JPH05214114A - Method for preventing additive for modifying resin from bleeding - Google Patents

Abstract

PURPOSE:To efficiently prevent an additive for modifying a resin from causing bleeding phenomena by including a prescribed amount of a specified oil absorbing crosslinked polymer in a resin composition composed of a plastic, etc., and the additive for modifying the resin. CONSTITUTION:An additive for modifying a resin is prevented from causing bleeding phenomena by including an oil absorbing crosslinked polymer obtained by polymerizing a monomer component composed of (A) 96-99.999wt.% monomer consisting essentially of a monomer having >=9 solubility parameter (SP value) and having one polymerizable unsaturated group in the molecule such as methyl (meth)acrylate and (B) 0.001-4wt.% crosslinking monomer having >=2 polymerizable unsaturated groups in the molecule such as divinylbenzene in an amount of 0.01-50 pts.wt. based on 100 pts.wt. resin composition composed of a plastic, etc., and the additive for modifying the resin therein.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for preventing bleeding of a resin modifying additive. More specifically, in a resin composition comprising a resin and a resin modifying additive, the resin modifying additive is uniformly dispersed in the resin, and the resin modifying additive is separated from the resin composition over time. Thus, the present invention relates to a method for preventing bleeding of a resin-modifying additive, which prevents the resin-modifying effect from decreasing and the resin-modifying additive from migrating to the surface of the resin composition and adversely affecting the physical properties of the resin surface.

[0002]

2. Description of the Related Art Conventionally, polymer compounds such as plastics and elastomers, so-called resins, include resin properties (workability, flexibility, elasticity, brittleness, handleability, etc.), resin performance (stability, stability,
Various additives are used for the purpose of modifying durability, flame retardancy, vibration control, heat retention, etc.) and processability (release property, kneading property, etc.). The additives include plasticizers, softeners, softening aids, flame retardants, smoke suppressants, antistatic agents, stabilizers, antiaging agents, copper damage inhibitors, metal deactivators, antioxidants. , Ozone deterioration inhibitor, ultraviolet absorber, light stabilizer, mastication accelerator, tackifier, lubricant, slip agent, internal release agent, colorant, antifouling agent, antifouling agent, antifogging agent, antiseptic Agent, mildew proofing agent, heat retaining agent, foaming agent, scorch inhibitor, anti-vibration agent, impact resistance improver, solvent, ant-preventive agent,
Repellent, fragrance, surface treatment agent, wetting agent, surfactant, emulsifier, destabilizing agent, slow coagulant, defoaming agent, defoaming agent, antifreezing agent, freeze-thaw stabilizer, creaming agent, dispersion Examples include a wide variety of additives such as agents, thickeners, coagulants, heat sensitive agents, foaming agents, bubble stabilizers, film-forming aids and modifiers for sealing gaskets. Further, these additives are rarely used singly, and most of them are used in combination.

However, in a resin composition prepared by blending these additives with a resin, an additive having poor compatibility with the resin is used or an additive having good compatibility and an additive having poor compatibility are used in combination. In the case where an additive having a good compatibility is used in excess of the amount solubilized in the resin, the additive is separated from the resin composition over time and the resin modifying effect is reduced, or the resin modifying additive is added. However, the bleeding phenomenon has been recognized, and the bleeding phenomenon may occur on the surface of the resin composition to adversely affect the physical properties of the resin surface such as adhesiveness, dust adhesion, and ink bleeding.

As a method of preventing the bleeding phenomenon of the resin-modifying additive from the resin composition, an article obtained by separating the resin composition from the resin composition or molding the resin composition by suppressing the molecular motion of the additive. There is the use of polymeric additives that prevent migration to the surface. Further, as another method, there is a method of adding a compatibilizer for improving the compatibility with the resin.
Further, there is a method of suppressing the bleeding of the additive by subjecting the surface of the resin molded product to crosslinking or coating.

However, the method of using, for example, a polymer plasticizer as a polymer-based additive has a drawback that it has a high cost and a limited application as compared with a low-molecular-weight plasticizer, although it has an effect of preventing bleeding. .. Further, in the method of using a compatibilizing agent such as a surfactant, it is necessary to change to a suitable one for the composition each time depending on the physical properties of each resin and the types and amounts of various additives. It was difficult to find the optimal formulation. Furthermore, in the method of crosslinking or coating the surface of the resin molded product,
A large amount of capital investment is required, and at the same time, it is troublesome to process them, resulting in cost increase, and there is a problem in versatility.

On the other hand, it has been empirically recognized that the addition of a porous inorganic powder such as calcium carbonate has the effect of preventing the bleeding of the resin modifying additive. However, there is a problem that a large amount of the inorganic powder needs to be contained in the resin, and the physical properties of the resin composition are changed or the transparency is lost due to the large amount of the inorganic powder.

[0007]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of conventional methods for preventing bleeding of resin modifying additives.

That is, an object of the present invention is to provide a resin composition comprising a resin and a resin-modifying additive, in which the resin-modifying additive is separated from the resin composition over time and the resin-modifying effect is reduced. Or to prevent the bleeding phenomenon of the resin modifying additive from migrating to the surface of the resin composition and adversely affecting the physical properties of the resin surface.

[0009]

Means for Solving the Problems The present inventor has found that a resin composition comprising a resin and a resin-modifying additive contains a specific oil-absorbing cross-linked polymer so that the resin-modifying additive is a resin. A resin-modifying additive that separates from the composition over time to reduce the resin-modifying effect or that the resin-modifying additive migrates to the resin composition surface and adversely affects the physical properties of the resin surface. The inventors have found that the bleeding phenomenon can be prevented, and completed the present invention.

That is, according to the present invention, a resin composition comprising a plastic and / or an elastomer (hereinafter referred to as a resin (X)) and a resin modifying additive (Y) has a solubility parameter (SP value) of 9 or less. 96-99.999% by weight of a monomer (A) containing a monomer as a main component and having one polymerizable unsaturated group in the molecule, and crosslinking having at least two polymerizable unsaturated groups in the molecule -Absorptive cross-linking obtained by polymerizing a monomer component composed of 0.001 to 4% by weight of a polymerizable monomer (B) (however, the total amount of the monomers (A) and (B) is 100% by weight) The polymer (I) is contained in an amount of 0.01 to 50 parts by weight with respect to 100 parts by weight of the resin composition, and the resin modifying additive (Y) is added to the resin composition over time. Separation reduces the resin modification effect or resin modification Pressurizing agent is related to bleeding prevention method of a resin modifying additive to prevent or adversely affect the migration to the resin surface properties to the surface resin composition.

[0011]

The solubility parameter (SP value) is generally used as a measure of the polarity of a compound, and in the present invention, the value derived by substituting the Hoy cohesive energy constant into the Small calculation formula is applied, The unit is (cal /
represented by cm ^{3) 1/2.}

The monomer constituting the main component of the monomer (A) used in the present invention is a monomer having a solubility parameter (SP value) of 9 or less and having one polymerizable unsaturated group in the molecule. It is the body. When a monomer having a solubility parameter (SP value) of more than 9 is used as the main component of the monomer (A), a crosslinked polymer having a high bleed preventing effect cannot be obtained, and the resin modifying additive is used as a resin composition. It is not preferable because it bleeds more with time and the resin modifying effect decreases.

