120.degree. C. .largecircle. 0.1 terephthalic amide 50 parts phate 0.02 wt % 20 hr. 2-Mercaptoethanol 10 parts Diethyl dithio- Tin octylate 0.1 part phosphate 0.02 wt %Comparative Dimethyl poly- .DELTA. 1.2Example 90 siloxane 0.04 wt %Comparative None XExample 91Example 47 Tetrabromobisphenol A Dimethyl thiophos- 130.degree. C. .largecircle. 0.1 diglycidyl ether 55 parts phate 0.01 wt % 20 hr. Bis(4-isocyanatocyclohexyl) Dioctyl thiophos- methane 15 parts phate 0.01 wt %Comparative Pentaerythritol tetrakis Stearylglyceryl .DELTA. 0.8Example 92 (thioglycolate) 30 parts ether 0.5 wt %Comparative Dibutyltin dilaurate 0.05 None XExample 93 partExample 48 Glycidyl methacrylate 34 Diisopropyl dithio- 60-100.degree. C. .largecircle. 0.1 parts phosphate 5.0 wt % 22 hr.Comparative 2,4,6-Tribromophenol 66 parts Tridecyl phosphate .DELTA. 1.1Example 94 Stannous chloride 0.1 part 0.05 wt %Comparative Lauroyl peroxide 0.5 par None XExample 95Example 49 Glycidyl methacrylate 10 Dibutyl thiophos- 30-95.degree. C. .largecircle. 0.0 parts phate 0.1 wt % 8 hr.Comparative Diethylene glycol bis(allyl Dibutyl phosphate .DELTA. 0.5Example 96 carbonate) 90 parts 0.1 wt %Comparative Diisopropyl peroxydicarbonate None XExample 97 3 partsExample 50 3,4-Epoxymethacryloxyloxytri- Dioctyl dithiophos- Metal ha- .largecircle. 0.1 cyclo [5,2,1,0.sup.2.6 ] decane phate 0.5 wt % lide lampComparative 100 parts Dioctyl phosphate 80 w/cm .DELTA. 0.9Example 98 Benzophenone 0.5 part 0.4 wt. % DistanceComparative 4-Phenylthiophenyldiphenyl- None 20 cm 10 XExample 99 sulfonium hexafluoroantimo- min. nate 1 partExample 51 Bisphenol A diglycidyl ether Dibutyl thiophos- 30-150.degree. C. .largecircle. 0.1 17 parts phate 1.0 wt % 20 hr.Comparative Pentaerythritol tetrakis Dibutyl phosphate .DELTA. 1.3Example 100 (3-mercaptopropionate) 10 1.0 wt %Comparative parts None XExample 101 Hexahydrophthalic anhydride 3 parts Dibutyltin dilaurate 0.15 part__________________________________________________________________________
EXAMPLES 52-63, COMPARATIVE EXAMPLES 102-125
Flat plate molded products of 70 mm in diameter and 9 mm in thickness were prepared by casting polymerization of olefin monomer compositions containing sulfur-containing acid phosphoric esters as internal release agents, containing a known internal release agent, or containing no release agents as shown in Table 3 in molds composed of a resin gasket and glass discs.
Evaluation for releasability was made by inserting a Teflon wedge between the molded product and the glass flat plate, and when released easily, it was designated as ".circle." and when released with resistance, it was designated as "X".
The turbidity of the molded product was determined by measuring the haze value at a portion of 9 mm thick with a digital haze computer HGM-2DP manufactured by Suga Shikenki K.K. to one place of decimals according to JIS- K- 7105, 6.4 . The results are shown in Table 3.
