JPS6049661B2 - synthetic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a synthetic resin composition with improved processability.

More specifically, it relates to a synthetic resin composition with improved processability and thermal stability, which contains a partial transesterification product of an α/β-olefinically unsaturated carboxylic acid alkyl ester oligomer and a polyalkylene glycol. .
Generally polyethylene, polypropylene, polystyrene,
Synthetic resins such as polyvinyl chloride and ABS have a high melt viscosity even during heat processing, and may overheat the processing machine due to frictional heat, or may stick to the processing machine, making it difficult to flow. In addition, the molded product may adhere to the surface of the mold, making it difficult to mold, or the films may adhere to each other, resulting in poor opening. These problems are caused by the lubricity of the resin, and in conventional technology, processability improving agents such as lubricants, fluidity improvers, mold release agents, slip agents, and anti-blocking agents are added to prevent such disadvantages. I came. The processability improving agent added and blended for this purpose must have an appropriate shape, have good dispersibility in the resin, lubricity, processability, and thermal stability, and maintain the lubricity effect throughout the entire processing process. Does not interfere with the gelation of the compound, does not inhibit the heat resistance and weather resistance of the resin, does not react with plasticizers, stabilizers, colorants, fillers and other resin additives, does not cause bloom, bleed, devitrification, It is necessary to meet certain conditions such as not causing whitening or having any adverse effect on the properties of the product. Conventionally used processability improving agents include fatty acids such as stearic acid and their metal soaps, esters, amides, higher alcohols such as stearyl alcohol, paraffins, waxes, and acrylate oligomers. - etc.

In addition, it is also known to add inorganic substances such as silicon oxide as an anti-blocking agent. However, these processability improving agents are still insufficient and none satisfy the above conditions. For example, stearic acid is prone to blooming and plate-out, and has poor transparency. Esters and amides have insufficient lubricity and poor thermal stability. Furthermore, amides bloom violently, impairing initial coloring and transparency. Paraffins generally tend to bloom, and metal soaps tend to plate out and are often unsuitable for clear formulations. Furthermore, acrylate oligomers have poor releasability. Furthermore, the addition of inorganic substances always has a negative effect on the optical, physical and electrical properties of the resin, and in many cases even reduces processability.

Moreover, these processability improving agents hardly improve impact resistance. As a result of intensive studies to solve this time-consuming problem, the present inventors found that it has excellent not only lubricity but also thermal stability, transparency, and especially roll releasability, does not cause bloom, bleed, or plate-out, and has optical properties. For the first time, we have identified a processability improver system that has little negative effect on electrical properties and also improves impact resistance and thermal stabilizers.

That is, the present invention uses an oligomer having an average degree of polymerization of 5 to 50 containing an acrylic acid alkyl ester or an itaconic acid alkyl ester as a main monomer, and a polyalkylene glycol monoether or a polyalkylene glycol monoester to 100 parts by weight of a synthetic resin. The object of the present invention is to provide a synthetic resin composition with improved processability, which comprises adding 0.005 to 5 parts by weight of a partial transesterification product with a polyester.

In the oligomer whose main monomer is an acrylic acid alkyl ester or an itaconic acid alkyl ester, which is a raw material for the partial transesterification product of the present invention, the alkyl group may be a straight chain, branched, cyclic, or substituted type thereof having one or more carbon atoms. can be used, for example methyl, ethyl,
Isopropyl, n-butyl, isobutyl, tert-butylpentyl, cyclohexyl, hexyl, n-octyl, isooctyl, 2-ethylhexyl, decyl, dodecyl,
Groups such as tritecyl, tetradecyl, hexadecyl, and octadecyl are mentioned, and the oligomer according to the present invention is a polymer having at least one monomer selected from these as a main monomer, and depending on the purpose, Other vinyl monomers such as ethylene, propylene, α-olefins such as butene-1, styrene, chlorostyrene, acrylonitrile,
It may contain monomer units such as vinyl acetate, butadiene, vinyl alcohol, vinyl butyral, and vinyl acetal.