Examples of the monomer having a solubility parameter (SP value) of 9 or less and having one polymerizable unsaturated group in the molecule include, for example, methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth). Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate,
Dodecyl (meth) acrylate, isobornyl (meth)
Acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, octylphenyl (meth)
Acrylate, nonylphenyl (meth) acrylate,
Unsaturated carboxylic acid esters such as dinonylphenyl (meth) acrylate, cyclohexyl (meth) acrylate, menthyl (meth) acrylate, dibutyl maleate, didodecyl maleate, dodecyl crotonate and didodecyl itaconate; (di) butyl ( (Meth) acrylamide, (di) dodecyl (meth) acrylamide,
(Meth) acrylamide having a hydrocarbon group such as (di) stearyl (meth) acrylamide, (di) butylphenyl (meth) acrylamide, (di) octylphenyl (meth) acrylamide; 1-hexene, 1-octene, isooctene, Α-Olefins such as 1-nonene, 1-decene, 1-dodecene; alicyclic vinyl compounds such as vinylcyclohexane; allyl ethers having a hydrocarbon group such as dodecyl allyl ether; vinyl caproate, vinyl laurate, palmitic acid Vinyl ester having a hydrocarbon group such as vinyl and vinyl stearate;
Vinyl ether having a hydrocarbon group such as butyl vinyl ether and dodecyl vinyl ether; aromatic vinyl compounds such as styrene, t-butyl styrene and octyl styrene, and the like, and one or more of these monomers can be used. You can

Among these, at least one aliphatic hydrocarbon group having 3 to 30 carbon atoms is used as the monomer (A) for providing the resin bleeding prevention method of the additive for resin modification which is more excellent in the above performance. And at least one selected from the group consisting of alkyl (meth) acrylate, alkylaryl (meth) acrylate, alkyl (meth) acrylamide, alkylaryl (meth) acrylamide, fatty acid vinyl ester, alkylstyrene and α-olefin. Those having an unsaturated compound (a) as a main component are preferable.

Such solubility parameter (SP value)
Is 9 or less, the amount used in the monomer (A) is
The proportion is 50% by weight or more, more preferably 70% by weight or more, based on the total amount of the monomer (A). When the amount of the monomer having a solubility parameter (SP value) of 9 or less in the monomer (A) is less than 50% by weight, a crosslinked polymer having a high bleeding-preventing effect cannot be obtained, and a resin modifying additive is obtained. Is not preferable because it bleeds with time from the resin composition and the resin modifying effect is reduced.

Therefore, in the present invention, 50 monomers having a solubility parameter (SP value) of 9 or less are contained in the monomer (A).
It is necessary to contain at least 50% by weight, but the solubility parameter (SP value) is 50% by weight or less in the monomer (A).
May contain more than 9 monomers. Examples of such a monomer include (meth) acrylic acid, acrylonitrile, maleic anhydride, fumaric acid, hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate. be able to.

Examples of the crosslinkable monomer (B) used in the present invention include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, polyethylene glycol-polypropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth)
Acrylate, 1,6-hexanediol di (meth) acrylate, N, N'-methylenebis (meth) acrylamide, N, N'-propylenebis (meth) acrylamide, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, tetramethylolmethane tetra (meth) acrylate, polyfunctional (meth) obtained by esterification of (meth) acrylic acid with an alkylene oxide adduct of polyhydric alcohol (eg glycerin, trimethylolpropane or tetramethylolmethane) Examples thereof include acrylate and divinylbenzene, and one or more of these crosslinkable monomers can be used.

The proportions of the monomer (A) and the crosslinkable monomer (B) in the monomer component used for producing the oil-absorbent crosslinked polymer (I) are as follows. The amount of the monomer (A) is 96 to 99.9 based on the total amount of the crosslinkable monomer (B).
99% by weight, the crosslinkable monomer (B) is 0.001-
It is in the range of 4% by weight.

When the amount of the monomer (A) is less than 96% by weight or the amount of the crosslinkable monomer (B) exceeds 4% by weight, the crosslink density of the obtained crosslinked polymer becomes too high and the crosslinked polymer is As a result of lowering the bleeding prevention effect, the resin modifying additive bleeds with time from the resin composition and the resin modifying effect is reduced, which is not preferable. Further, the monomer (A) is 99.99.
If it exceeds 9% by weight, the compatibility of the resulting cross-linked polymer with the resin and the resin-modifying additive will increase excessively, resulting in insufficient bleeding prevention effect of the resin-modifying additive or a resin molded article. It is not preferable because it causes tackiness.

To produce the oil-absorbing crosslinked polymer (I),
The monomer component may be copolymerized using a polymerization initiator. The copolymerization can be carried out by a known method such as suspension polymerization, bulk polymerization or emulsion polymerization.

In the suspension polymerization, for example, an emulsifier having a high HLB value or a protective colloid agent such as polyvinyl alcohol, hydroxyethyl cellulose or gelatin is used to suspend the monomer component in water to prepare an oil-soluble polymerization initiator. The polymerization may be carried out in the presence of Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, 2,2′-azobisisobutyronitrile, and 2,2′-azobisdimethylvaleronitrile. The azo compound can be used, and the polymerization temperature is preferably in the range of 0 to 150 ° C. The obtained cross-linked resin suspension having a particle size of about 10 to 1000 μm is filtered and dried to obtain the desired crosslinked polymer (I).

In the bulk polymerization, for example, a monomer component is poured into a mold in the presence of the above-mentioned polymerization initiator, and the polymerization is carried out under the condition of 0 to 150 ° C. to obtain a desired crosslinked polymer (I). Be done.

In emulsion polymerization, the monomer components are suspended in water using, for example, an anionic or nonionic emulsifier or a composite emulsifier thereof, and a persulfate such as ammonium persulfate or potassium persulfate or a water-soluble azo compound is suspended. It is possible to use it as a polymerization initiator, and use a reducing agent, a pH adjuster, an antioxidant, an antistatic agent, etc. together, if necessary, and carry out the polymerization under the condition of 0 to 150 ° C. The desired crosslinked polymer (I) is obtained.

The method for preventing bleeding of the resin modifying additive of the present invention is effective for all resins called plastics and / or elastomers. Examples of the resin (X) that can constitute the resin composition in the present invention include polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polystyrene, (meth) acrylic resin, polyvinyl alcohol,
Polyolefin, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polycarbonate, polyamide, acetyl cellulose, fluororesin,
Phenolic resin, urea resin, melanin resin, polyester resin, allyl resin, silicone resin, epoxy resin,
Mention may be made of homopolymers and copolymers of AS resins, ABS resins, synthetic rubbers, natural rubbers and the like, or mixtures of these resins.

The resin modifying additive (Y) constituting the resin composition of the present invention is not particularly limited as long as it is added for the purpose of resin modification, and for example, a plasticizer,
Softeners, softening aids, flame retardants, smoke suppressants, antistatic agents, stabilizers, antiaging agents, copper damage inhibitors, metal deactivators, antioxidants, antiozonants, UV absorbers , Light stabilizer, mastication accelerator, tackifier, lubricant, slip agent, internal release agent, colorant, antifouling agent, antifouling agent, antifogging agent, antifungal agent, preservative, heat retaining agent, Foaming agent, anti-scorch agent, anti-vibration agent, impact resistance improver, solvent, anti-termite agent, repellent, fragrance, surface treatment agent, wetting agent, surfactant, emulsifier, destabilizing agent, slow coagulant , Antifoam, defoamer, antifreeze, freeze-thaw stabilizer, creaming agent, dispersant, thickener, coagulant,
Examples thereof include a heat sensitive agent, a foaming agent, a bubble stabilizer, a film forming aid, and a sealing gasket modifier.

