JPS60208349A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a composition having high impact strength, transparency, heat-resistance and flame-retardance, and composed of a chlorine-containing resin and a copolymer resin obtained by the polymerization of alpha-alkylstyrene monomer, a nitrile monomer, etc. in the presence of a diene rubber grafted with a methacrylate. CONSTITUTION:The objective composition can be produced by compounding (A) 15-85pts.(wt.) of copolymer resin prepared by the suspension or bulk polymerization of (a) 5-50pts. of a diene rubber grafted with 5-40wt% methacrylate (based on the rubber) and (b) 95-50pts. of a monomer system consisting of (i) 30-85pts. of an alpha-alkylstyrene monomer, (ii) 15-40pts. of a nitrile monomer, (iii) 10-65pts. of a methacrylate monomer and (iv) 0-10pts. of a monomer copolymerizable therewith, with (B) 85-15pts. of a chlorine-containing resin. The polymerization initiator of the component A is a polyfunctional peroxide and/or an azo compound. The component B is e.g. chlorinated polyvinyl chloride, etc.

Description

[Detailed description of the invention]

The present invention relates to a resin composition having excellent transparency, flame resistance, heat resistance, and button impact resistance. ], I.U.
UWt, % vs. 1-7) is graph h (-Tanoeno Itoko J, 5-50 market weight ff1s (hereinafter simply referred to as part)
Skip-Full Kills Hand Thread Thumbnail-80~85 FRI
, = I-II Lua fz% / / -15~4 (
] For river use, methacrylic acid ester yarn pick-1+1~
65, and 0 to 10 parts of a monomer capable of copolymerizing with these monomers, preferably a polyfunctional peroxide having a half-life temperature of 6() to 20° C. Copolymer resin 15 to 8 which can be obtained by suspension polymerization or bulk polymerization using (-〇-〇- compound with multiple negative bonds) and/or azo compound (-, 4yB by suspension polymerization or bulk polymerization
5 parts and 85 to 15 parts of a chlorine-based resin. Transparency is listed as one of the physical properties aimed at by the resin of the present invention, but in order to achieve this objective it is necessary to remove impurities as much as possible. For example, milk (1m polymerized diene thread rubber grafted in powder state and 15
In addition, heat resistance as used in the present invention"1. : Polymer (α
- a copolymer of alkyl-restyrene, nidol-11, methacrylic acid ester, etc.) was obtained by suspension polymerization, and the above-mentioned graph l
[Rubber and chlorine-based resin and extrusion] A method of blending using a machine or the like is considered. 711 L, in this case, two effects are expressed on the impact strength of the rubber.1. Hateful,. Another method is to obtain the α-1 lugylstyrene i copolymer by emulsion polymerization instead of by suspension polymerization, blend it with graph 1 rubber latex in a latex state, coagulate and dry it, and make a powdery resin. A possible method is to blend it with a chlorine-based resin after cooling. 7D) In this case, milky white turbidity appears, which is thought to be caused by the coagulant, etc., and thermal stability is generally poor. In view of this situation, the inventors of the present invention have found that the present inventors have developed a method that provides good transparency and makes it easy for the eyes to see.
The present invention was developed as a result of extensive research in an attempt to obtain a flame-retardant resin with high impact strength. That is, the present invention is a method for producing a rubber yarn obtained by suspension polymerization or bulk polymerization of an α-alkyl styrene monomer, a nitrile monomer, and a methacrylic acid ester thread rubber in the presence of a diene thread rubber grafted with a methacrylic acid ester. Eri to blend 1 copolymer resin and chlorine resin,
The present invention provides a flame-retardant resin composition that has excellent impact strength, transparency, thermal stability, etc. In order to obtain a 3-elastomer-reinforced thermoplastic resin with excellent heat deformation resistance by using a high proportion of +α-alkyl styrene monomers as in the present invention, by suspension or bulk polymerization, tertiary 11-butylbarbenzoate is used. 1
-, ditarsha 11-butylbenzoate 1-, tanternary rubber oxide 1-, and other organic peroxides as polymerization initiators.

