JPS60208345A - Heat-resistant, flame-retardant and impact-resistant resin composition - Google Patents

Abstract

PURPOSE:To produce a composition having excellent heat-resistance, flame- retardance and impact resistance, by compounding an alpha-methylstyrene/acrylonitrile copolymer with a rubber such as MBS resin and a chlorine-containing resin. CONSTITUTION:The objective composition can be produced by compounding (A) a copolymer obtained by the suspension or bulk polymerization of 30-80pts.(wt.) of alpha-methylstyrene, 15-50pts. of acrylonitrile and 0-50pts. of other monomer copolymerizable therewith, (B) a rubber selected from chlorinated polyethylene, MBS resin, acrylic rubber resin, styrene-butadiene resin and NBR resin, and (C) a chlorine-containing resin. The polymerization initiator of the component A is a polyfunctional organic peroxide and/or an azo compound. The component C is e.g. ethylene-vinyl chloride copolymer, aryl chloride-vinyl chloride copolymer, etc. having an average polymerization degree of 400-800.

Description

[Detailed description of the invention]

The present invention relates to a white (thermal, flame retardant, impact resistant) resin composition. Specifically, (a) it is produced by suspension polymerization or bulk type method and is composed of alpha methyl styrene 3.
A copolymer consisting of 0 to 80 parts, 15 to 50 parts of acrylonitrile, and 11 parts of O to 50 parts of other monomers that can be co-combined with this, and (b) chlorinated polyethylene, MBS resin, acrylic rubber system 111 The present invention relates to a heat-resistant, flame-retardant, -(impact-resistant) 1H resin composition comprising at least one rubber selected from oil, styrene-nibutadiene-based resin, and NBR resin, and (C) a chlorine-containing resin. Recently, demand for i44i, i!l [P, fi (impact resins) has been increasing in the fields of electrical products and automobile parts. A mixed system of ABS resin and polyvinyl chloride resin is known, but its heat resistance is still insufficient.
It was also known that because 1 fat is highly emulsified, its thermal stability deteriorates when mixed with polyvinyl chloride resin. The present invention relates to a heat-resistant, high-impact resin composition that has improved the above-mentioned drawbacks. Specifically, it is obtained by suspension polymerization or polymerization, and the composition consists of alphanotyl styrene 30 to 80%. Parts by weight, preferably 50-80tRit parts, acrylonitrile 15
~50 parts by weight, preferably 20 to 35 parts by weight, and 0 to 50 parts by weight of other small polymers copolymerizable therewith, preferably 0 to 35 parts by weight
30 to 90 parts by weight of a copolymer (hereinafter referred to as suspension copolymer) consisting of 35 parts by weight, and chlorinated polyethylene, M B
1 S-based group (5 to 30 parts by weight of at least one type selected from fat, acrylic rubber resin, styrene-butadiene resin, NBR resin, and 5 to 6 parts by weight of chlorine-containing resin)
Heat resistant, flame retardant, iti resistant consisting of 5 parts by weight! ! The present invention relates to a synthetic resin composition. In the present invention, alpha methylstyrene is not only alpha methylstyrene but also alpha methylstyrene Hensen apparatus +j! ! Also included are alpha methylstyrene derivatives having substituents such as methyl, ethyl, and halogen groups. Moreover, acrylonitrile refers to acrylonitrile and methacryl 1]nitrile. Monomers that can be copolymerized with these include styrene,
Styrene substituted with Hensen's nucleus, such as styrene derivatives having substituents such as methyl group, ethyl group, L-butyl group, halogen group, methacrylic acid, acrylic acid, maleic anhydride, N-methylmaleimide, N-phenylmaleimide, etc. These include known small vinyl compounds such as maleimide compounds. These may be used singly or in combination of two or more. When obtaining the suspension copolymer of the present invention, the initiator used is a polyfunctional organic peroxide, which has a 10-hour half-life temperature of 60
~+20°C. Compounds corresponding to this include di-t-butylbaroginohequinabitrotyrephthalate-I, 2.5dimedyl 2.5bis(2-ethylhquinanoylbaroxy):tozan, 1.1' −G

[-butylperoxy 3,3.51-limethylcyclohexane, 1.1'-di-L-butylperoxycyclohexane, di-butylperoxyazele 1., 2゜5-dimethyl-2,5bis( benzoylperoxy)hexano, 2,2'-di(t-butylperoxy)-butane, 4,4'-di-t-butylbaroxyvaleric acid-〇-butyl ester, di-L-butylperoxytrimethyl a difunctional growing peroxide such as adibate, or 2. 4. Trifunctional tJII such as 6-1-ri-t-butylperoxyperoxy-1,3,5-triazine