Among such additives (Y), examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diethyl phthalate, diheptyl phthalate and di-2.
-Ethylhexyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, dicapryl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, diisobutyl phthalate, dibenzyl phthalate, butyl benzyl phthalate , Dicyclohexyl phthalate, butylbenzyl phthalate, dimethoxyethyl phthalate, dibutoxyethyl phthalate, dimethyl cyclohexyl phthalate, octyl decyl phthalate, octyl benzyl phthalate, n-hexyl n-decyl phthalate,
Phthalic acid ester derivatives such as n-octyl / n-decyl / phthalate; phthalic acid isomers such as dimethyl isophthalate, dioctyl isophthalate, di-2-ethylhexyl terephthalate; di2-ethylhexyl tetrahydrophthalate, di n-octyl tetrahydrophthalate, etc. Tetrahydrophthalic acid derivatives of tricresyl phosphate, trioctyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, trichloroethyl phosphate, bisphenol A diphenyl phosphate,
Phosphate ester derivatives such as bisphenol A dixylenyl phosphate; dimethyl adipate, dibutyl adipate, diisodecyl adipate, diisobutyl adipate, diisononyl adipate, di2-ethylhexyl adipate, di n-octyl adipate, didecyl adipate, n-octyl n- Adipic acid derivatives such as decyl adipate, n-heptyl n-nonyl adipate, benzyl octyl adipate, dibutyl diglycol adipate; di n-butyl sebacate, di n-octyl sebacate, diisooctyl sebacate, di2-ethylhexyl sebacate, Sebacic acid derivatives such as butylbenzyl sebacate; di-2-ethylhexyl azelate, di-n-hexyl azelate, dimethyl azelate, dibenzyl azelate, Azelaic acid derivatives such as butoxyethyl azelate and diisooctyl azelate; citric acid-based compounds such as triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate and acetyl trioctyl citrate; epoxidized soybean oil, Epoxy type such as epoxy butyl stearate, octyl epoxy stearate, dioctyl epoxy hexahydrophthalate; polyester type such as polypropylene adipate, polypropylene sebacate;
Chlorinated paraffins, chlorinated fatty acid esters and other chlorinated systems; methylphthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate and other glycolic acid systems; tri-2-ethylhexyl trimellitate, tri n Examples include trimellitic acid compounds such as octyl n-decyl trimellitate; ricinoleic acid compounds such as methyl acetyl ricinoleate and butyl acetyl ricinoleate; butyl oleate and the like, and one or two of these compounds can be mentioned. More than one species can be used.

Examples of softening agents and softening aids include paraffinic process oils, aromatic process oils,
Mineral oils such as special process oils, oligomers of ethylene and α-olefins, paraffin wax, liquid paraffin, white oil, petroleum dam, petroleum sulfonates, giesonite, petroleum asphalt, and petroleum resins; castor oil, cottonseed oil, rapeseed oil, soybean oil, Balm oil, coconut oil,
Vegetable oils such as peanut oil, wax, rosin, pine oil, dipentene, softener containing pine tar, tall oil, refined tall oil; sub-systems such as black sub, white sub, candy sub, etc .;
Examples thereof include fatty acids such as ricinoleic acid, palmitic acid, mistyric acid, barium stearate, calcium stearate, magnesium stearate, and zinc stearate, and fatty acid salt systems. One or more of these compounds are used. be able to.

Examples of the flame retardant include alkyl diallyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, triallyl phosphate, tributyl phosphate, triphenyl phosphate, tris (β-chloroethyl) phosphate, tris (dichloropropyl) phosphate. , Tris (2,3
Phosphoric acid-based compounds such as dibromopropyl) phosphate and tris (bromochloropropyl) phosphate; Chlorinated compounds such as chlorinated paraffin, chlorinated polyphenyl and perchloropentacyclodecane; Tetrabromoethane, Tetrabromobutane, Hexabromobenzene Bromines such as decabromodiphenyloxide, polydibromophenyloxide, bis (tribromophenoxy) ethane, ethylenebisdibromonorbornanedicarboximide, ethylenebistetrabromophthalimide; chlorendic anhydride, tetrabromophthalic anhydride, tetrabromobisphenol A , Diethoxy-bis- (2-hydroxyethyl) -aminomethyl phosphate, dibromocresyl glycidyl ether, etc. can be mentioned. Can be used alone or two or more, it can be used in combination stabilizer for flame retardant such as epoxy-based stabilizer.

Examples of the antistatic agent include cationic activators, quaternary ammonium salts, stearoamidopropyldimethyl-β-hydroxyethylammonium nitrate, stearoamidopropyldimethyl-β-hydroxyethylammonium dihydrogenphosphate, special Amine compounds, alkyl phosphates, Na-alkyl diphenyl ether disulfonates, modified aliphatic dimethylethylammonium ethosulfates, anionic activators, polyoxyethylene alkylamines, polyhydric alcohol derivatives, nonionics such as sorbitan monooleate -Based activators, alkylamine derivatives, alkylphosphate amine salts, fatty acid esters, alkyldiethanolamides, polyethylenediglycol esters, organoboron-based activators, electrification Examples thereof include an inhibitor masterbatch, and one or more of these compounds can be used.

Examples of the stabilizers include lead salt stabilizers, metal soaps, metal salt liquid stabilizers, organic tin stabilizers, antimony stabilizers, non-metal stabilizers, and the like. One kind or two or more kinds can be used.

Examples of the antiaging agent include phenyl-α.
-Naphthylamines such as naphthylamine and phenyl-β-naphthylamine; p- (p-toluenesulfonylamide) -diphenylamine, 4,4 '-(α, α'-dimethylbenzyl) diphenylamine, 4,4'-dioctyldiphenylamine and the like Diphenylamine type; N,
N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine,
P-phenylenediamine system such as N, N'-di-2-naphthyl-p-phenylenediamine; amine system other than the above such as condensation product of aromatic amine and aliphatic ketone, butyraldehyde-aniline condensation product; phenyl- a mixture of α-naphthylamine and diphenyl-p-phenylenediamine,
Amine mixture such as a mixture of phenyl-β-naphthylamine and diphenyl-p-phenylenediamine, a mixture of phenyl-β-naphthylamine and p-isopropoxydiphenylamine and diphenyl-p-phenylenediamine; 2,2,4-trimethyl Polymer of -1,2-dihydroquinoline, 6-ethoxy-2,2,4-trimethyl-
Quinoline compounds such as 1,2-dihydroquinoline; 2,5-
Di- (tertiary amyl) hydroquinone, 2,5-di-tertiary 3-
Butylhydroquinone, hydroquinone derivatives such as hydroquinone monomethyl ether; 1-oxy-3-methyl-
Monophenolic compounds such as 4-isopropylbenzene and 2,6-di-tert-butylphenol; 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2′-methylene- Bis- (4-methyl-6-
Cyclohexylphenol), 4,4'-methylene-bis- (4,6-di-tert-butylphenol), 2,
2′-methylene-bis- (6-αmethyl-benzyl-p
-Cresol), methylene-bridged polyhydric alkylphenols, bis such as 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris, Polyphenols;
Thiobisphenols such as 4,4′-thiobis- (6-tert-butyl-3-methylphenol) and 4,4′-thiobis- (6-tert-butyl-o-cresol);
1,1,3-tris- (2-methyl-4-hydroxy-
Hindered phenols such as 5-tert-butylphenyl) butane, 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol); tris (nonylphenyl) phosphite, tris (mixed mono-and The-
Nonylphenyl) phosphite, phenyl-diisdecyl phosphite, and other phosphite ester systems; dilauryl thiodipropionate, distearyl thiodipropionate, dimistyl-3,3′-thiodipropionate,
Ditridecyl-3,3′-thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thiopropionate), dilauryl thiodipropionate, β
-Alkyl thioester propionate, sulfur-containing ester compounds, 1,1 'thiobis (2-naphthol), 2
-Mercaptobenzimidazole, mixture of 2-mercaptobenzimidazole and phenol condensate, zinc salt of 2-mercaptobenzimidazole, zinc salt of 2-mercaptomethylbenzimidazole, zinc salt of 4-mercaptomethylbenzimidazole, dioctadecyl disulfide , A reaction product of morpholine-N-oxydiethylenedithiocarbamate and dibenzothiazyl disulfide, nickel dimethyldithiocarbamate, nickel diethyldithiocarbamate, nickel dibutyldithiocarbamate, nickel diisobutyldithiocarbamate, nickel isopropylxanthogenate, 1,3-bis (dimethyl Aminopropyl) -2-thiourea, tributylthiourea, bis [2-methyl-4- {3-n-alkyl (C
12 or C14) thiopropionyloxy} -5-tert-butylphenyl] sulfide, antigen OS, mixed lauryl stearyl thiodipropionate, cyclic acetal, Sumilizer AZ, Sumilizer MPS, silica gel, Ozonock 733, Antage BOUR, Antage BOP, AD-51, AD-400, Ozonone EX,
Ozonone EX-3 and the like can be mentioned, and one or more of these compounds can be used.