[7] When using these starting materials n1, it is necessary to use a large amount regardless of the polymerization temperature, and therefore the Mad II polymer of the resulting thermoplastic resin is 〃The degree of polymerization of the phase is extremely low, and it tends to be of poor usefulness in molding (groups O and 1).Furthermore, if the amount of initiator is decreased in the first step, when the degree of polymerization is increased by these initiators, so-called d , (3a, d,
en(J, Tff), and a high conversion rate that can be achieved industrially cannot be obtained, or an extremely long polymerization time is required to obtain a high conversion rate. Furthermore, when using an organic peroxide such as benzoyl peroxide, it is difficult to obtain a thermoplastic resin with a high conversion rate that can be used industrially even if a suitable polymerization temperature is used. 4- The above tll+<, if you try to obtain Nidistomer'J (tα-furkylstyrene-nitrile thermoplastic resin) using the conventional suspension polymerization technique, you will not be able to obtain a copolymer that can be used industrially as a molding material. Otherwise, the productivity will be extremely low from an industrial perspective.In view of this, the present invention
Short "High polymerization conversion rate of 1 @ in suspension polymerization or bulk polymerization of Morikoku"
Succeeded in obtaining an elastomer-reinforced α-alkyl yarn thermoplastic resin with excellent heat deformation temperature and impact resistance, and blended this resin with a chlorine-based resin. This has led to the provision of the resin composition of the present invention, which is a yarn with a low impurity content.
Compounds with a 10-hour half-life temperature of 60 to 120°C are suitable, and examples of compounds that fall under this category include di-t-butyl peroxyhexahydroterephthalate, 2.5-bis-2.5-bis(2-ethyl Hegisanoyl peroxy)
Hexano, 1,1'-di-mo-ip-rubaroxy 3,3
．． 5-1-lime4-rusikl]l\gisan, 1.1'-
Sea 1. - Buchirubaroxycyclo I\Kisan, Gt
, -butylperoxyazele-1,2,5-dimethyl-
2,5 bis (penzo oil bar ogishi) l\can, 2.
2'-C1. -Bulperoxyvalericm -r
Examples include 1-butyl ester, 1-butyl ester, and 11-butyl adibate. Among them, in particular, G-L-bu-ruperogishino\gisahide VJ terephthalate and H1.1'-di-dithylboxy-8
, 3, 5-1 Reme f-look and 1・＼gi→J-n is ridiculous. Father, 7zo yarn ILO' product and l-, 1.1'-7zobis-cyclono\gisan-l-carbonitrile, 2-phenylaso-2,4-cymetyl-4-methoxyvaleronitrile + 7zobisisobutylonitrile, 2 .2'-7zobis(2I4-dimethylmolenidol), etc. 01 to 3 parts (1 to 3 parts) of the initiator 11
0t11rl vs. 11), and if it is less than 0.1 part, no industrially practical conversion rate can be obtained.
7 (requires extremely long polymerization using the lower pestle) [1. However, if the molecular weight is low (1), only a material with a significant decrease in strength (1) can be obtained when molded. −
Nobi-furkyl (including 01-C41 styrene and the substituted derivatives of these compounds), such as Mels, is used to lower the deformation temperature of the resin. Therefore, the amount used It is preferable to use a large amount of α-furucylcene (7), but due to the polymerization rate and conversion rate, 111
1. Range Cuff - [Sh. Next, nitrile thread monomers include γ-crylonitrile, meta-7-crylonitrile, etc., which are used to control the reaction rate and conversion rate. However, (7) If a large amount of nitrile yarn is used, it may cause coloring during molding, so it may cause cavities.
7 such as 11-ruic acid ester, ethyl methacrylic acid ester, etc.
7 - Contains an algyl ester of grilled acid, and when using it, it should be determined that the 4rl Vi ratio of the grafted material and the alkyl styrene yarn copolymer are close to each other. It is. Father, these chemical compounds and Jl;-IT (compoundable monomers include, for example, maleic anhydride, 1-mer acid 1-mer-1-ethyl chloride, N-no-1-lumaleimide + N-noenylmaleimide). etc. The present invention: The diene rubber used in this invention includes butadiene rubber, styrene-butadiene rubber, and Aku-10.
Nido 11 Lubutadiengo 11, Isoprene rubber, RiU
J I: Diene thread rubber such as Isolen rubber etc.