TABLE 3__________________________________________________________________________ Polymeriza- Haze Internal release tion condi- Releas- value Monomer composition agent tion ability (%)__________________________________________________________________________Example 52 Diethylene glycol bis(allyl Dibutyl thiophos- 20-90.degree. C. .largecircle. 0.2 carbonate) 100 parts phate 0.01 wt % 20 hr.Comparative Diisopropyl peroxy di- Butyl phosphate .largecircle. 1.8Example 120 carbonate 3 parts 0.01 wt %Comparative None X 0.2Example 121Example 53 2,2-Bis(4-allyletherethoxy- Dioctyl thiophos- 70-100.degree. C. .largecircle. 0.7 3,5-dibromophenyl) propane phate 0.1 wt % 12 hr. 100 partsComparative Benzoyl peroxide 3 parts Stearyl alcohol X 1.0Example 122 0.1 wt %Comparative None X 0.7Example 123Example 54 1,2-Bis(acryloyloxyethylthio) Dioctadecyl thio- 50-110.degree. C. .largecircle. 0.3 ethane 100 parts phosphate 1.0 wt % 20 hr.Comparative t-Butylperoxy(2-ethylhexa- Stearyl glyceryl .largecircle. 1.1Example 124 nate) 0.5 part ether 0.2 wt %Comparative None X 0.2Example 125Example 55 S-Methylthiomethacrylate Dimethyl dithio- 50-90.degree. C. .largecircle. 0.3 100 parts phosphate 0.001 wt % 30 hr.Comparative 2,2'-Azobis(2,4-dimethyl- Dimethyl polysilo- X 0.9Example 114 valeronitrile) 0.5 part xane 0.001 wt %Comparative None X 0.3Example 115Example 56 p-Methylthiostyrene Dioctadecyl dithio- 30-90.degree. C. .largecircle. 0.2 100 parts phosphate 0.8 wt % 20 hr.Comparative t-Butylperoxy(2-ethylhexa- Octyl stearate 0.8 .largecircle. 0.6Example 116 nate) 1 part wt %Comparative None X 0.2Example 117Example 57 Diethylene glycol bis(allyl Diethyl thiophos- 30-80.degree. C. .largecircle. 0.5 carbonate) 65 parts phate 0.05 wt % 22 hr.Comparative Dially isophthalate 20 parts Diethyl phosphate .largecircle. 0.9Example 118 Benzyl methacrylate 15 parts 0.05 wt %Comparative Diisopropyl peroxydicarbo- None X 0.5Example 119 nate 3 partsExample 58 Methyl methacrylate 90 Dimethyl thio- 70-100.degree. C. .largecircle. 0.8 parts phosphate 0.1 wt % 10 hr. Cyclohexyl maleimide 10 Dioctyl thiophos- parts phate 0.1 wt %Comparative Azobisisobutyronitrile 0.5 Stearic acid tri- .largecircle. 1.4Example 108 part glyceride 0.2 wt %Comparative None X 0.8Example 109Example 59 Styrene 50 parts Dibutyl thiophos- 30-90.degree. C. .largecircle. 0.4 Bis(2-methacryloylthioethyl) phate 0.5 wt % 15 hr. sulfide 40 parts Dibutyl Dithio- Acrylonitrile 10 parts phosphate 0.5 wt %Comparative Azobisisobutyronitrile 0.1 Dibutyl phosphate .largecircle. 0.8Example 110 part 1.0 wt %Comparative None X 0.3Example 111Example 60 2,5-Di(methacryloyloxy)-1,4- Diisopropyl di- 60-120.degree. C. .largecircle. 0.3 dithiane 50 parts thiophosphate 20 hr. Styrene 50 parts 0.2 wt %Comparative Benzoyl peroxide 1 part Unidain DS-403 .RTM. .largecircle. 2.8Example 112 (fluorine type, Daikin Kogyo K.K.) 0.2 wt %Comparative None X 0.3Example 113Example 61 2,2-Bis(4-methacryloxyethoxy- Diethyl thiophos- 50-110.degree. C. .largecircle. 0.6 3,5-dibromophenyl) propane phate 0.1 wt % 19 hr.Comparative 47 parts Zinc stearate 0.01 X 8.2Example 102 1-Acryloxyethoxy-2,4,6--tri- wt %Comparative bromobenzene 18 parts None X 0.6Example 103 Styrene 20 parts .alpha.-Methylstyrene 15 parts Lauroyl peroxide 1 partExample 62 m-Divinylbenzene 10 parts Dioctyl dithio- 50-100.degree. C. .largecircle. 