Examples of the copper damage inhibitor and the metal deactivator include 1,2,3-benzotriazole, tolyltriazole, tolyltriazole amine salt, tolyltriazole potassium salt, 3- (N-salicyloyl) amino-1, 2,4-triazole, triazine derivative, tolyltriazole derivative, decamethylenedicarboxylic acid disalicyloyl hydrazide, acid amine derivative, MarkZ
S-81 and the like can be mentioned, and one or more of these compounds can be used.

As the antioxidant, for example, a reaction product of amine and aldehyde such as a condensation product of aniline and an aliphatic aldehyde, a condensation product of naphthylamine and an aldol, a condensation product of an aliphatic amine and an aromatic aldehyde; aniline Condensation products of amines and acetone, condensation products of 4-substituted aniline and acetone, reaction products of amines and ketones such as condensation products of diphenylamine and acetone; phenylnaphthylamine, substituted diphenylamine, substituted p-phenylenediamine, second Aromatic secondary amines such as primary allylamine and derivatives thereof; substituted phenols, substituted phenol sulfides, substituted phenol alkanes, 2,5
Examples thereof include phenols such as -substituted hydroquinone, and one or more of these compounds can be used.

As the ozone deterioration preventing agent, for example, a substitution p
-Phenylenediamine, substituted dihydroquinoline, nickel salt of dithio acid, diallyl osazone, substituted thiourea,
Microcrystalline wax and the like can be mentioned, and one or more of these compounds can be used.

As the ultraviolet absorber and the light stabilizer,
For example, salicylic acid derivatives such as phenyl salicylate and p-tertiary butyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy- 4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-
2'-carboxybenzophenone, 2-hydroxy-4
-Methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxy) Phenyl) methane and other benzophenones; 2-
(2'-Hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-
Chlorobenzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-
3-octylphenyl) benzotriazole, 2-
(2'-Hydroxy-3 ', 5'-di-tertiary-amylphenyl) benzotriazole, 2- [2'-hydroxy-3'-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl ) -5'-Methylphenyl] benzotriazole, 2,2'-methylenebis [4- (1,1,
3,3-Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] and other benzotriazoles; bis (2,2,6,6-tetramethyl-4)
-Piperidyl) sebacate, bis (1,2,2,6,6)
-Pentamethyl-4-piperidyl) sebacate, 1-
[2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4-
{3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9-
Tetramethyl-3-octyl-1,2,3-triazaspiro [4,5] undecane-2,4-dione, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, dimethyl succinate-1 -(2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, poly [[6- (1,1,3,3-tetramethylbutyl) imino-1,3 5-triazine-
2,4-diyl] [(2,2,6,6-tetramethyl-
4-piperidyl) imino] hexamethylene [(2,2,
6,6-Tetramethyl-4-piperidyl) imino]],
2- (3,5-ditert-butyl-4-dihydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6)
6-pentamethyl-4-piperidyl), 1,2,3,4
A condensation product of butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6 -Condensation product of tetramethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-
Butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro Condensation product of [5,5] undecane) diethanol, 1,2,3,4-butanetetracarboxylic acid and 2,
2,6,6-tetramethyl-4-piperidinol and β,
β, β ′, β′-tetramethyl-3,9- (2,4,
8,10-Tetraoxaspiro [5,5] undecane)
Condensate with diethanol, 1,2,2,6,6-tetramethyl-4-piperidyl-methacrylate, 2,2
Hindered amines such as 6,6-tetramethyl-4-piperidyl-methacrylate; acetic acid anilide derivatives, 2
-Ethoxy-5-tert-butyl-2'-ethyloxalic acid bisanilide, 2-ethoxy-2-ethyloxalic acid bisanilide, 2,4-di-tert-butyl-3,5-di-tertiary Butyl-4-hydroxybenzoate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 1,3-bis- (4-benzoyl-3-hydroxyphenoxy) -2-propyl acrylate, 1,3-bis- (4-benzoyl-3-hydroxyphenoxy) -2-propyl methacrylate, 2-
Hydroxy-4-methoxybenzophenone-5-sulfonic acid, methyl o-benzoylbenzoate, ethylhexyl-2-cyano-3,3-diphenylacrylate, 2-
Hydroxy-4-benzyloxybenzophenone,
[2,2'-thiobis- (4-tertiary octylphenolato)]-n-butylamine nickel II, [2,2'-thiobis- (4-tertiary octylphenolato)]-n-ethylhexylamine nickel II , Nickel dibutyldithiocarbamate, nickel thiobisphenol complex, organic light stabilizer containing nickel, organic-inorganic complex containing barium / sodium / phosphorus, semicarbazone type light stabilizer, zinc oxide type ultraviolet stabilizer, etc. And one or more of these compounds can be used.

As the mastication accelerator, for example, pentachlorothiophenol-based, mixed dixylyl disulfide, di- (ο-benzamidophenyl) disulfide, 2-benzamidothiophenol zinc salt, alkylated phenol sulfide, aromatic sulfur compound, Polymer oil-soluble sulfonate, others Pepton44, Renacit8 /
LG, Renacit9, AktiplastT, Ak
tiplastPP, AktiplastF, Stru
ktora-86, Struktora-82, and the like, and one or two of these compounds can be used.
More than one species can be used.

As the tackifier, for example, coumarone / indene resin, coumarone resin / coumarone resin / naphthalene oil / phenol resin / rosin mixture, etc .; p-third
-Phenol / terpene resin systems such as butylphenol / acetylene resin, phenol / formaldehyde resin, tempene phenol resin, polyterpene resin, xylene / formaldehyde resin; Quinton A100, Quinton B170, Quinton D100, Quinton M
100, Quinton U185, Wingtack95,
WingpackExtra, Wingpack86,
Synthetic polyterpene resin system such as Wingpack 10;
Aromatic hydrocarbon resins such as Nisseki Neopolymer 80, Nisseki Neopolymer 120, Nisseki Neopolymer 140, Nisseki Neopolymer 160, Nisseki Neopolymer E-100, Nisseki Neopolymer T, Nisseki Neopolymer S System; Escore
z1102, Escore z1202U, Escore
z1205, Escorez1271, Tucky Roll 1
000, Takkyroll 5000, Piccopale, and other aliphatic hydrocarbon resins; Alcon P-90, Alcon P-100, Alcon P-115, Highlets G-1
Aliphatic cyclic hydrocarbon resin system such as 00X and Hiletz T-100X; Aliphatic / alicyclic petroleum resin system such as Escorez1401; Escorez2101, Esco
aliphatic aromatic petroleum resin system such as rez 2203; Esc
unsaturated hydrocarbon polymer systems such as orez 8030; Es
corez 5380, Escorez 5300 and other hydrogenated hydrocarbon resin systems; YS resin 75, Piccot
Hydrocarbon-based tackifying resin system such as ac resins A;
Petroleum-based hydrocarbon resin systems such as polybutene, atactic polypropylene, liquid polybutadiene, cis-1,4-polyisoprene rubber, hydrogenated polyisoprene rubber, Claprene LIR-290; pentaerythritol ester of rosin, glycerol ester of rosin, hydrogen Added rosin, advanced rosin methyl ester, hydrogenated rosin methyl ester, hydrogenated rosin triethylene glycol ester, hydrogenated rosin pentaerythritol ester, hydrogenated rosin ester, high melting point ester resin, polymerized rosin, resin acid Examples thereof include rosin derivative-based compounds such as zinc and hardened rosin; turpentine-based tackifiers, co-condensates of synthetic resins and phthalic acid esters, nonionic activators, and the like. One or two of these compounds can be used.
More than one species can be used.