The oligomer according to the present invention includes adjusting the degree of polymerization using an initiator,
It can be easily produced by known methods such as polymerization in an active solvent, ionic low polymerization, and low polymerization using an organometallic complex.

Specific examples of oligomers according to the present invention include methyl acrylate oligomer (■:9), ethyl acrylate oligomer (i:10), ethyl acrylate oligomer (i:13), and isopropyl acrylate oligomer (i:13). , butyl acrylate oligomer (i:18), butyl acrylate oligomer (i:
15), butyl acrylate to 4-vinyl-2-pyrrolidone oligomer (41 mol, i:12), butyl acrylate to allyl chloride oligomer (10:0.
5 mol, i: 10), isobutyl acrylate to p-chlorostyrene oligomer (3″ 1 mol, h: 15),
Butyl acrylate to acrylonitrile oligomer (4
: 1 mol, i: 13), 2-ethylhexyl acrylate oligomer (i: 7), 2-ethylhexyl acrylate oligomer (b: 15), ethyl acrylate ~
Styrene oligomer (31 mol, i:11), diethyl itaconate oligomer (i:48), diethyl itaconate oligomer (i:7), diethyl itaconate oligomer (i:21), dibutyl acrylate oligomer ( i:13), dioctyl itaconate
oligomer (i: 13), dioctyl itaconate oligomer (i: 22), dioctyl itaconate oligomer (i: 8), butyl lauryl itaconate oligomer (i: 11), butyl stearyl itaconate oligomer (i :11) Dilauryl itaconate oligomer (i: 14), dibenzyl itaconate oligomer (i: ・22), diethyl itaconate ~ styrene oligomer (21 mol, i: 18), dibutyl itaconate ~ styrene ~ octene 1. Oligomer (4:2
゜1 mol, i: 19), diethyl itaconate - octene-1 oligomer (41 mol, ) i: 15), diethyl itaconate - acrylonitrile oligomer (15)
:1 mol, i:15), etc.

On the other hand, the polyalkylene glycol in the polyalkylene glycol monoether or monoester includes polyethylene glycol and polypropylene glycol, and those with a degree of polymerization of 4 to 50 are preferred, and those with a degree of polymerization of 10 to 25 are particularly preferred.

Specific examples of these include polyethylene glycol*alkyl ether, polyethylene glycol*alkylaryl ether, polyethylene glycol*polypropylene glycol*alkyl ether, polyethylene glycol*fatty acid ester, and the like. The alkyl groups mentioned above include methyl, butyl, 2-ethylhexyl, octyl, nonyl, lauryl, tridecyl, cetyl, stearyl, oleyl, and the like, and the alkylaryl groups include octylphenyl, nonylphenyl, and the like.

Examples of fatty acids include lauric acid, stearic acid, oleic acid, palmitic acid, and tall oil fatty acids. The polyalkylene glycol component content in the transesterified product of the oligomer of the present invention and polyalkylene glycols is preferably 5 to 5% by weight, and if it is 5% by weight or less, the difference in performance from the raw material oligomer is small; amount%
If the roll is above, there is a lot of dirt on the roll and the peeling property is also poor.

An example of the synthesis of the partial transesterification product used in the present invention is as follows.

That is, first, an oligomer of acrylic acid alkyl ester or itaconic acid alkyl ester constituting the target compound is synthesized, and then transesterification is performed with polyalkylene glycols in the presence of a transesterification catalyst to remove excess monovalent monovalent ester. Synthesized by removing alcohol. In some cases, it is also possible to use it as it is after removing the alcohol. The partially transesterified product added to the synthetic resin of the present invention can be produced by commonly used general synthesis methods, and the present invention is not limited in any way by these production methods.