, 5 to 4 (l) of methacrylic ester to these rubbers.
WL% (gono. l (1 Fl W't.% to l
,) is used. The rubber may be in the form of rubber itself, or it may be used in the form of latex. The chemical compound used in Graph 1 may be methacrylic acid ester Ij alone, or other chemical compounds such as styrene, acrylonitrile, vinyltoluene, etc. may be used in combination. 1. , 7
1) L, Graph 10 should be extremely light (it should be avoided to impair the function as an elastomer, and the craft rate should be 5 to 4 U W+,% or preferably 11,00%.Using rubber latex+ The method of suspending and combining the α-γ-alkyl styrene yarn monomer is to add a coagulant to a stirrer to break up the latex. After that,
A method of adding monomer threads and carrying out suspension polymerization can be obtained. Suspension stabilizers and 1, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone,
71/There are organic suspension stabilizers such as cellulose, and inorganic suspension stabilizers such as tricalcium phosphate, magnesium phosphate, sodium silicate, zinc oxide, fugnesium carbonate, etc. In the case of inorganic suspension stabilizers, When aniono surfactants such as sodium dodecylbenzenesulfonate and α-olefin sulfonate are used in combination, the suspension stabilizer's young fruit will be significantly reduced (
−<Good. Coagulant and 1. In this case, all lkm inorganic salts can be used as acids and /11 used when coagulating ordinary emulsion polymers. In addition, water-based organic compounds such as methanol can also be used. Typical acids include hydrochloric acid, sulfuric acid,
These are inorganic acids such as nitric acid and organic acids such as acetic acid. Water-bathable inorganic salt and 1. Sulfates, chlorides, acetates, etc. of various metals such as IIum and magnesium sulfate can be used. Next, the chlorine-based resin is not particularly limited, but
For example, polyvinyl chloride-11dene, chlorinated polyvinyl chloride,
Polyvinyl chloride, chlorinated polyethylene (Ce amount 411
(wt% or more), etc. The next best thing is to show an example, but is it thermal deformation? Crystallinity (]8.6 to 9
/ cd load II l) 'l' l is 1 'r
S-K-7207, notched r 7. O+) Impact strength is -, lTS K-7110, transparency evaluation is JI
Ii+11 was determined according to SK-6714. Examples 1 to 6, Comparative Examples] ~3 Stirrer [t] The following raw materials were placed in an autoclave,
Polymerization was carried out at 115°C for 8 hours, and the temperature was further raised to 115°C for 4 hours. Polymer resin A was obtained. Water 240 Parts by weight 11 Vinyl alcohol 03 Anhydrous calcium chloride 1.5 Alkylar 11-Rus I Rephonate surfactant Bamboo 1 0
．． 01 Latex A* (MBS Ly solid content) 25α
-Methylstyrene 38 Arylonitrile ]8 Methyl methacrylate 19 Di-t-bu-rubberoxyhexahydrothyrephthalate-1-0,5 Di-t-but-rubberoxy8. a,5-trimethylcyclohexane 0
．． 10 *Latex A is a styrene-butadiene random copolymer latex (particle size 700μ, butadiene content 70%) using an emulsion polymerization method, and methyl methacrylate-1.