Examples of lubricants and slip agents include paraffin waxes such as liquid paraffin, natural paraffin, microwax, polyethylene wax, chlorinated paraffin, fluorocarbon, and synthetic paraffin; stearic acid, palmitic acid, myristic acid, behenic acid, arachidine. Fatty acid-based compounds such as aliphatic amides, alkylene bis-fatty acid amides and other aliphatic amides; butyl stearate and other fatty acid lower alcohols; polyhydric alcohols, polyglycol esters, higher alcohol esters and other ester-based compounds; magnesium stearate, Metal soaps such as calcium stearate and ronozinc; polyhydric alcohols such as fatty alcohols, ethylene glycol, diethylene glycol and triethylene glycol;
Examples thereof include partial esters of fatty acids and polyhydric alcohols, partial esters of fatty acids and polyglycols / polyglycerols, and one or two of these compounds.
More than one species can be used.

Examples of the internal release agent include perfluoroalkyl betaines, perfluoroalkyl ethylene oxide adducts, ether type phosphoric acid esters, synthetic organic acid ester derivatives, nonionic activators, and the like. One kind or two or more kinds can be used from the inside.

As the anti-adhesive agent, for example, a condensate of a fatty acid salt such as Toyozex and a polyether compound, mold 57, mold G-98, new mold EX, GY-
110F, GY-171, EXN-22, PN-11
8, Nobucomaru MS-40, Nobuco LB-550, St
Raktol FZ-04 and the like can be mentioned, and one or more of these compounds can be used.

As the anti-fog agent (anti-drip agent, anti-fog agent),
For example, Mark39, Leodol SP-L10, Leodol SP-P10, Leodol SP-S10, Leodol SP-O10, Leodol TW-L120, Leodol TW-P120, Leodol TW-O120, AD-339, SS-60, Remaquel L-300. , Limacare P-300, Limacare S-300, Limacare O-
300, Limaquer L-250A, Limaquer P-25
0, sorbitan fatty acid ester type such as Limachale S-250, Limacelle O-250; fatty acid diethanolamide type such as amizole CDE, amizole ODE, amizole SDE; registered AF101, registered 8200, antox DFM, PA-1743, P
A-5221, Denon 4190, Rheostat DGS
(B), Limacale S-105, Limacale S-12
0, limaker O-105, limaker O-120, limaker O-320, polyethylene glycol monooleate, polyethylene glycol monolaurate and the like, and one or two of these compounds may be mentioned.
More than one species can be used.

Examples of the anti-scorch agent include organic acids such as phthalic anhydride, salicylic acid, benzoic acid and malic acid,
Nitroso compounds such as N-nitrosodiphenylamine,
N- (cyclohexylthio) phthalimide, sulfonic acid amide derivative, diphenylurea, bis (tridecyl)
Pentaerythritol diphosphite, 2-mercaptobenzimidazole, trichlormelamine and other halides, octadecylamine, dibenzylamine, thiocarbamide, 2-mercaptobenzothiazoline, benzothiazyl, disulfide, dicatecholborate di-
ο-Tolylguanidine salt, N, N'-Disalicylidene-
1,2-alkanediamine, Am. Cyanamid
(MOTS No. 1) and the like, and one or more of these compounds can be used.

Examples of the termiticide include Termite Trivent-K, Termite Trivent-LK1212, Briventol KI, Deldrine HEOD, Aldrin and the like, and one or two of these compounds can be used.
More than one species can be used.

Examples of the repellent include cycloheximide compounding agents such as naramycin and rhamlarin, tert-butylsulfanyldimethyldithiocarbamate such as R-55, dibutyltin fluoride, dihydridylbutylamine and the like. One kind or two or more kinds can be used from the inside.

As the fragrance, for example, AlamaskA
F, AlamaskAO, AlamaskCY, Ala
maskH, AlamaskAA, AlamaskH,
Alamask ND, Rodo No. 0, Rodo
No. 4, Rodo No. 10, sodium borohydride, lithium borohydride, phthalic anhydride,
Examples thereof include peroxides such as sodium perborate and vanilla essence, and one or more of these compounds can be used.

As the surfactant, for example, carboxylate, fatty acid salt, cyclic fatty acid salt, special polycarboxylic acid salt type surfactant, sulfonate, alkyl or alkenyl sulfonate, alkyl allyl sulfonate, alkyl allyl sulfone. Polycondensates of acid salts, sulfates, alkyl sulfates, polyoxyethylene alkyl ether sulfates,
Anionic surfactants such as polyoxyethylene / alkyl phenyl ether sulfate, phosphoric acid ester, alkyl phosphoric acid ester, polyoxyethylene / alkyl (phenyl) ether phosphoric acid ester salt, and inorganic phosphoric acid salt;
Polyoxyethylene derivative, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene alkylamine, Nonionic surfactants such as polyoxyethylene alkyl amides and polyhydric alcohol derivatives; cationic surfactants such as alkylamine salts and quaternary ammonium salts; amphoteric surfactants such as alkyl betaines; fluorochemical surfactants; Examples thereof include silicon-based surfactants and reactive surfactants, and one or more of these compounds can be used.

As the wetting agent, for example, alkylnaphthalene sulfonate, alkyl sulfosuccinate, sulfate,
Polyoxyethylene derivatives such as ADEKA TOL NP-675, Hyonic DE series, Nobuko 2272-R
-SN, Nobu Cowet 50, etc. can be given,
One or more of these compounds can be used.

Examples of the destabilizing agent include organic acid esters, formalin, ammonium salts of strong inorganic and organic acids such as ammonium formate and ammonium acetate, proteolytic enzymes such as glycine and trypsin, and water-soluble alcohols. Organic solvent, mercaptobenzothiazole zinc salt, mercaptobenzimidazole zinc salt,
Examples thereof include diphenylguanidine, higher fatty acid amines, higher alcohols, and silicon defoaming agents, and one or more of these compounds can be used.

Examples of preservatives and fungicides include pentachlorophenol, P-chloro-m-xylenol, dehydroobiethylamine pentachlorophenol, 4-chloro-2-phenylphenol, N- (trichloromethylthio) phthalimide, N, N. -Dimethyl-N'-phenyl- (N'fluorodichloromethylthio)
Sulfamide, N- (trichloromethylthio) -4-chlorohexene-1,2-dicarboximide, 2,4
Organic chlorine compounds such as 5,6-tetrachloro-iso-phthalonitrile; organic copper compounds such as copper-8-quinolinolate; organics such as bis (tri-n-butyltin) oxide, tributyltin laurate, tributyltin chloride Tin compound system; 10,10'-oxybisphenoxacin, vinylidene SB-1, vinylidene SB-
Organic arsenic compounds such as 5-2; quaternary ammonium carboxylate, 2- (4-thiazolyl)
Examples thereof include benzimidazole, and one or more of these compounds can be used.

As the modifier for the sealing gasket,
For example, benzyl alcohol, erucylamide, naphthalenesulfonic acid-formaldehyde condensate / sodium salt, α-cis-9-octadecenyl-O-hydroxypoly (oxyethylene), 4,4′-oxybis (benzenesulfonylhydrazide), sodium tridecylsulfate, Sulfated beef tallow, maleic anhydride-styrene copolymer,
Polyisobutylene, maleic anhydride-ethylene copolymer, sodium di-2-ethylhexyl sebacate polyacrylate, glycerin ester of 12-hydroxystearic acid, calcium zinc stearate, calcium stannous stearate salt, stannous stearate zinc , Tris (nonylphenyl) phosphate, oleyl alcohol, sodium decyl sulfate, sodium lauryl sulfate,
Sodium mistylsulfate, sodium cetylsulfate, polyoxypropylene-polyoxyethylene block polymer, sodium dihexyl sulfosuccinate, coconut oil fatty acid amide, stearic acid amide, arachidyl behylamide, polyethylene glycol fatty acid ester,
Hydrogenated castor oil, hexylene glycol and the like can be mentioned, and one or more of these organic compounds can be used.