There is peroxide. Among them, di-t-butylperoxyhexahydroterephthalate-1. and 1.1'-di-1-butylperoxy-3,3,5i-limethylcyclohexane have a good polymerization time, and 2, 4. 6-tri-L-butylperoxy] and 3,5-tridian are preferable because processability improves as the degree of polymerization increases. The Ab-based compounds used in the present invention include azobisisobutyronitrile, dimethyl 2.2 to 7zobisisocynate, l
, 1'-a, 77-cyclohexane-1 carbonitrile, 7-zoformamito, 2-phenyl-2,4-dimethyl 4-methocinovaleronitrile, and other ab compounds. Preferably, 1.1'-Abbisunk II+for hexane=carbonitrile. If an ab-based compound is used, a colorless copolymer with less coloring can be obtained than when a polyfunctional organic compound is used, and therefore the molded article of the resin composition of the present invention can be colored better. The amount of the polyfunctional organic peroxide and/or ab-based compound used as an initiator for the suspension copolymer in the present invention is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the monomer mixture. Further, these initiators may be used in combination. The invention'! ! ! The polymerization temperature to obtain +41 copolymer is 80
~130°C is good. If an initiator other than those mentioned above is used as an initiator, the conversion rate will not increase and this will be extremely disadvantageous industrially. From the point of view of
Because alpha methylstyrene-acrylic [J2]-based copolymers containing high alpha methylstynonone could not be commercially obtained by suspension polymerization or bulk synthesis, in the present invention, special polymerization was initiated. One of the features of the present invention is that the content of alpha methylstyrene is 30 to 30%.
80 parts by weight, preferably 11 parts of 5o-8oIIi'!
! ．． It is better to use a cloudy copolymer. The dirt is a culm with a large amount of alpha methylstyrene, i(?JS +'t
Because it will also get better. In general, 11 with high alpha methylstyrene content! Although it has not been possible to obtain a cloudy copolymer in the past, it can be produced industrially by using the open kI3 agent of the present invention, as described above. In the present invention! ! ! As the polymerization method for obtaining the cloudy copolymer, known hanging polymerization or bulk polymerization is employed. Particularly in the case of suspension polymerization, known dispersants are used in the aqueous medium. Examples of dispersants include organic dispersants such as polyvinyl alcohol, polyvinyl vinyl c+ IJton, and methylcell I-cose, and inorganic dispersants such as calcium phosphate kingate, magnesium phosphate, sodium silicate, curved lead oxide, and magnesium carbonate. In the case of a dispersing agent, the effect of the dispersing agent is significantly enhanced when an anionic surfactant such as sodium dodecylhensensulfonate or sodium α-olefin sulfonate is used in combination. Furthermore, when using the initiator in the present invention, it is essential to select the polymerization temperature. That is, the polymerization temperature is 80 to 130
'C is good, more preferably 90-120°C. Below 80℃, the conversion rate becomes extremely low, and below 130℃
If the molecular weight exceeds 100%, the molecular weight decreases, and it is difficult to obtain a copolymer that is collectively useful. The chlorine-containing resin used in the present invention is a polyvinyl chloride thread resin and/or a chlorinated polyvinyl chloride resin. As the chlorine-containing resin, it is preferable to use a chlorine-containing resin having an average degree of polymerization of 400 to 800. This is because if the IP uniformity degree is less than 400, it becomes difficult to develop impact strength, and if the average degree of polymerization exceeds 800, processability becomes poor. Examples of polyvinyl chloride resin include polyvinyl chloride resin,
There are copolymers of vinyl chloride and vinyl monomers that can be copolymerized with vinyl chloride. As a copolymerized +17-chain beer monomer,
There are known l1 isomers such as ethylene, propylene, 1-butene, vinylidene chloride, and allyl chloride. The content of these vinyl monomers in the copolymer is preferably 0 to IOwL%, preferably 0 to 5wi%. This is because if the content exceeds 10-t%, the copper p'i value decreases, which is undesirable. Among these copolymers, ethylene vinyl chloride, allyl chloride-vinyl chloride, pyrene-vinyl chloride, and l-butene-vinyl chloride copolymers are most preferred.