0.7 Methyl methacrylate 80 parts phosphate 0.5 wt % 16 hr.Comparative Methacrylic amide 10 parts Dioctyl phthalate .largecircle. 1.2Example 104 Azobisisobutyronitrile 0.5 0.5 wt %Comparative part None X 0.7Example 105Example 63 Diallylidene pentaerythritol Dimethyl thio- Metal ha- .largecircle. 0.6 50 parts phosphate 0.1 wt % lide lampComparative 1,1,1-Trimethylolpropane tri- Dimethyl phosphate 3 kw 2 min. .largecircle. 0.8Example 106 acrylate 50 parts 0.1 wt %Comparative Benzophenone 0.5 part None X 0.6Example 107__________________________________________________________________________
EXAMPLES 64-74, COMPARATIVE EXAMPLES 126-147
Flat plate molded products of 70 mm in diameter and 9 mm in thickness were prepared by injection molding of acrylic resins composed of monomer compositions containing sulfur-containing acid phosphoric esters as internal release agents, or containing no release agents as shown in table 4.
Evaluation for releasability was made by inserting a wedge between the molded product and a metal mold and when released easily, it was designated as ".circle.", and when released with resistance, it was designated as "X".
The turbidity of the molded product was determined by measuring the haze value at a portion of 9 mm thick with a digital haze computer HGM-2DP manufactured by Suga Shikenki K.K. to one place of decimals according to JIS- K-7105, 6.4. The results are shown in Table 4.
TABLE 4__________________________________________________________________________ Releas- Haze value Acrylic resin composition Internal release agent ability (%)__________________________________________________________________________Example 64 Methyl methacrylate 100 wt % Dimethyl thiophosphate .largecircle. 0.1 0.001 wt %Comparative Stearic acid 0.2 wt % .largecircle. 0.7Example 126Comparative None X 0.1Example 127Example 65 Methyl methacrylate 95 wt % Dioctyl thiophosphate .largecircle. 0.1 Ethyl acrylate 5 wt % 0.01 wt %Comparative Behenic acid 0.04 wt % .largecircle. 0.4Example 128 Stearyl alcohol 0.02 wt %Comparative None X 0.1Example 129Example 66 Methyl methacrylate Dioctadecyl thiophos- .largecircle. 0.4 90 wt % phate 0.3 wt %Comparative N-cychohexyl maleimide Arachic acid 0.2 wt % .largecircle. 0.8Example 130 10 wt % Stearyl alcohol 0.1 wt %Comparative None X 0.4Example 131Example 67 Methyl methacrylate 80 wt % Dimethyl dithiophos- .largecircle. 0.3 Tribromophenyl methacrylate phate 0.05 wt %Comparative 20 wt % Lignoceric acid 0.2 .largecircle. 0.8Example 132 wt % Cetyl alcohol 0.04 wt %Comparative None X 0.3Example 133Example 68 Methyl methacrylate 70 wt % Dioctadecyl dithio- .largecircle. 0.2 Styrene 30 wt % phosphate 1.0 wt %Comparative Stearyl alcohol 1.0 .largecircle. 0.9Example 134 wt %Comparative None X 0.1Example 135Example 69 Methyl methacrylate 90 wt % Dibutyl thiophosphate .largecircle. 0.1 Methacrylonitrile 10 wt % 0.2 wt %Comparative Stearyl glyceryl ether .largecircle. 0.5Example 136 0.2 wt %Comparative None X 0.1Example 137Example 70 Methyl methacrylate 70 wt % Dibutyl dithiophosphate .largecircle. 0.2 S-methyl thioacrylate 30 0.1 wt %Comparative wt % Dibutyl phosphate 0.1 .largecircle. 0.7Example 138 wt %Comparative None X 0.2Example 139Example 71 Cyclohexyl acrylate 90 wt % Dimethyl thiophos- .largecircle. 