Further, the resin modifying additive (Y) used in the present invention is not limited to the above-mentioned additives, but other additives used for the purpose of resin modifying, for example, issued by Rubber Digest Co. The additives described in "Handbook Latest edition of rubber / plastic compounding chemicals" (issued in March 1989) and "New edition plastic compounding agents-basic and applied-" issued by Taisei Co., Ltd. can be mentioned.

To carry out the method of the present invention, resin (X)
The oil-absorbing crosslinked polymer (I) may be contained in a resin composition containing the resin-modifying additive (Y). The method for incorporating the oil-absorbing crosslinked polymer (I) into the resin composition is not particularly limited, and for example, the resin (X) may be added and mixed, and the resin (X) and the resin modifying additive (Y) may be added. The oil-absorptive crosslinked polymer (I) may be added and mixed at the time of mixing using a ribbon blender, a Banbury mixer, a Heisil mixer, or other compounding machine or mixer, and when the resin composition is molded by various molding machines. It is also possible to add and mix an oil-absorptive crosslinked polymer during premixing or molding.

The resin-modifying additive (Y) is mixed in advance with the oil-absorbing cross-linked polymer (I), and the oil-absorbing cross-linked polymer (I) is swollen with the resin-modifying additive (Y). It can also be used as a mixture with the resin (X). Further, a mixture of the resin modifying additive (Y) and the oil-absorptive crosslinked polymer (I) is heated within a range in which the resin modifying additive (Y) does not volatilize or deteriorate, and the resin modifying additive is added. The absorption rate of the agent to the oil-absorbing crosslinked polymer can also be increased.

In order to prevent the bleeding of the resin modifying additive by the method of the present invention, it is preferable to disperse the oil-absorbing crosslinked polymer (I) in the resin composition as uniformly as possible. When the resin composition and the oil-absorbing crosslinked polymer (I) are mixed, the mixture is heated to the extent that the resin-modifying additive (Y) does not volatilize or deteriorate. It is also possible to achieve uniform dispersion.

The mixing ratio of the oil-absorptive crosslinked polymer (I) is 100 parts by weight of the resin composition.
It is in the range of 0.01 to 50 parts by weight. When the amount of the oil-absorbent crosslinked polymer (I) used is less than 0.01 parts by weight, the resin modifying additive (Y) is separated from the resin composition over time, and the resin modifying effect is reduced. The effect of preventing is insufficient. Further, when the oil-absorbing crosslinked polymer (I) is used in an amount of more than 50% by weight, the properties of the resin composition are significantly changed and the modifying effect of the resin modifying additive is deteriorated, which is not preferable.

The resin composition which is prevented from bleeding by the method of the present invention is a molded product which is molded by various molding methods and has the resin modifying effect and preferable surface properties maintained for a long period of time. As the molding method, when the resin (X) is a thermoplastic resin, for example, injection molding method, extrusion molding method, blow molding method, vacuum molding method, inflation molding method, calender molding method, slush molding method, dip molding method, When the resin (X) is heat, light, radiation and other curable resin, for example, a compression molding method, a transfer molding method, an injection molding method, a low pressure molding method, a laminated molding can be adopted. The law etc. can be adopted.

In the resin composition used in the present invention, if necessary, alumina, antimony trioxide, asbestos, barite, calcium carbonate, anhydrite, kaolin clay,
Carbon black, diatomaceous earth, feldspar powder, acid clay, quartz, graphite, magnesium carbonate, magnesium hydroxide, magnesium oxide, mica, molybdenum disulfide,
Woolstone clay, sericite, finely divided silicic acid, silica side, slate powder, talc, titanium oxide, vermiculite, volcanic ash, whiting, precipitated calcium carbonate, heavy calcium carbonate, hydrous silicic acid, anhydrous silicic acid, hydrous silicate, It may contain fillers such as kaolin clay, hard clay, calcined clay, and fine powder talc, and reinforcing agents such as glass yarn, roving, chopped strand, chopped strand mat, glass cloth, glass tape, roving cloth, and milled fiber. ..

When the resin composition containing the oil-absorptive crosslinked polymer (I) used in the method of the present invention is recovered after use, it can be repeatedly used in the present invention.

[0059]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In the examples, parts and% are based on weight unless otherwise specified.

[0060]

[Reference Example 1] 3 parts of gelatin and 3 parts of water were placed in a 500 ml flask equipped with a thermometer, a stirrer, a gas inlet tube and a reflux condenser.
It was dissolved in 00 parts and charged, and the inside of the flask was replaced with nitrogen while stirring, and the mixture was heated to 40 ° C. under a nitrogen stream. Then, nonylphenyl acrylate (SP value:
8.3) 99.794 parts, 0.206 parts of 1,6-hexanediol diacrylate as a crosslinkable monomer (B), and benzoyl peroxide 0.5 as a polymerization initiator.
Part solution at once at 400 rpm
The mixture was vigorously stirred under the conditions of.

Then, the temperature inside the flask was raised to 80 ° C. and maintained at the same temperature for 2 hours to carry out the polymerization reaction. Then, the temperature inside the flask was further raised to 90 ° C. and maintained for 2 hours to complete the polymerization. Let After completion of the polymerization, the granular product was filtered off, washed with water and dried at 60 ° C. to give a particle size of 10
A crosslinked polymer (1) having a size of 0 to 1000 μm was obtained.

[0062]

Reference Example 2 In Reference Example 1, 57.772 parts of dodecyl acrylate (SP value: 7.9) and N, N-dioctyl acrylamide (SP value: 8.) as the monomer (A).
2) 38.515 parts, polypropylene glycol dimethacrylate (molecular weight 400 as crosslinkable monomer (B)
0) A crosslinked polymer (2) having a particle size of 100 to 1000 μm was obtained by the same method as in Reference Example 1, except that 3.713 parts were used instead.

[0063]

Reference Example 3 Stearyl acrylate (SP value: 7.8) 99.855 as the monomer (A) in Reference Example 1
And a particle size of 100 to 1000 μm by the same method as in Reference Example 1 except that 0.145 parts of 1,4 butanediol diacrylate was used as the crosslinkable monomer (B).
A cross-linked polymer (3) was obtained.

[0064]

Reference Example 4 Isobornyl acrylate (SP value: 8.4) 99.796 as the monomer (A) in Reference Example 1
Part, a crosslinked polymer (4) having a particle size of 100 to 1000 μm was obtained by the same method as in Reference Example 1, except that 0.204 part of ethylene glycol diacrylate was used as the crosslinkable monomer (B) instead. It was

[0065]

[Reference Example 5] A glass casting polymerization mold (a tray shape having a size of 5 x 5 x 1 cm) equipped with a thermometer and a gas introduction tube,
Dodecyl acrylate as monomer (A) (SP value:
7.9) A mixed solution consisting of 99.823 parts, 0.177 parts of ethylene glycol diacrylate as a crosslinkable monomer (B), and 0.1 parts of 2,2′-azobisdimethylvaleronitrile as a polymerization initiator. Inject and under a nitrogen stream 60
Polymerization reaction was carried out by heating at 0 ° C for 2 hours, then heated to 80 ° C and maintained for 2 hours to complete the polymerization. After cooling, the gel-like material was peeled from the mold to obtain a crosslinked polymer (5).

[0066]

Reference Example 6 Hexadecyl methacrylate (SP value: 7.8) 49.93 as the monomer (A) in Example 5.
0 part and N-octyl methacrylamide (SP value:
8.6) except that 49.930 parts and 0.140 parts of divinylbenzene as the crosslinkable monomer (B) are used instead.
A crosslinked polymer (6) was obtained in the same manner as in Reference Example 5.