[Preferably. As the chlorinated polyvinyl chloride resin 1 resin, the above-mentioned polyvinyl chloride resin is chlorinated. A chlorinated polyvinyl chloride resin having a chlorine content of 60 wL% to 70 wt% is preferable. The dirt is 6. If it is wt%t%, the heat resistance improvement effect of 91-J on polyvinyl chloride-based cedar fat is small, and if it exceeds 7011L%,
It is undesirable because it deteriorates the quality of the product. The chlorine-containing resin used in the present invention is preferably produced by a suspension type method or a bulk polymerization method. This is because they are more transparent and have better thermal stability than emulsion polymerized products. In the present invention, it is preferable to use a chlorinated polyvinyl chloride resin as the chlorine-containing resin. This is PA basicization 2J!
This is because heat resistance and thermal stability are improved by using a vinyl-based resin. Conventionally, chlorinated polyvinyl chloride resins were said to have poorer thermal stability than polyvinyl chloride resins, but it has been found that they have better thermal stability according to the method of the present invention. The reason for this is not clear, but it is thought to be due to the synergistic effect of the suspension copolymer, NBR resin, acrylic rubber resin, chlorinated polyethylene, styrene-butadiene rubber, MBS resin, and chlorine-containing resin. The chlorine content of the chlorinated polyethylene used in the present invention is 30
~40wt% is good. If it is less than 30 wt%, it becomes difficult to develop impact resistance. Moreover, if it exceeds 40-t%, impact resistance becomes difficult to develop and thermal stability also deteriorates, which is not preferable. MBS resin used in the present invention, acrylic rubber thread 111
As the resin, styrene-butage 41h resin, and NBR resin, all commonly known resins can be used. In the present invention, chlorinated polyethylene, MBS resin, acrylic rubber resin, styrene-butadiene resin, NBR+
) I fats may be used alone or in combination. Equivalent impact strength, - (develops thermal properties and improves flame retardancy)
For lining, it is better to use chlorinated polyethylene. Chlorinated polyethylene, NBR resin, MBS of the present invention
The amount of at least one resin selected from resins, acrylic rubber resins, and styrene-butadiene resins is 5 to 30 parts by weight, preferably 10 to 20 parts by weight. This is because if it is less than 5 parts by weight, it is difficult to develop impact strength.
If it exceeds 30 parts by weight, heat resistance decreases, which is not preferable. The amount of the suspension copolymer of the present invention used is 30 to 90 parts by weight, preferably 40 to 70 parts by weight. This is because if it is less than 30 parts by weight, the effect of improving heat resistance is small, and if it exceeds 70 parts by weight, the flame retardant effect is reduced. The amount of the chlorine-containing resin used in the present invention is 5 to 65 parts by weight, preferably 40 to 60 parts by weight. This is because if it is less than 5 parts by weight, the effect of flame retardancy decreases, and if it exceeds 65 parts by weight, the effect of improving heat resistance decreases. In the present invention, processability improvers such as low molecular weight AS resins and low molecular weight polyalphamethylstyrene, known stabilizers such as dibutyltin maleate, mercaptotin maleate, metal soaps, lead compounds, bromine-based stabilizers, phosphorous, etc. A small amount of a known N repellent such as a dye, a known coloring agent such as a pigment, etc. may be used in combination. The resin composition of the present invention is subjected to molding processes such as extrusion, rolling, and injection into molded bodies for various uses. The resin embodiments of the present invention are disclosed below, but these do not limit the present invention in any way. Examples 1 to 11, Comparative Example 1 Production of suspension copolymer (A): In an autoclave with a stirrer, 110 parts by weight of water, 0.24 parts by weight of tricalcium phosphate, and 0.2 parts by weight of sodium V-decylbenzenesulfonate. 003 parts by weight, sodium chloride 0.