Graft polymerization of styrene in the following proportions 1. It is something that ? The solids content of the latex was 28%. 60 Parts by weight (solid content) of methyl methacrylate 20 Styrene 20 This resin A has a bell θ: ;1 manufactured by Kagaku Co., Ltd., polyvinyl chloride l
Shikikane Vinyl S-1 (1 (17)) and chlorinated polyvinyl chloride fLI-5271 were extruded and blended in the proportions shown in Table 1, and the physical properties were measured by in-die injection molding. Obtained measurements The results are shown in Table 1. Table 1 1) VC: Polyvinyl chloride CPVC: Chlorinated polyvinyl chloride However, Comparative Example II: Except for J, processing was performed using the following formulations. Knob handle tin malate 1.5 P l (R ester thread lubricant 1. U i-' 11 R flame retardant evaluation: 5
Test pieces of Tomo'1101m and K1m were ignited with a burner, and their flammability was determined. t'll'? Seven Senichi j'): The flames of Ura E-cho and Tess I-Heath will go out\: Barley! 1l11′? From Table 1, it can be seen that the ζ11 composition of the present invention has a good balance of strength, transparency, and flame retardancy, with a heat resistance of 11%. Comparative Example 4 to 7 In the polymerization using ir as in Examples 1 to 6, = ;n, r, rklilA (j excluding calcium and latex A), except for the same procedure,
α-messengers and itoki 1 finger that does not contain ゛l・■
Resin No. 1 and mark T) were obtained. This tree 11 effect and →Text A Tra C',, rtC,), coagulated with C2, dried 71) M +1 S-chlorinated bottle 11 1L vinyl? Shikoku Hitomi side 11 - 1I-R271 manufactured by Gaku Co., Ltd. was pushed out by 1 degree and blended, and the physical properties were measured and the results shown in Table 2 were obtained. 1) fko. Resin r ((7)
D M F O, 2'iin'; Al(D 3 (PiC
Teno η, ■, ft was 0.12 (1. The formulation was learned from Example 1. Table 2 fil, Table 2jl), Invention 0) uJ, 'lHff
It is understood that the 111h'Z material has good transparency (l/.01) and good transparency. Comparative Example 8 Copolymer 0-resin △ of Examples 1 to 6 i) Power/1.1 and styrene was used instead of methyl methacrylate. Similarly, L-(拉1) finger (
: Got. Using this resin, polyvinyl chloride (S-I U U 71, Shobuchi Kagaku 4) manufactured by Shobuchi Ijigaku Co., Ltd., and phosphorized polyvinyl 1iAir vinyl (IT-F) 27) was used. I took the test. All Zanobles are completely opaque and hot. Comparative Examples 9 to 12 - 15- Chain transfer of 1;-todecylmercasothane using the usual fL +U IIFα method! Used as 1 to 1tIl 1, tree,
Finger 1' (same thing-1-elbow 111Z). Then C++, Cl 2, center circle l-1 dry I, tree, 1
11 I) was fi). l) M t' (12
%m liquid η, -to, was 128. The resin used in Comparative Examples 4 to 7 (S, made by Shogaku TP44) V C11-527 was extruded (-blend) at a ratio of rJ<- as shown in Table 3. , Material I' measurement was carried out.The formulation was the same as in Example 1.Table 3
The results are shown in 1. F-ko. From Table 3, it can be seen that if less fat obtained by emulsion polymerization was used, the transparency t/l' would be much worse than in Comparative Example 1. -16- Comparative Examples 13 to 5 Comparative Examples 9 to 1 to the latex l used in Examples 1 to 6
The latex used in 2 was prepared in the proportions shown in Table 4.
Drying 1. Te, bell/l:'CPVCH- manufactured by AIL Gaku Co., Ltd.
527 and 111jL Zorento, and the physical property tests were conducted in the same manner as [)F, and the results shown in Table 4 were obtained. Table 4 From the comparison of Tables 1 and 4, the resin composition of the present invention has T7.
OD, transparency should be good.Special 2γ1 Applicant: Hitomi Chemical Co., Ltd.

Claims (1)

[Claims] 1. 5 to 40 wt% methacrylic acid ester (Gono, 1 (
The diene yarn Gono who crafted the vs.
5-5 () Tonkabe (hereinafter referred to as 1 and -1 parts T) and α-alky I restyrene yarn; 80 to 85 parts of Nanatsuma, 15 to 40 parts of 2L/Lil yarn monomer, methacrylic acid ester type 10 to 65 parts of monomers and 0 to 1 parts of these monomers and 1 (polymerization + i) monomer yarn consisting of 95 to 50 parts
Suspension polymerization or bulk polymerization? [
1 taste navy blue 11jlj item. 2j (The polymeric resin is a polyfunctional peroxide and/or an azo compound as an initiator. Prone oxide or sea 1.-Bulperoxyhegisahide-terephthalate-1.
At least one member selected from \xane + 1-lith(1,-butylperAA)triazine π1-Claim 2-1; 4 Azo thread compound or 1. ．． 1'-7 Zobi Sunku II
/\Gisan]-Carboni lil special fF Claim 2 rfIl 1 H-subset. 5. The chlorinated resin is chlorinated polyvinyl chloride and/or polyvinyl chloride = TT. Claim 41(d).