[0067]

Reference Example 7 Cyclohexyl methacrylate (SP value: 8.3) 99.7 as the monomer (A) in Reference Example 5
A crosslinked polymer (7) was obtained in the same manner as in Reference Example 5 except that 71 parts and 0.229 parts of N, N ′ methylenebisacrylamide as the crosslinkable monomer (B) were used instead.

[0068]

Reference Example 8 Isobornyl acrylate (SP value: 8.4) 99.796 as the monomer (A) in Reference Example 5
A crosslinked polymer (8) was obtained in the same manner as in Reference Example 5, except that 0.204 part of ethylene glycol diacrylate was used as the crosslinkable monomer (B).

[0069]

[Reference Example 9] In a 500 ml flask equipped with a thermometer, a stirrer, a gas introduction tube, two dropping funnels and a reflux condenser,
Charge 3 parts of polyoxyethylene glycol (degree of polymerization 17) monononylphenyl ether and 100 parts of water, and
The inside of the flask was replaced with nitrogen while stirring under the condition of 00 rpm, and the flask was heated to 70 ° C. under a nitrogen stream.

On the other hand, t-butylstyrene (SP value: 7.9) 54.881 parts and 1-decene (SP value: 7.0) 44.903 parts as the monomer (A), a crosslinkable monomer As the monomer (B), a monomer composed of 0.216 parts of divinylbenzene was added to polyoxyethylene glycol (degree of polymerization 17).
In an aqueous solution in which 150 parts of water was dissolved 3 parts of monononyl phenyl ether, a homogenizer was used to mix for 10 minutes at 5000 rpm to prepare 253 parts of an aqueous dispersion of a monomer. Further, 1 part of sodium persulfate as a polymerization initiator was dissolved in 50 parts of water to prepare 51 parts of an aqueous solution of the polymerization initiator.

Each of the aqueous dispersion of the monomer and the aqueous solution of the polymerization initiator was placed in a separate dropping funnel, and 50 parts of the aqueous dispersion of the monomer and 5 parts of the aqueous solution of the polymerization initiator were placed in a flask. Polymerization was initiated. Then, while maintaining the inside of the flask under a nitrogen stream at 70 ° C., the remaining aqueous dispersion of the monomer was dropped over 120 minutes, and at the same time, the remaining aqueous sodium persulfate solution was dropped over 240 minutes. After completion of the dropping, the polymerization was further completed by maintaining at 70 ° C. for 120 minutes to obtain an aqueous dispersion of the crosslinked polymer (9). The average particle size of this crosslinked polymer (9) was 0.2 μm, and the content of the crosslinked polymer (9) in the obtained aqueous dispersion was 25.5%.

[0072]

Reference Example 10 Nonylphenyl acrylate (SP value: 8.3) 74.7 as the monomer (A) in Reference Example 9
93 parts and hydroxyethyl acrylate (SP value:
10.3) 24.931 parts and a crosslinked polymer (using the same method as in Reference Example 9 except that 0.276 parts of 1,6-hexanediol diacrylate was used as the crosslinkable monomer (B) instead. An aqueous dispersion of 10) was obtained. The average particle size of the crosslinked polymer (10) was 0.15 μm, and the content of the crosslinked polymer (10) in the obtained aqueous dispersion was 25.0%.
Met.

[0073]

Reference Example 11 In Reference Example 9, 99.811 parts of vinyl laurate (SP value: 7.9) as the monomer (A) and 0.187 parts of trimethylolpropane triacrylate as the crosslinkable monomer (B). An aqueous dispersion of the crosslinked polymer (11) was obtained by the same method as in Reference Example 9 except that was used instead. The average particle size of this crosslinked polymer (11) was 0.1.
5 μm, and the crosslinked polymer (1
The content of 1) was 25.0%.

[0074]

Reference Example 12 In Reference Example 9, t as the monomer (A)
-Butyl acrylate (SP value: 8.7) 98.991
Parts, except that 0.204 parts of polyethylene glycol diacrylate (molecular weight 500) was used instead as the crosslinkable monomer (B), an aqueous dispersion of the crosslinked polymer (12) was prepared in the same manner as in Reference Example 9. Obtained. This crosslinked polymer (12)
Had an average particle diameter of 0.2 μm, and the content of the crosslinked polymer (12) in the obtained aqueous dispersion was 25.0%.

[0075]

Comparative Reference Example 1 A method similar to Reference Example 1 except that the amount of nonylphenyl acrylate was changed to 94.541 parts and the amount of 1,6 hexanediol diacrylate was changed to 5.459 parts. Thus, a comparative crosslinked polymer (1) was obtained.

[0076]

Comparative Reference Example 2 Instead of 99.794 parts of nonylphenyl acrylate in Reference Example 1, 39.713 parts of nonylphenyl acrylate and acrylonitrile (SP
Value 9.2) 59.570 parts were used, and the comparative crosslinked polymer (2) was prepared in the same manner as in Reference Example 1 except that the amount of 1,6 hexanediol diacrylate was changed to 0.717 parts.
Got

[0077]

Comparative Reference Example 3 A comparative polymer (3) was obtained in the same manner as in Reference Example 1 except that 1,6 hexanediol diacrylate was not used in Reference Example 1.

[0078]

Comparative Reference Example 4 Comparative cross-linking weight was the same as in Reference Example 5, except that the amount of dodecyl acrylate was changed to 94.637 parts and the amount of ethylene glycol diacrylate was changed to 5.363 parts. United (4)
Got

[0079]

Comparative Reference Example 5 In Reference Example 5, dodecyl acrylate 3 was used instead of 99.823 parts of dodecyl acrylate.
9.854 parts and methacrylic acid (SP value: 10.1)
A comparative crosslinked polymer (5) was obtained in the same manner as in Reference Example 5 except that 59.780 parts were used and the amount of ethylene glycol diacrylate was changed to 0.366 part.

[0080]

Comparative Reference Example 6 A comparative polymer (6) was obtained in the same manner as in Reference Example 5, except that 1,6 hexanediol diacrylate was not used in Reference Example 5.

[0081]

Comparative Reference Example 7 Reference Example 11 except that the amount of vinyl laurate was changed to 94.619 parts and divinylbenzene 5.381 parts was used instead of 0.216 parts of trimethylolpropane triacrylate. An aqueous dispersion of the comparative crosslinked polymer (7) was obtained by the same method as described above.

[0082]

Comparative Reference Example 8 Instead of 99.811 parts of vinyl laurate in Reference Example 11, vinyl laurate 39.91 was used.
1 part and hydroxyethyl acrylate (SP value: 1
0.3) 59.867 parts were used, and divinylbenzene 0.2 was used instead of trimethylolpropane triacrylate.
An aqueous dispersion of comparative crosslinked polymer (8) was obtained in the same manner as in Reference Example 11 except that the amount was changed to 22 parts.

[0083]

Comparative Reference Example 9 An aqueous dispersion of Comparative Polymer (9) was obtained in the same manner as in Reference Example 11 except that trimethylolpropane triacrylate was not used in Reference Example 11.

[0084]

Example 1 Crosslinked polymer (1) obtained in Reference Examples 1 to 4
To (4) and 0.5 parts of each of the comparative polymers (1) to (3) obtained in Comparative Reference Examples 1 to 3, 100 parts of polyvinyl chloride having a polymerization degree of 1000, and 35 parts of di2-ethylhexyl phthalate. Epoxidized soybean oil (2 parts), barium zinc (2 parts) and polyethylene glycol monolaurate (2 parts) were mixed in a mixer, and then mixed at 150 ° C. with a biaxially stretching roll to give a 0.2.
Sheet-shaped resin composition (1) having a thickness of 6 mm
(4) and comparative resin compositions (1) to (3) were molded. For comparison, a sheet-shaped blank resin composition to which a crosslinked polymer or a comparative polymer was not added was molded. An outdoor exposure dust adhesion test was conducted on these compositions by the following method, and the results are shown in Table 1.