Synthesis Example 1 2-ethylhexyl acrylate oligomer (i:12
) and methoxypolyethylene glycol (MW55O..
i±12) in 500771 L in a four-wall flask with dioctyltin oxide (a) as a catalyst. 1%) and 1
A transesterification reaction was carried out in a nitrogen stream at 70'C for 2 hours, and then dealcoholization was carried out under a reduced pressure of 15 kg Hg for 5 hours to obtain a pale yellow viscous liquid.

The usable amount of the partially transesterified product according to the present invention is 0.005 to 5 parts by weight per 10 parts by weight of resin.

At 0.005 parts by weight or less, almost no effect is observed;
Even if more than 1 part by weight is added, no significant improvement in effect is observed.

In the present invention, phthalate plasticizers, other ester plasticizers, polyester plasticizers, phosphate ester plasticizers, epoxy plasticizers, chlorine plasticizers, and other plasticizers are used depending on the application. Various plasticizers such as those disclosed in Japanese Unexamined Patent Publication No. 49-5705 can be used as specific examples.

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

These antioxidants include phenolic antioxidants, phosphite antioxidants, amine antioxidants, sulfur-containing compounds, etc. Specific examples include JP-A-49-17
Various antioxidants such as those disclosed in 869 Trowel Publication can be used. By adding an ultraviolet absorber to the composition of the present invention, the photostability can be improved, so it is possible to appropriately select and use these depending on the purpose of use.

These include benzophenone, benzotriazole,
Salicylates, substituted acrylonitriles, various metal salts or metal chelates, especially nickel or chromium salts or chelates, triazine, piperidine, etc. are included, and are specifically disclosed in JP-A-49-78692. Generally, when metal soaps are used as stabilizers for halogen-containing synthetic resins, there are some that are often used alone, such as organotin stabilizers and lead soaps.

Metal soaps such as cadmium, barium, zinc, calcium, magnesium, strontium, potassium, and sodium are often used in combination of two or more of these. For example, Cd1? , Cd Kazuomi-Zn. ．． Ba-Zn
．． ．． Ca-Zn. sCa-Mgl-Ca-Mg-Znl
Cd-? one organotin, Cd Kazuomi-PdlCa-Sr. ．． Z
n-X,. Many combinations are adopted depending on the intended use of Zn-Na and the like. Others as necessary, such as epoxy stabilizers, organic chelators, pigments, fillers, blowing agents, etc.
Antistatic agents, antifogging agents, plate-out prevention agents, surface treatment agents, other lubricants, anti-hardening agents, flame retardants, light stabilizers, ultraviolet absorbers, luminescent agents, antifogging agents, bactericidal agents, metal deactivation It is possible to include agents, photodegradants, nonmetallic stabilizers, epoxy resins, borate esters, thiourea derivatives, processing aids, mold release agents, and the like.

Examples of the synthetic resins according to the present invention include polyvinyl chloride, polyvinyl bromide, polyvinylidene fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, brominated polyethylene, chlorinated rubber, and vinyl chloride. Vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene copolymer Maleic anhydride terpolymer, vinyl styrene chloride-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer,
Vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylic nitrile copolymer , halogen-containing synthetic resins such as internally plasticized polyvinyl chloride, α-olefin polymers such as polyethylene, polypropylene, polybutene, and poly-3-methylbutene, or polyolefins such as ethylene-vinyl acetate copolymers and ethylene-propylene copolymers; co-weighted. combinations, polystyrene, polyvinyl acetate, acrylic resins, styrene and other monomers (e.g. maleic anhydride,
butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, methacrylic ester-butadiene-styrene copolymers, methacrylate resins such as polymethyl methacrylate, Polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, linear polyester, polyamide, polycarbonate, polyacetal, polyurethane, cellulose resin, phenolic resin, area resin, melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, etc. Furthermore, rubbers such as natural rubber, isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, and blends of these resins may also be used. The present invention will be explained using examples, but the present invention is not limited to the following examples.