0.4 Acrylamide 10 wt % phate 0.01 wt % Dioctyl thiophosphate 0.04 wt %Comparative Dimethylpolysiloxane .largecircle. 1.1Example 140 0.05 wt %Comparative None X 0.4Example 141Example 72 Methyl methacrylate 70 wt % Diethyl thiophosphate .largecircle. 0.3 Dibutyl maleate 30 wt % 0.01 wt % Diethyl dithiophos- phate 0.01 wt %Comparative octyl stearate 0.2 wt % .largecircle. 0.8Example 142Comparative None X 0.3Example 143Example 73 Methyl methacrylate 50 wt % Dioctyl thiophosphate .largecircle. 0.5 N-Cyclohexyl maleimide 25 0.5 wt %Comparative wt % Dioctyl phosphate .largecircle. 1.2Example 144 Cyclohexyl methacrylate 15 wt % 0.5 wt %Comparative .alpha.-Methylsyrene 10 wt % None X 0.4Example 145Example 74 Methyl methacrylate 65 wt % Diethyl thiophosphate .largecircle. 0.3 2,4,6-Tribromophenyl meth- 0.005 wt %Comparative acrylate 20 wt % Stearic acid mono- .largecircle. 0.8Example 146 Cyclohexyl methacrylate glyceride 0.1 wt %Comparative 10 wt % None X 0.3Example 147 Methyl acrylate 5 wt %__________________________________________________________________________
EXAMPLES 75-84, COMPARATIVE EXAMPLES 148-167
Flat plate molded products composed of a polyene-polythiol resin of 70 mm in diameter and 9 mm in thickness were prepared by casting polymerization of monomer compositions containing sulfur-containing acid phosphoric esters as internal release agents, or containing no release agent as shown in Table 5 in molds composed of a resin gasket and glass discs.
Evaluation for releasability was made by inserting a Teflon wedge between the molded product and the glass flat plate, and when released easily, it was designated as ".circle.", and when released with resistance, it was designated as "X".
The turbidity of the molded product was determined by measuring the haze value at a portion of 9 mm thick with a digital haze computer HGM-2DP manufactured by Suga Shikenki K.K. to one place of decimals according to JIS- K-7105, 6.4. The results are shown in Table 5.
TABLE 5__________________________________________________________________________ Polymeriza- Haze Internal release tion condi- Releas- value Monomer composition agent tion ability (%)__________________________________________________________________________Example 75 m-Divinylbenzene 35 parts Dimethyl thiophos- 50-100.degree. C. .largecircle. 0.4 Pentaerythritol tetrakis phate 0.001 wt % 20 hr.Comparative (3-mercaptopropionate) Dimethylpolysilox- X 0.8Example 148 65 parts ane 0.001 wt %Comparative t-Butylperoxy(2-ethyl- None X 0.4Example 149 hexanoate) 0.5 partExample 76 m-Divinylbenzene 70 parts Dioctadecyl thio- 50-100.degree. C. .largecircle. 0.5 Pentaerythritol tetrakis (3- phosphate 1.0 wt % 20 hr.Comparative mercaptopropionate) 25 parts Octyl stearate .largecircle. 1.4Example 150 1,2-Dimercaptoethane 5 parts 1.0 wt %Comparative t-Butylperoxy(2-ethylhexa- None X 0.4Example 151 noate) 0.5 partExample 77 Diethylene glycol dimeth- Diethyl thiophos- 40-100.degree. C. .largecircle. 0.3 acrylate 66 parts phate 0.05 wt % 12 hr. Ethylene glycol dithio- Diethyl dithiophos- acrylate 34 parts phate 0.05 wt %Comparative Azobisisobutyronitrile Stearyl alcohol X 0.7Example 152 0.5 part 0.1 wt %Comparative None X 0.3Example 153Example 78 Trimethylolpropane triacry- Dimethyl dithio- 40-100.degree. C. .largecircle. 