(Outdoor exposure dust adhesion test) The sheet-shaped resin composition was cut into a rectangle of 10 cm x 5 cm to prepare a test piece. Each of the test pieces was fixed on a south-facing exposure table on the roof of a 6-story research office building of Nippon Shokubai Co., Ltd. Kawasaki Laboratory, and the adhesion state of dust after 3 months was visually and visually observed.

[0086]

[Table 1]

[0087]

Example 2 Crosslinked polymer (5) obtained in Reference Examples 5-8
To (8) and Comparative Polymers (4) to (6) obtained in Comparative Reference Examples 4 to 6, 0.5 parts of each, 15 parts of chlorinated paraffin, 0.1 part of zinc stearate, a lubricant (Kao By dipping and swelling for 24 hours in a mixture consisting of 1 part of Electrostripper H) manufactured by the same company and 10 parts of dioctyl sebacate, a slurry composition comprising a crosslinked polymer and a resin modifying additive was obtained. Mixing each of these slurry-like compositions with 100 parts of polystyrene pellets,
Then roll kneading at 175 ° C for 10 minutes, then 175 ° C
Sheet-shaped resin compositions (5) to (8) and comparative resin compositions (4) to (5) having a thickness of 0.5 mm after press working for 5 minutes.
(6) was obtained. For comparison, a sheet-shaped blank resin composition to which a crosslinked polymer or a comparative polymer was not added was molded. A toner ink transfer test was conducted on these compositions by the following method, and the results are shown in Table 2.

(Toner Ink Transfer Test) A sheet-shaped resin composition was cut into a 2 cm × 7 cm strip to prepare a test piece. On each of the test pieces, a paper blackened with copy toner was placed so that the black surface was on the test piece side. Three pieces of the test pieces thus stacked were sandwiched between glass plates having a 10 cm square and a thickness of 2 mm, and a weight of 2 kg was placed on the glass plate, and the plate was allowed to stand at 80 ° C. for 17 hours. Then, the black paper was peeled off from the test piece, and the transfer state of the toner ink to each sheet composition was visually observed.

[0089]

[Table 2]

[0090]

Example 3 Aqueous dispersions of crosslinked polymers (9) to (12) obtained in Reference Examples 9 to 12 and comparative polymers (7) to (9) obtained in Comparative Reference Examples 7 to 9 were prepared. 2 parts each, 100 parts polypropylene powder, 2,6-di-tert-butyl-
A sheet having a thickness of 0.6 mm after mixing 0.5 parts of 4-methylphenol, 0.5 part of calcium stearate, 10 parts of octyl azelate and 4 parts of tetrabromobisphenol A, and extruding at 260 ° C. by a T-die method. -Shaped resin compositions (9) to (12) and comparative resin compositions (7) to (9) were obtained. For comparison, a sheet-shaped blank resin composition to which a crosslinked polymer or a comparative polymer was not added was molded. An alkaline boiling water test was conducted on these compositions by the following method, and the results are shown in Table 3.

(Alkali Boiling Water Test) The sheet-shaped resin composition was cut into a 2 cm × 7 cm strip to prepare a test piece. Each of the test pieces was treated with 100 of a pH 12 NaOH aqueous solution.
It was immersed in ml and boiled at 100 ° C. for 1 hour. The appearance of the test piece after boiling was visually observed.

[0092]

[Table 3]

[0093]

Example 4 Crosslinked polymer (1) obtained in Reference Examples 1 to 4
To (4) and 2 parts of each of the comparative polymers (1) to (3) obtained in Comparative Reference Examples 1 to 3, 100 parts of a polyol having a hydroxyl value of about 56, 0.3 part of triethylenediamine, and a silicon-based foam control. Agent (TSA772 manufactured by Toshiba Silicone Co., Ltd.)
1.0 part, trichlorofluoromethane 5.0 parts, stanna octoate 0.1 part, wax (BASF Corp. W
ax-LGE) 3 parts, carbon black 25 parts and trioctyl phosphate 1 part were mixed. By mixing each of these mixtures with 1.05 equivalent of a cross-linking agent, 2,6-tolylene diisocyanate, by a one-shot method,
Soft polyurethane sheet-shaped resin compositions (1 ′) to (4 ′) and comparative resin compositions (1 ′) to (3 ′) having a thickness of 0.6 mm were obtained. For comparison, a sheet-shaped blank resin composition to which a crosslinked polymer or a comparative polymer was not added was molded. Example 2 for these compositions
A toner ink transfer test was conducted in the same manner as in, and the results are shown in Table 4.

[0094]

[Table 4]

[0095]

According to the method for preventing bleeding of the resin modifying additive of the present invention, the resin modifying effect incorporated into the resin composition is separated from the resin composition over time, and the resin modifying effect is obtained. It is possible to effectively prevent the deterioration of the resin composition and the transfer of the resin modifying additive to the surface of the resin composition to adversely affect the physical properties of the resin surface.

The method for preventing bleeding according to the present invention can simplify the conventional formation for preventing bleeding, which has been complicated depending on the combination of a wide variety of additives and resins, and can prevent cross-linking of the surface of a resin molded product. Unlike the coating method, the number of manufacturing steps does not increase and the cost does not increase, so that it is highly industrially practical. Further, the oil-absorbing crosslinked polymer (I) used in the method of the present invention
Has a small effect on the physical properties of the resin composition, and does not impair the transparency.

Therefore, according to the method of the present invention, resin modifying additives and a large amount of additives which could not be used until now due to the decrease in strength of the resin composition, the opacity and the contamination due to bleed, were added to the resin. It becomes possible to add it to the composition.

The resin modification effect sustained by the bleed prevention method of the present invention includes, for example, processability, adhesiveness, moldability, low temperature embrittlement prevention property, transparency, light transmission, plasticity, softness and flame retardancy. , Smoke prevention, antistatic property, stability, anti-aging property, copper damage prevention property, anti-oxidation property, ozone deterioration prevention property, UV deterioration prevention property, light stability, mastication promoting property, tackiness, lubricity, Slip, releasability, coloring, antifouling, anti-adhesion, anti-fog, anti-condensation, dust adhesion prevention, antiseptic, heat retention, foaming, scorch prevention, earthquake resistance, impact resistance , Ant-repellent, repellent, scented, surface physical properties, wettability, printing characteristics, slow coagulation, heat sensitivity, film-forming property and antifungal property.

Therefore, the present invention is effective as a method for preventing bleeding of resin modifiers for all plastics and / or elastomers, and can be used in a wide range of fields.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C08L 25:00 27:06 33:06

Claims (2)

[Claims] 1. A plastic and / or elastomer (hereinafter referred to as a resin (X)) and a resin modifying additive (Y)
In a resin composition consisting of, a monomer (A) 96 to 9 having one polymerizable unsaturated group in the molecule whose main component is a monomer having a solubility parameter (SP value) of 9 or less.
9.999% by weight and 0.001 to 4 crosslinkable monomers (B) having at least two polymerizable unsaturated groups in the molecule
% By weight (however, the sum of monomers (A) and (B) is 10
The oil-absorptive crosslinked polymer (I) obtained by polymerizing a monomer component consisting of 0% by weight) is contained in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the resin composition. Characteristically, the resin modifying additive (Y) is separated from the resin composition over time and the resin modifying effect is reduced, or the resin modifying additive (Y) migrates to the surface of the resin composition. A method for preventing bleeding of an additive for resin modification, which prevents the physical properties of a resin from being adversely affected. 2. The monomer (A) has at least one aliphatic hydrocarbon group having 3 to 30 carbon atoms and is alkyl (meth) acrylate, alkylaryl (meth) acrylate, alkyl (meth) acrylamide. , Alkylaryl (meth) acrylamide, fatty acid vinyl ester,
The method for preventing bleeding of an additive for resin modification according to claim 1, which comprises at least one unsaturated compound (a) selected from the group consisting of alkylstyrene and α-olefin as a main component.