2 parts by weight of di[-butylperoxy-hexahydroterephthalate] and 0.4 parts by weight of di[-butylperoxy-hexahydroterephthalate] were added under stirring.
．． A mixed monomer mixture of 0.2 parts by weight of 1'-di-butylperoxy-3.3.5-)lyntylcyclohexane, 55 parts by weight of alpha methylstyrene, 30 parts by weight of acrylonitrile, and 1 part of styrene + 51ii was introduced into the cough system. Then, the temperature was raised to 95°C, and polymerization was carried out for 7 hours.
Then, the temperature was raised to 115°C, and polymerization was carried out for 3 hours. After cooling, dehydration and drying, a suspension copolymer (A) was obtained. The conversion rate was 99.8 wt%. Production of suspension copolymer (B): In production of suspension copolymer (A), 0.7 parts by weight of di-t-butylperoxy-hexahydrothylephthalate, 1,1 '-di-t-butylperoxy-3,3,5-
0.2 parts by weight of trimedelcyclohexane, 7 parts by weight of alpha methylstyrene (1 weight 1 fl'fl, 3 parts by weight of acrylonitrile)
Suspension copolymer resin C was prepared in the same manner except that the amount was 0 parts by weight.
B) was obtained. The conversion rate was 99.7%. vA construction of suspension copolymer (C): In the production of suspension copolymer (A), 50 parts by weight of alpha methylstyrene, 20 parts by weight of acrylonitrile, 1
A suspension copolymer (C) was obtained in the same manner except that 25 parts by weight of methacrylic acid and 5 parts by weight of methacrylic acid were used. Conversion rate is 99.7
It was wt%. Production of resin composition and evaluation of physical properties: The above g-shoulder polymers (A), (B), (C,), chlorinated polyethylene, MBS resin, acrylic rubber resin, styrene-butadiene resin, polyvinyl chloride , chlorinated polyvinyl chloride were blended in the proportions shown in Table 1. At this time, 30 parts of dibutyltin maleate and 20 parts of an ester lubricant were mixed per 100 parts by weight of these mixed resins. The above mixture was kneaded with a roll at 170° C. for 5 minutes, and the physical properties were evaluated. The results are shown in Table 1. Table 1 also shows the results of physical property evaluation when using AS+)l fat, which is generally obtained by emulsion polymerization. The heat resistance in Table 1 was determined by measuring the heat distortion temperature (+-1r)T) according to JIS-7207. The measured rtI amount is 18.6 kg/cj. Thermal stability is the blackening time (min) of the sample in a Gima oven at 180"C.
was measured. 1h impact strength is -7 to 11S-
1] The notched IZOr) value was measured according to 0. *1 Emulsion m consisting of 50 parts by weight of alpha methylstyrene, 20 parts by weight of acrylonitrile, and 25 parts by weight of styrene.
Polymer *2 Styrene-butadiene block copolymer containing 160 wt% butadiene *3 Chlorinated polyethylene containing 135 wt% chlorine From Table 1, f! It can be seen that using a shoulder polymerized product has better thermal stability. It is also found that the use of chlorinated polyvinyl chloride resin has better heat resistance and thermal stability. Examples 12 to 14 M production of suspension type copolymer (D): In the production of suspension type copolymer (A), 2.4.6-tree [
t! in the same manner except that 1.4 parts by weight of -butylperoxy-1,3,5-toridian was used and the polymerization was carried out at 115°C for 13 hours. A cloudy copolymer (D) was obtained. What is the conversion rate? 19.8
It was wLoA. In the production of suspension type copolymer (E) and aItA copolymer, 1.1'-
abbiscyclohexane-1-carbonyl 0.6m, 1
A suspension copolymer (E) was obtained in the same manner except that 711 was used. The conversion rate was 99.8 wt%. Production of resin composition and evaluation of physical properties: The suspension copolymers (A), <D), and (E), acrylic rubber, and polyvinyl chloride resin were blended and roll kneaded in the same manner as in Example 1-11, Physical properties were evaluated. The results are shown in Table 2. For evaluation of colorability in Table 2, use roll sorting]