0.5 late 80 parts phosphate 0.01 wt % 12 hr.Comparative 1,3-Dimercaptobenzone Stearyl glyceryl .largecircle. 0.9Example 154 20 parts ether 0.2 wt %Comparative Azobisisobutyronitrile None X 0.5Example 155 0.5 partExample 79 1,2-Bis(4-vinylbenzylthio) Dioctadecyl dithio- 50-90.degree. C. .largecircle. 0.3 ethane 95 parts phosphate 0.5 wt % 2 hr.Comparative Pentaerythritol tetrakis Stearic acid tri- .largecircle. 1.2Example 156 (3-mercaptopropionate) 5 glyceride 0.5 wt %Comparative parts None X 0.3Example 157 t-Butylperoxy(2-ethyl- hexanoate) 0.8 partExample 80 4,4'-Dimercaptodiphenyl- Dibutyl thiophos- 30-100.degree. C. .largecircle. 0.4 sulfide dimethacry- phate 0.1 wt % 20 hr. late 70 parts Dioctyl thiophos- Pentaerythritol tetrakis(3- phate 0.1 wt %Comparative mercaptopropionate) 30 parts Unidain DS-403 .RTM. .largecircle. 2.7Example 158 2,2'-Azobis(2,4-dimethyl- (fluorine, manuf. valeronitrile) 0.5 part by Daikin Kogyo)Comparative None X 0.4Example 159Example 81 Diethylene glycol bis(allyl Dioctyl thiophos- 30-90.degree. C. .largecircle. 0.4 carbonate) 70 parts phate 0.2 wt % 30 hr.Comparative 1,3-Bis(mercaptomethyl) Zinc stearate 0.01 X 7.6Example 160 benzene 30 parts wt %Comparative t-Butylperoxy(2-ethylhexa- None X 0.4Example 161 noate) 0.5 partExample 82 2,2-Bis(4-allyloxyethoxy- Diisopropyl dithio- 50-120.degree. C. .largecircle. 0.6 phenyl) propane 60 parts phosphate 0.2 wt % 24 hr.Comparative 1,2,4-Tris(mercaptoethyl- Diisopropyl phos- .largecircle. 1.0Example 162 thiobenzene) 40 parts phate 0.2 wt %Comparative Lauroyl peroxide 1 part None X 0.6Example 163Example 83 Diallyl isophthalate 60 Diethyl thiophos- 40-110.degree. C. .largecircle. 0.4 parts phate 0.05 wt % 20 hr.Comparative 1,4-Dithiane-2,5-diol bis Diethyl phosphate .largecircle. 0.7Example 164 (3-mercaptopropionate)35 0.05 wt %Comparative parts None X 0.4Example 165 3,4-dimercaptothiophene 5 parts Azobisisobutyronitrile 0.5 partExample 84 Diallylidenepentaerythritol Dioctyl thiophos- Metal ha- .largecircle. 0.5 30 parts phate 0.2 wt % lide lampComparative 1,1,1-Trimethylolpropane Dioctyl phthalate 3 kw 2 min. .largecircle. 1.2Example 166 triacrylate 30 parts 0.2 wt %Comparative 1,1,1-TrimethylolpropaneExample 167 tri(3-mercaptopropionate) 40 parts None X 0.5 Benzophenone 0.5 parts__________________________________________________________________________
EXAMPLES 85-94, COMPARATIVE EXAMPLES 168-173
Flat plates of 70 mm in diameter and 9 mm in thick were prepared by injecting into metal molds at 130.degree. C. a composition of 2.2-bis(4-hydroxyphenyl) propane type polycarbonate powder having an average molecular weight of 15,000 and an internal release agent, or said powder without adding any internal release agent as shown in Table 6, after melted at a resin temperature of 250.degree. C.-270.degree. C.
Evaluation for releasability was made by inserting a wedge between the molded product and the metal mold, and when released easily, it was designated as ".circle.", and when released with resistance, it was designated as "X".
The optical strain of the molded product was measured by Toshiba tester SVP-100. When there was no strain, the molded product was designated as ".circle.". When there was strain, it was designated as "X".