Example 1 In order to examine the effect of the compound according to the present invention as a lubricant on soft polyvinyl chloride resin, a kneading test was conducted using a calendar roll using the following formulation, and the onset time of adhesion on the roll and the occurrence of coloring were investigated.

A thermal stability test, transparency, peelability and roll staining tests were also conducted. The results are shown in Table 1 below. <Composition> PVC (GeOnlO3EP) 10 parts DOP6O epoxidized soybean oil
2 Hikiichi Nonyl phenate 0.5 parts by weight Zn-toluate 0
．． 5 octyl diphenyl phosphite 0.5
Lubricant 0.5 Example 2 In order to examine the effect of the compound of the present invention on hard PVC, the adhesion time to the roll was measured in the same manner as in Example 1 using the following formulation, and the peelability was also examined.

The results are shown in Table 2. Blend> PVC (GeOnlO3EP-8) 1 part by weight dibutyltin bis(butyl malate) 2.0 Lubricant. ．． 0.5 Example 3 PVC resin and ABS resin of the compound according to the invention. In order to see the effect on the polymer blend, the following formulation was kneaded for 5 minutes on a heated roll at 150°C, and the peelability from the roll was examined.

The results are shown in Table 3 below. Compound> PVC (GeOnlO3EP-8) 5 Saliva volume ABS (Toyorak 102) 5
0 dibutyltin mercaptopropionate 1.

5 Additives 1.0 Example 4 To see the effect of the processing aid of the present invention, 1.0 parts of the processing aid was added to 10 parts of comb-modified polystyrene resin (Dialex HT886: Mitsubishi Monsanto). A respiral flow test was conducted using an injection molding machine under the conditions of 200'Cl8OOk9lcTl with addition of a saliva portion.

The results are shown in Table 4 below. Example 6 In order to examine the processability of the ethylene-vinyl acetate copolymer resin composition of the present invention, a formulation consisting of the following formulation was kneaded on rolls (roll temperature 140°C, roll gap 0.3T!!
The peelability from the roll was observed after 5 minutes (30 rpm).

The results are shown in Table 6. Blend> Ethylene-vinyl acetate copolymer resin (vinyl acetate content 14%)
10 weighing section BHTO. l additive
0.4 Example 5 After mixing 3 parts by weight of the processing aid listed in Table 5 with 10 parts by weight of a commercially available ABS resin, a test piece was prepared by injection molding.

Next, the isot value was measured using an impact tester, and the flow characteristics were measured using a spiral flow using an injection molding machine. The results are shown in Table 5. Example 7 In order to examine the lubricity effect of the processability improving agent system according to the present invention, 1.0 parts of lubricant (Table 7) was added to 10 parts of resin. The amount of plunger descent (TrOnlsec) of the resin formulation obtained by adding the volume part was measured using a Koka-type flow tester.

The results are shown in Table 7. The measurement conditions for the Koka type flow tester are as follows.

PE: 1200C50k91cItPS (GP): 190〃 PS: 200〃 PMMA: 200〃 Hereinafter, unless otherwise specified, the following abbreviations and products were used for the resins.

PE: Polyethylene (Shorex 60501 manufactured by Nippon Olefin Chemical KK), SS (GP): GP polystyrene (Copal 8, manufactured by Nippon Olefin Chemical KK), PP:
Polypropylene (Profax 6501, manufactured by Hercules), PMMA: polymethyl methacrylate resin (
Acrypet M1 made by Mitsubishi Rayon).

Claims (1)

[Claims] 1 Partial ester of an oligomer with an average degree of polymerization of 5 to 50 containing acrylic acid alkyl ester or itaconic acid alkyl ester as the main monomer and polyalkylene glycol monoether or polyalkylene glycol monoester, based on 100 parts by weight of synthetic resin. Replacement 0.005~5
A synthetic resin composition with improved processability, which comprises adding parts by weight.