Judgment was made from the coloration of a press plate (thickness: 5 mm) that was pressed for 15 minutes at 75°C and 1150 kg/-. The criteria for judgment are as follows; A: Almost no coloration B: Slight coloration Table 2 From Table 2, coloring property improves when an Ab-based compound is used as a polymerization initiator for the suspension copolymer. I understand that. Examples 15 to 24, Comparative Examples 2 to 4 40 parts by weight of the suspension copolymer (E), containing nitrile 113
A mixture consisting of 15 parts by weight of 54% NBR resin, 45 parts by weight of various chlorine-containing resins, 3.0 parts of dibutyltin maleate, and 1.0 parts of ester wax was kneaded with a roll at 160°C for 5 minutes to form a sheet. I got it. From this sheet B
method flow (nozzle 1φ x 10t m/m, load 150
kg/cd, temperature 190°C) Table 3 shows the results of impact strength, thermal stability, and heat resistance. For comparison, the physical property evaluation results (Comparative Example 4) of an emulsion polymer product consisting of 55 parts by weight of alpha methylstyrene, 30 parts by weight of acrylonitrile, and 15 parts by weight of styrene and a polyvinyl chloride resin are also shown. 0 From Table 3, the average m synthetic leather of polyvinyl chloride resin is 400 to 8
It can be seen that 00 is preferable for IZOD and flow parant soot. It is also found that the flow is significantly improved when a vinyl chloride copolymer resin is used. Among vinyl chloride copolymer resins, ethylene-vinyl chloride, allyl chloride-
It is found that vinyl chloride, propylene-vinyl chloride, and l-butene-vinyl chloride copolymers have a good balance of IZOD, flow, and thermal stability. Furthermore, it has been found that the use of emulsion polymerization copolymers results in poor thermal stability. Reference Examples 1 to 3 In the production of suspension copolymers (A), (B), and (C),
Polymerization was carried out in the same manner except that 1.0 parts by weight of benzoyl peroxide was used as a polymerization initiator. The conversion rates were as shown in the table. 4 Table 4 From the results in Table 4, if the polymerization initiator of the present invention is used (if
It is t1 that there is an extremely large industrial advantage.

Claims (1)

[Claims] 1. (a) also methylsunarene 30 to 80 years old;
Acrylic 1'' 21/ri Monthly 5 = 50 units, together with this Ut
A copolymer obtained by suspending or bulk polymerizing monomers at a usage rate of 0 to 50 parts by weight; Consisting of at least one type of rubber selected from S thread resin, acrylic rubber-based resin, styrene butadiene thread resin, Nts R4!I fat, and (c) lij element-containing heat lubricant. Resin silk composition resistant to il, gas combustion, and south impact. 2 Both H and E combinations are alpha methylstyrene 50 to 80.
M part, acrylic r+ 20-35 parts of nitrile, these and
4Δ (fat composition) according to claim 1, consisting of parts by weight. Ill r(',
thing. 4. Multi'1) ability +4 own machine i1! l oxide is di 1
Luperoxy ＼-1-blade high 1 day-Rusotare 1 le 0
/ 1.1 t Final par, 1-1- 3.3
．． 5 l Rich Look U to Kirin's 1゛) function + 4 auto peroxide (resin composition according to claim 31'fi) 5. polyfunctional (-1 auto peroxide is 2,4) .ξ1lit
Butyl peroxy
rri) phylum 1 fat composition. 6. Ano thread compound or 1.1'
Claim 3 which is Kirin l-carbonitrile
The resin composition described in . 7. Contains chlorine (8 fat is polychlorinated, Neil yarn (geshu) khi/mata (J chlorinated, 1 mm vinyl chloride J-ru! Village 1 fat goren,
The resin 411 composition according to claim 1. 8) 11 uniform market degree is 400-BO(10)k',
, 4' Contains 1) Color 1 Patent claim using fat! [! Ti
ll No. Vjf item 1 11 fat 411th generation. 9 Echin'lj+ cation E--)1,
l! 4 Il no'ri no I 膓口 VINYL, PU 1''
The resin composition according to claim 7, which uses a vinyl non-vinyl chloride copolymer and a 1-butene vinyl chloride copolymer.