The turbidity of the molded product was determined by measuring the haze value of a flat plate resin of 9 mm thick with a digital haze computer HGM-2DP manufactured by Suga Shikenki K.K. to one place of decimals according to JIS-K-7105, 6.4. The results are shown in Table 6.
TABLE 6__________________________________________________________________________ Releas- Optical Haze Internal release agent ability strain value (%)__________________________________________________________________________Example 85 Dimethyl thiophosphate 0.001 wt % .largecircle. .largecircle. 0.0Example 86 Diethyl thiophosphate 0.005 wt % .largecircle. .largecircle. 0.0Example 87 Dioctyl thiophosphate 0.1 wt % .largecircle. .largecircle. 0.0Example 88 Dioctadecyl thiophosphate 1.0 wt % .largecircle. .largecircle. 0.0Example 89 Dimethyl Dithiophosphate 0.05 wt % .largecircle. .largecircle. 0.0Example 90 Diisopropyl dithophosphate 0.5 wt % .largecircle. .largecircle. 0.0Example 91 Dioctyl dithiophosphate 0.2 wt % .largecircle. .largecircle. 0.0Example 92 Dioctadecyl dithiophosphate 0.8 wt % .largecircle. .largecircle. 0.0Example 93 Dimethyl thiophosphate 0.01 wt % .largecircle. .largecircle. 0.0 Dioctadecyl thiophosphate 0.1 wt %Example 94 Dibutyl thiophosphate 0.01 wt % .largecircle. .largecircle. 0.0 Dibutyl dithiophosphate 0.01 wt %Comparative Stearyl glyceryl ether 0.2 wt % .largecircle. .largecircle. 0.4Example 168Comparative Behenyl behenate 0.04 wt % X X 0.3Example 169Comparative Stearic acid monoglyceride .largecircle. .largecircle. 0.4Example 170 0.1 wt %Comparative Dimethyl polysiloxane 0.04 wt % X X 0.8Example 171Comparative Dioctyl phosphate 0.1 wt % X X 0.7Example 172Comparative None X X 0.0Example 173__________________________________________________________________________

Number	Date	Country
4-015878	Jan 1992	JPX
4-017497	Feb 1992	JPX
4-019620	Feb 1992	JPX
4-026471	Feb 1992	JPX
4-044532	Mar 1992	JPX
4-046661	Mar 1992	JPX
4-048277	Mar 1992	JPX

Number	Name	Date
2735836	Fanning	Feb 1956
2906731	Hill et al.	Sep 1959
3098057	Baum	Jul 1963
3124556	Merrifield et al.	Mar 1964
3300440	Prevorsek	Jan 1967
3516957	Gray et al.	Jun 1970
3919165	Hechenbleickner	Nov 1975
3933407	Tu et al.	Jan 1976
4018939	Merrill et al.	Apr 1977
4257995	McLaughlin et al.	Mar 1981
4258169	Prather et al.	Mar 1981
4560716	Sato et al.	Dec 1985

Number	Date	Country
351073	Jan 1990	EPX
212444	Aug 1984	DEX
42-12535	Jul 1967	JPX
1-295201	Nov 1989	JPX
1-315460	Dec 1989	JPX
2-84409	Mar 1990	JPX
2-105844	Apr 1990	JPX
3-81320	Apr 1991	JPX

Sulfur-containing acid phosphoric ester internal release agent

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Entry
Patent Abstracts of Japan, vol. 14, No. 149, (C-705).
Database WPIL Week 9206, Derwent Publications Ltd. AN 92-044401, 18 Dec. 1991.
Database WPIL Week 8550, Derwent Publications Ltd. AN 88-356364, 2 Nov. 1988.
Database WPIL Week 8840, Derwent Publications, Ltd. AN 88-282667, 29 Aug. 1988.
Patent Abstracts of Japan, vol. 13, No. 524 (P-964) 22 Nov. 1989.
Patent Abstracts of Japan, vol. 14, No. 204 (P-1042) 25 Apr. 1990.